US20150104642A1 - Production method of electrically conductive graphene composite fiber - Google Patents

Production method of electrically conductive graphene composite fiber Download PDF

Info

Publication number
US20150104642A1
US20150104642A1 US14/577,609 US201414577609A US2015104642A1 US 20150104642 A1 US20150104642 A1 US 20150104642A1 US 201414577609 A US201414577609 A US 201414577609A US 2015104642 A1 US2015104642 A1 US 2015104642A1
Authority
US
United States
Prior art keywords
graphene
composite fiber
polymer
fiber
hyperbranched
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US14/577,609
Inventor
Chao Gao
Xiaozhen HU
Xiaosong ZHOU
Yan Xu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huawei Technologies Co Ltd
Zhejiang University ZJU
Original Assignee
Huawei Technologies Co Ltd
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to CN201310332049.2A priority Critical patent/CN103541043A/en
Priority to CN201310332049.2 priority
Priority to PCT/CN2014/072689 priority patent/WO2015014124A1/en
Application filed by Huawei Technologies Co Ltd, Zhejiang University ZJU filed Critical Huawei Technologies Co Ltd
Assigned to ZHEJIANG UNIVERSITY, HUAWEI TECHNOLOGIES CO., LTD. reassignment ZHEJIANG UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GAO, CHAO, HU, Xiaozhen, ZHOU, XIAOSONG, XU, YAN
Publication of US20150104642A1 publication Critical patent/US20150104642A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/06Wet spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00Treatment of filament-forming or like material
    • D01D1/02Preparation of spinning solutions
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/12Stretch-spinning methods
    • D01D5/14Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/09Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/50Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/16Chemical after-treatment of artificial filaments or the like during manufacture of carbon by physicochemical methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2927Rod, strand, filament or fiber including structurally defined particulate matter

Abstract

A graphene composite fiber includes graphene sheets and a polymer for aggregating the graphene sheets together. The polymer includes either or both of a hyperbranched polymer and polyvinyl alcohol. The graphene sheets and the polymer are stacked on each other to form a layered structure, and the graphene sheets are regularly arranged along an axial direction of the graphene composite fiber. In a production method of the graphene composite fiber, a graphene oxide is used as a raw material, which significantly improves tensile strength of the graphene composite fiber. Addition of the polymer provides good tenacity for the composite fiber. In a spinning process, rotated coagulant is used to increase a tensile force of a gelatinous fiber, so that the gelatinous fiber has high orientation and tacticity, thereby significantly improving strength of an obtained solid fiber. The final reduction process restores electrical conductivity of a graphene fairly well.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is a continuation of International Patent Application No. PCT/CN2014/072689, filed on Mar. 3, 2014, which claims priority to Chinese Patent Application No. 201310332049.2, filed on Aug. 1, 2013, both of which are hereby incorporated by reference in their entireties.
  • TECHNICAL FIELD
  • The present invention relates to a composite fiber material, and in particular to an electrically conductive graphene composite fiber and a production method thereof.
  • BACKGROUND
  • A carbon fiber is a new material with excellent performance, which has not only an intrinsic property of a carbon material, but also flexible process ability of a textile fiber. Compared with a traditional glass fiber, the Young's modulus of the carbon fiber is more than 3 times that of the traditional glass fiber; compared with a Kevlar fiber (KF-49), not only the Young's modulus of the carbon fiber is approximately 2 times that of the Kevlar fiber, but also the carbon fiber has notable performance such as corrosion resistance and tensile strength. Therefore, the carbon fiber is widely used in the civil use, military, construction, chemical, industry, aerospace, and supercar fields.
  • Graphene is a two-dimensional layer of carbon atoms linked by means of sp2 hybridization, and has many excellent properties such as ultrahigh strength, extremely large specific surface area, high thermal conductivity and carrier mobility, and therefore has a broad application prospect in many fields such as transistors, super capacitors, selectively permeable membranes, and enhanced materials. If the ultrahigh strength of a single graphene sheet can be transferred to a macroscopic material, the strength of the single graphene sheet in the macroscopic material is comparable to that of the carbon fiber. Research finds that, by using a wet spinning technique, a liquid crystalline solution of a graphene oxide can be converted into a macroscopic graphene fiber. However, the strength of the obtained graphene fiber is approximately 100 to 200 MPa, which is still much lower than the strength of the single graphene sheet. The obtained graphene fiber can meet practical application requirements only when its strength and electrical conductivity are further improved.
  • SUMMARY
  • An objective of the present invention is to provide a production method of an electrically conductive graphene composite fiber having high strength and electrical conductivity.
  • A graphene composite fiber includes graphene sheets and a polymer for aggregating the graphene sheets together, where the polymer includes either or both of a hyperbranched polymer and polyvinyl alcohol, the graphene sheets and the polymer are stacked on each other to form a layered structure, and the graphene sheets are regularly arranged along an axial direction of the graphene composite fiber.
  • A production method of an electrically conductive graphene composite fiber includes: step 1, adding 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stirring, so as to obtain nanocomposite material spinning slurry of the polymer and graphene, where the polymer includes either or both of a hyperbranched polymer and polyvinyl alcohol; step 2, extruding the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 μm at a rate of 1 to 100 mL/h, retaining the spinning slurry in rotated coagulant for 1 to 3600 s to coagulate the spinning slurry into fibers; and step 3, washing the coagulated fiber product, drying the coagulated fiber product in a vacuum, and then performing reduction to obtain the graphene composite fiber.
  • Strength of the graphene composite fiber mainly depends on interactions between graphene sheets. For a fiber formed by graphene sheets, there are mainly Van der Waals force and π-πinteractions between the graphene sheets. However, a polymer having a large number of functional groups exists between the graphene sheets in this embodiment, and the polymer and hydroxyl and carboxyl groups in the graphene sheets form hydrogen bonds or ionic bonds, which act like glue to “bond” adjacent graphene sheets together, thereby increasing the strength and electrical conductivity of the graphene composite fiber.
  • BRIEF DESCRIPTION OF DRAWINGS
  • FIG. 1 is a digital camera photo of a graphene composite fiber wound around a roller of polytetrafluoroethylene according to an embodiment of the present invention;
  • FIG. 2 is a partial SEM image of a graphene composite fiber wound around a roller of polytetrafluoroethylene according to an embodiment of the present invention; and
  • FIG. 3 is a cross-sectional SEM image of the graphene composite fiber according to an embodiment of the present invention in FIG. 2.
  • DESCRIPTION OF EMBODIMENTS Embodiment 1
  • As shown in FIG. 1 to FIG. 3, a graphene composite fiber provided by an embodiment of the present invention includes graphene sheets and a polymer for aggregating the graphene sheets together. The graphene sheets and the polymer are closely stacked to form a layered structure, and the graphene sheets are regularly arranged along an axial direction of the graphene composite fiber. The polymer includes either or both of a hyperbranched polymer and polyvinyl alcohol. The graphene composite fiber is a black fiber having a diameter of 5 to 5000 μm.
  • Particularly, as shown in FIG. 2, the graphene sheets 1 in the fiber are all arranged along the axial direction of the fiber, and therefore have a very high tacticity. Particularly, as shown in FIG. 3, the graphene sheets 1 and the added polymer are closely stacked to form a layered structure, laying a basis for high strength of the graphene sheets.
  • The hyperbranched polymer includes one or more of hyperbranched polyester, a hyperbranched polyamide, and hyperbranched polyglycidyl ether.
  • Strength of the graphene composite fiber in this embodiment of the present invention mainly depends on interactions between graphene sheets 1. For a fiber formed by graphene sheets 1 alone, there are mainly Van der Waals force and π-πinteractions between the graphene sheets. However, in this embodiment, a polymer having a large number of functional groups is introduced into the graphene sheets, and the polymer and hydroxyl and carboxyl groups in the graphene sheets 1 form hydrogen bonds or ionic bonds, which act like glue to “bond” adjacent graphene sheets 1 together, thereby increasing the strength of the graphene composite fiber.
  • Embodiment 2
  • This embodiment of the present invention provides a production method of an electrically conductive graphene composite fiber, including:
  • Step 1: Add 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stir, so as to obtain a nanocomposite material spinning slurry of the polymer and graphene, where the polymer includes either or both of a hyperbranched polymer and polyvinyl alcohol.
  • Step 2: Extrude the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 μm at a rate of 1 to 100 mL/h, and retain the spinning slurry in rotated coagulant for 1 to 3600 s to coagulate the spinning slurry into fibers.
  • Step 3: Wash the coagulated fiber product, dry the coagulated fiber product in a vacuum, and then perform reduction to obtain the graphene composite fiber.
  • A diameter of the electrically conductive graphene composite fiber ranges from 5 pm to 5000 μm.
  • The hyperbranched polymer includes one or more of hyperbranched polyester, a hyperbranched polyamide, and hyperbranched polyglycidyl ether.
  • The solvent in step 1 includes one or more of N-methyl-2-pyrolidone, N,N-dimethylformamide, and water.
  • The coagulant in step 2 includes one or more of a NaOH aqueous solution, a KOH aqueous solution, a CaCl2 aqueous solution, a NaOH methanol solution, a KOH methanol solution, a CaCl2 methanol solution, a NaOH ethanol solution, a KOH ethanol solution, a CaCl2 ethanol solution, diethyl ether, ethyl acetate, acetone, and petroleum ether.
  • A reduction method in step 3 includes thermal reduction and chemical reduction. A reducing agent used in the chemical reduction includes one or more of hydrazine hydrate, vitamin C, lysine, potassium hydroxide, sodium hydroxide, hydroiodic acid, and acetic acid.
  • The production method of the graphene composite fiber in this embodiment of the present invention may include the following specific implementation manners
  • 1. In another embodiment of the present invention, the foregoing steps may be specifically:
  • In the foregoing step 1, the adding 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stirring, so as to obtain a nanocomposite material spinning slurry of the polymer and graphene, specifically includes: adding 20 mg of the graphene oxide, 1 g of an N-methyl-2-pyrolidone solvent, and 2 g of hyperbranched polyester to the reactor, and stirring for 1 hour, so as to obtain a nanocomposite material spinning slurry of the hyperbranched polyester and graphene.
  • In the foregoing step 2, the extruding the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 μm at a rate of 1 to 100 mL/h, and retaining the spinning slurry in rotated coagulant for 1 to 3600 s to coagulate the spinning slurry into fibers, specifically includes: extruding the nanocomposite material spinning slurry of the hyperbranched polyester and graphene through a spinning nozzle with a diameter of 5000 μm at a rate of 1 mL/h, and retaining the nanocomposite material spinning slurry in a rotated KOH methanol solution for 50 s to coagulate the nanocomposite material spinning slurry into fibers.
  • In the foregoing step 3, the washing the coagulated fiber product, drying the coagulated fiber product in a vacuum, and then performing reduction to obtain the graphene composite fiber, specifically includes: collecting the coagulated fiber product by using a winder, washing the coagulated fiber product, drying the coagulated fiber product in a vacuum at 40 degrees for 24 hours, and then performing reduction by using hydrazine hydrate, so as to obtain a composite fiber of the hyperbranched polyester and graphene, where the composite fiber has a diameter of 5000 μm, a breaking strength of 400 MPa, a breaking elongation of 5%, and an electrical conductivity of 200 S/m.
  • 2. In yet another embodiment of the present invention, the foregoing steps may be specifically:
  • In the foregoing step 1, the adding 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stirring, so as to obtain a nanocomposite material spinning slurry of the polymer and graphene, specifically includes: adding 20 mg of the graphene oxide, 0.5 g of an N-methyl-2-pyrolidone solvent, and 2 mg of a hyperbranched polyamide to the reactor, and stirring for 4 hours, so as to obtain a nanocomposite material spinning slurry of the hyperbranched polyamide and graphene.
  • In the foregoing step 2, the extruding the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 μm at a rate of 1 to 100 mL/h, and retaining the spinning slurry in rotated coagulant for 1 to 3600 s to coagulate the spinning slurry into fibers, specifically includes: extruding the nanocomposite material spinning slurry of the hyperbranched polyamide and graphene through a spinning nozzle with a diameter of 5 μm at a rate of 100 mL/h, and retaining the nanocomposite material spinning slurry in a rotated NaOH methanol solution for 5 s to coagulate the nanocomposite material spinning slurry into fibers.
  • In the foregoing step 3, the washing the coagulated fiber product, drying the coagulated fiber product in a vacuum, and then performing reduction to obtain the graphene composite fiber, specifically includes: collecting the coagulated fiber product by using a winder, washing the coagulated fiber product, drying the coagulated fiber product in a vacuum at 60 degrees for 24 hours, and then performing reduction by using vitamin C, so as to obtain a composite fiber of the hyperbranched polyamide and graphene, where the composite fiber has a diameter of 5 μm, a breaking strength of 450 MPa, a breaking elongation of 10%, and an electrical conductivity of 2000 S/m.
  • 3. In yet another embodiment of the present invention, the foregoing steps may be specifically:
  • In the foregoing step 1, the adding 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stirring, so as to obtain a nanocomposite material spinning slurry of the polymer and graphene, specifically includes: adding 20 mg of the graphene oxide, 40 g of an N,N-dimethylformamide solvent, and 100 mg of hyperbranched polyglycidyl ether to the reactor, and stirring for 6 hours, so as to obtain a nanocomposite material spinning slurry of the hyperbranched polyglycidyl ether and graphene.
  • In the foregoing step 2, the extruding the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 μm at a rate of 1 to100 mL/h, and retaining the spinning slurry in rotated coagulant for 1 to 3600 s to coagulate the spinning slurry into fibers, specifically includes: extruding the nanocomposite material spinning slurry of the hyperbranched polyglycidyl ether and graphene through a spinning nozzle with a diameter of 100 μm at a rate of 10 mL/h, and retaining the nanocomposite material spinning slurry in rotated diethyl ether for 3600 s to coagulate the nanocomposite material spinning slurry into fibers.
  • In the foregoing step 3, the washing the coagulated fiber product, drying the coagulated fiber product in a vacuum, and then performing reduction to obtain the graphene composite fiber, specifically includes: collecting the coagulated fiber product by using a winder, washing the coagulated fiber product, drying the coagulated fiber product in a vacuum at 60 degrees for 24 hours, and then performing reduction by using vitamin C and lysine, so as to obtain a composite fiber of the hyperbranched polyglycidyl ether and graphene, where the composite fiber has a diameter of 100 μm, a breaking strength of 500 MPa, a breaking elongation of 15%, and an electrical conductivity of 3000 S/m.
  • 4. In yet another embodiment of the present invention, the foregoing steps may be specifically:
  • In the foregoing step 1, the adding 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stirring, so as to obtain a nanocomposite material spinning slurry of the polymer and graphene, specifically includes: adding 20 mg of the graphene oxide, 10 g of an N,N-dimethylformamide solvent, and 200 mg of polyvinyl alcohol to the reactor, and stirring for 24 hours, so as to obtain a nanocomposite material spinning slurry of the polyvinyl alcohol and graphene.
  • In the foregoing step 2, the extruding the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 μm at a rate of 1 to 100 mL/h, and retaining the spinning slurry in rotated coagulant for 1 to 3600 s to coagulate the spinning slurry into fibers, specifically includes: extruding the nanocomposite material spinning slurry of the polyvinyl alcohol and graphene through a spinning nozzle with a diameter of 50 μm at a rate of 20 mL/h, and retaining the nanocomposite material spinning slurry in rotated acetone for 360 s to coagulate the nanocomposite material spinning slurry into fibers.
  • In the foregoing step 3, the washing the coagulated fiber product, drying the coagulated fiber product in a vacuum, and then performing reduction to obtain the graphene composite fiber, specifically includes: collecting the coagulated fiber product by using a winder, washing the coagulated fiber product, drying the coagulated fiber product in a vacuum at 60 degrees for 24 hours, and then performing reduction by using hydroiodic acid, so as to obtain a composite fiber of the polyvinyl alcohol and graphene, where the composite fiber has a diameter of 50 μm, a breaking strength of 550 MPa, a breaking elongation of 8%, and an electrical conductivity of 3500 S/m.
  • 5. In yet another embodiment of the present invention, the foregoing steps may be specifically:
  • In the foregoing step 1, the adding 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stirring, so as to obtain a nanocomposite material spinning slurry of the polymer and graphene, specifically includes: adding 20 mg of the graphene oxide, 10 g of a water solvent, and 200 mg of a hyperbranched polyamide to the reactor, and stirring for 3 hours, so as to obtain a nanocomposite material spinning slurry of the hyperbranched polyamide and graphene.
  • In the foregoing step 2, the extruding the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 μm at a rate of 1 to 100 mL/h, and retaining the spinning slurry in rotated coagulant for 1 to 3600 s to coagulate the spinning slurry into fibers, specifically includes: extruding the nanocomposite material spinning slurry of the hyperbranched polyamide and graphene through a spinning nozzle with a diameter of 800 μm at a rate of 1 mL/h, and retaining the nanocomposite material spinning slurry in a rotated CaCl2 aqueous solution for 1 s to coagulate the nanocomposite material spinning slurry into fibers.
  • In the foregoing step 3, the washing the coagulated fiber product, drying the coagulated fiber product in a vacuum, and then performing reduction to obtain the graphene composite fiber, specifically includes: collecting the coagulated fiber product by using a winder, washing the coagulated fiber product, drying the coagulated fiber product in a vacuum at 80 degrees for 24 hours, and then performing reduction by using acetic acid, so as to obtain a composite fiber of the hyperbranched polyamide and graphene, where the composite fiber has a diameter of 800 μm, a breaking strength of 450 MPa, a breaking elongation of 5%, and an electrical conductivity of 1000 S/m.
  • 6. In yet another embodiment of the present invention, the foregoing steps may be specifically:
  • In the foregoing step 1, the adding 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stirring, so as to obtain a nanocomposite material spinning slurry of the polymer and graphene, specifically includes: adding 10 mg of the graphene oxide, 10 g of a water solvent water, and 200 mg of a hyperbranched polyamide to the reactor, and stirring for 24 hours, so as to obtain a nanocomposite material spinning slurry of the hyperbranched polyamide and graphene.
  • In the foregoing step 2, the extruding the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 μm at a rate of 1 to100 mL/h, and retaining the spinning slurry in rotated coagulant for 1 to 3600 s to coagulate the spinning slurry into fibers, specifically includes: extruding the nanocomposite material spinning slurry of the hyperbranched polyamide and graphene through a spinning nozzle with a diameter of 5000 μm at a rate of 1 mL/h, and retaining the nanocomposite material spinning slurry in a rotated CaCl2 ethanol solution for 50 s to coagulate the nanocomposite material spinning slurry into fibers.
  • In the foregoing step 3, the washing the coagulated fiber product, drying the coagulated fiber product in a vacuum, and then performing reduction to obtain the graphene composite fiber, specifically includes: collecting the coagulated fiber product by using a winder, washing the coagulated fiber product, drying the coagulated fiber product in a vacuum at 80 degrees for 24 hours, and then performing reduction by using a mixture of hydroiodic acid and acetic acid, so as to obtain a composite fiber of the hyperbranched polyamide and graphene, where the composite fiber has a diameter of 5000 μm, a breaking strength of 515 MPa, a breaking elongation of 5%, and an electrical conductivity of 5000 S/m.
  • 7. In yet another embodiment of the present invention, the foregoing steps may be specifically:
  • In the foregoing step 1, the adding 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stirring, so as to obtain a nanocomposite material spinning slurry of the polymer and graphene, specifically includes: adding 10 mg of the graphene oxide, 10 g of an N,N-dimethylformamide solvent, and 200 mg of hyperbranched polyester to the reactor, and stirring for 10 hours, so as to obtain a nanocomposite material spinning slurry of the hyperbranched polyester and graphene.
  • In the foregoing step 2, the extruding the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 μm at a rate of 1 to 100 mL/h, and retaining the spinning slurry in rotated coagulant for 1 to 3600 s to coagulate the spinning slurry into fibers, specifically includes: extruding the nanocomposite material spinning slurry of the hyperbranched polyester and graphene through a spinning nozzle with a diameter of 5000 μm at a rate of 1 mL/h, and retaining the nanocomposite material spinning slurry in rotated ethyl acetate for 50 s to coagulate the nanocomposite material spinning slurry into fibers.
  • In the foregoing step 3, the washing the coagulated fiber product, drying the coagulated fiber product in a vacuum, and then performing reduction to obtain the graphene composite fiber, specifically includes: collecting the coagulated fiber product by using a winder, washing the coagulated fiber product, drying the coagulated fiber product in a vacuum at 80 degrees for 24 hours, and then performing reduction by using KOH, so as to obtain a composite fiber of the hyperbranched polyester and graphene, where the composite fiber has a diameter of 5000 μm, a breaking strength of 545 MPa, a breaking elongation of 5%, and an electrical conductivity of 4500 S/m.
  • 8. In yet another embodiment of the present invention, the foregoing steps may be specifically:
  • In the foregoing step 1, the adding 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stirring, so as to obtain a nanocomposite material spinning slurry of the polymer and graphene, specifically includes: adding 10 mg of the graphene oxide, 10 g of an N,N-dimethylformamide solvent, and 200 mg of a hyperbranched polyamide to the reactor, and stirring for 10 hours, so as to obtain a nanocomposite material spinning slurry of the hyperbranched polyamide and graphene.
  • In the foregoing step 2, the extruding the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 μm at a rate of 1 to 100 mL/h, and retaining the spinning slurry in rotated coagulant for 1 to 3600 s to coagulate the spinning slurry into fibers, specifically includes: extruding the nanocomposite material spinning slurry of the hyperbranched polyamide and graphene through a spinning nozzle with a diameter of 100 μm at a rate of 10 mL/h, and retaining the nanocomposite material spinning slurry in rotated petroleum ether for 50 s to coagulate the nanocomposite material spinning slurry into fibers.
  • In the foregoing step 3, the washing the coagulated fiber product, drying the coagulated fiber product in a vacuum, and then performing reduction to obtain the graphene composite fiber, specifically includes: collecting the coagulated fiber product by using a winder, washing the coagulated fiber product, drying the coagulated fiber product in a vacuum at 80 degrees for 24 hours, and then performing reduction by using NaOH, so as to obtain a composite fiber of the hyperbranched polyamide and graphene, where the composite fiber has a diameter of 100 μm, a breaking strength of 460 MPa, a breaking elongation of 5%, and an electrical conductivity of 1200 S/m.
  • 9. In yet another embodiment of the present invention, the foregoing steps may be specifically:
  • In the foregoing step 1, the adding 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stirring, so as to obtain a nanocomposite material spinning slurry of the polymer and graphene, specifically includes: adding 10 mg of the graphene oxide, 10 g of an N-methyl-2-pyrolidone solvent, and 200 mg of hyperbranched polyester to the reactor, and stirring for 5 hours, so as to obtain a nanocomposite material spinning slurry of the hyperbranched polyester and graphene.
  • In the foregoing step 2, the extruding the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 μm at a rate of 1 to 100 mL/h, and retaining the spinning slurry in rotated coagulant for 1 to 3600 s to coagulate the spinning slurry into fibers, specifically includes: extruding the nanocomposite material spinning slurry of the hyperbranched polyester and graphene through a spinning nozzle with a diameter of 50 μm at a rate of 5 mL/h, and retaining the nanocomposite material spinning slurry in rotated petroleum ether for 50 s to coagulate the nanocomposite material spinning slurry into fibers.
  • In the foregoing step 3, the washing the coagulated fiber product, drying the coagulated fiber product in a vacuum, and then performing reduction to obtain the graphene composite fiber, specifically includes: collecting the coagulated fiber product by using a winder, washing the coagulated fiber product, drying the coagulated fiber product in a vacuum at 80 degrees for 24 hours, and then performing thermal reduction at 500 degrees, so as to obtain a composite fiber of the hyperbranched polyester and graphene, where the composite fiber has a diameter of 50 μm, a breaking strength of 525 MPa, a breaking elongation of 5%, and an electrical conductivity of 2100 S/m.
  • 10. In yet another embodiment of the present invention, the foregoing steps may be specifically:
  • In the foregoing step 1, the adding 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stirring, so as to obtain a nanocomposite material spinning slurry of the polymer and graphene, specifically includes: adding 10 mg of the graphene oxide, 10 g of an N-methyl-2-pyrolidone solvent, and 200 mg of polyvinyl alcohol to the reactor, and stirring for 20 hours, so as to obtain a nanocomposite material spinning slurry of the polyvinyl alcohol and graphene.
  • In the foregoing step 2, the extruding the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 μm at a rate of 1 to 100 mL/h, and retaining the spinning slurry in rotated coagulant for 1 to 3600 s to coagulate the spinning slurry into fibers, specifically includes: extruding the nanocomposite material spinning slurry of the polyvinyl alcohol and graphene through a spinning nozzle with a diameter of 5 μm at a rate of 15 mL/h, and retaining the nanocomposite material spinning slurry in a rotated KOH ethanol solution for 50 s to coagulate the nanocomposite material spinning slurry into fibers.
  • In the foregoing step 3, the washing the coagulated fiber product, drying the coagulated fiber product in a vacuum, and then performing reduction to obtain the graphene composite fiber, specifically includes: collecting the coagulated fiber product by using a winder, washing the coagulated fiber product, drying the coagulated fiber product in a vacuum at 80 degrees for 24 hours, and then performing reduction by using acetic acid, so as to obtain a composite fiber of the polyvinyl alcohol and graphene, where the composite fiber has a diameter of 5 μm, a breaking strength of 520 MPa, a breaking elongation of 5%, and an electrical conductivity of 1300 S/m.
  • The spinning nozzle in the foregoing specific implementation manners includes spinning capillaries.
  • In the embodiments of the present invention, large graphene oxide sheets are used as raw materials, which significantly improve tensile strength of a graphene composite fiber. Addition of a polymer provides good tenacity for the composite fiber. In a spinning process, tedious steps such as aeration, heating, reaction, centrifugation, and washing are removed, so that a process is significantly simplified, and is easy to operate, energy saving, and environment friendly. In the spinning process, rotated coagulant is used to increase a tensile force of a gelatinous fiber, so that the gelatinous fiber has high orientation and tacticity, thereby significantly improving strength of an obtained solid fiber. The final reduction process restores electrical conductivity of a graphene fairly well, so that an obtained fiber has an electrical conductivity comparable to that of graphene paper (which is a macroscopic material formed by means of suction filtration of a graphene solution, and is similar to paper in form). The graphene composite fiber obtained in the embodiments of the present invention has advantages of high strength, good tenacity, and high electrical conductivity, may be produced on a large scale, and may be widely used in the fields of electrically conductive fabrics, reinforcement of materials, electrically conductive devices, and the like.
  • The foregoing specifically describes the present invention by using the embodiments. The embodiments are merely intended to further describe the present invention, and should not be construed as a limitation on the protection scope of the present invention. Unessential changes and adjustments made by a person skilled in the art according to content of the present invention shall fall within the protection scope of the present invention.

Claims (10)

What is claimed is:
1. A graphene composite fiber, comprising:
graphene sheets; and
a polymer for aggregating the graphene sheets together, wherein the polymer comprises at least one of a hyperbranched polymer and polyvinyl alcohol, the graphene sheets and the polymer are interleaved and stacked to form a layered structure, and the graphene sheets are arranged along an axial direction of the graphene composite fiber.
2. The graphene composite fiber according to claim 1, wherein the hyperbranched polymer comprises one or more of hyperbranched polyester, a hyperbranched polyamide, and hyperbranched polyglycidyl ether.
3. The graphene composite fiber according to claim 1, wherein the polymer comprises one or two of hyperbranched polyester, a hyperbranched polyamide, hyperbranched polyglycidyl ether, and the polyvinyl alcohol.
4. The graphene composite fiber according to claim 1, wherein the graphene composite fiber has a diameter of 5 to 5000 μm.
5. A production method of an electrically conductive graphene composite fiber, the method comprising:
adding 1 part by weight of a graphene oxide, 50 to 2000 parts by weight of a solvent, and 0.1 to 100 parts by weight of a polymer to a reactor, and stirring, so as to obtain a nanocomposite material spinning slurry of the polymer and graphene, wherein the polymer comprises at least one of a hyperbranched polymer and polyvinyl alcohol;
extruding the spinning slurry through a spinning nozzle with a diameter of 5 to 5000 pm at a rate of 1 to 100 mL/h, retaining the spinning slurry in rotated coagulant for 1 to 3600 s, to coagulate the spinning slurry into fibers; and
washing the coagulated fibers, drying the coagulated fibers in a vacuum, and then performing reduction to obtain the graphene composite fiber.
6. The production method of an electrically conductive graphene composite fiber according to claim 5, wherein the polymer comprises one or two of hyperbranched polyester, a hyperbranched polyamide, hyperbranched polyglycidyl ether, and the polyvinyl alcohol.
7. The production method of an electrically conductive graphene composite fiber according to claim 6, wherein the solvent of 50 to 2000 parts by weight comprises one or more of N-methyl-2-pyrolidone, N,N-dimethylformamide, and water.
8. The production method of an electrically conductive graphene composite fiber according to claim 6, wherein the coagulant comprises one or more of a NaOH aqueous solution, a KOH aqueous solution, a CaCl2 aqueous solution, a NaOH methanol solution, a KOH methanol solution, a CaCl2 methanol solution, a NaOH ethanol solution, a KOH ethanol solution, a CaCl2 ethanol solution, diethyl ether, ethyl acetate, acetone, and petroleum ether.
9. The production method of an electrically conductive graphene composite fiber according to claim 6, wherein the reduction method comprises thermal reduction or chemical reduction, wherein a reducing agent used in the chemical reduction comprises one or more of hydrazine hydrate, vitamin C, lysine, potassium hydroxide, sodium hydroxide, hydroiodic acid, and acetic acid.
10. The production method of an electrically conductive graphene composite fiber according to claim 5, wherein the spinning nozzle comprises spinning capillaries.
US14/577,609 2013-08-01 2014-12-19 Production method of electrically conductive graphene composite fiber Abandoned US20150104642A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201310332049.2A CN103541043A (en) 2013-08-01 2013-08-01 Preparation method of electric graphene composite fiber
CN201310332049.2 2013-08-01
PCT/CN2014/072689 WO2015014124A1 (en) 2013-08-01 2014-03-03 Method for preparing conductive graphene composite fiber

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/072689 Continuation WO2015014124A1 (en) 2013-08-01 2014-03-03 Method for preparing conductive graphene composite fiber

Publications (1)

Publication Number Publication Date
US20150104642A1 true US20150104642A1 (en) 2015-04-16

Family

ID=49964870

Family Applications (1)

Application Number Title Priority Date Filing Date
US14/577,609 Abandoned US20150104642A1 (en) 2013-08-01 2014-12-19 Production method of electrically conductive graphene composite fiber

Country Status (5)

Country Link
US (1) US20150104642A1 (en)
EP (1) EP2871268A4 (en)
JP (1) JP2015530492A (en)
CN (1) CN103541043A (en)
WO (1) WO2015014124A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108624980A (en) * 2017-03-24 2018-10-09 中国石化仪征化纤有限责任公司 A kind of conducting PET fiber and preparation method thereof

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103541043A (en) * 2013-08-01 2014-01-29 华为技术有限公司 Preparation method of electric graphene composite fiber
CN104328533A (en) * 2014-11-10 2015-02-04 沙嫣 Preparation method of high-strength and high-modulus polyvinyl alcohol-graphene nano composite fibers
CN104451925B (en) * 2014-11-21 2017-01-04 东华大学 A kind of water-soluble polymer/Graphene composite fibre and its preparation method and application
CN105126764A (en) * 2015-06-26 2015-12-09 中国航空工业集团公司北京航空材料研究院 Graphene macroscopic body material for sewage treatment
CN105126750A (en) * 2015-06-26 2015-12-09 中国航空工业集团公司北京航空材料研究院 Preparation method of graphene macroscopic body material for sewage treatment
CN105289539A (en) * 2015-11-11 2016-02-03 华南理工大学 Graphene/ polyvinyl alcohol nanofibers membrane adsorbent, preparation method and appliance
WO2018010575A1 (en) * 2016-07-11 2018-01-18 济南圣泉集团股份有限公司 Graphene composite polyvinyl alcohol masterbatch and graphene composite polyvinyl alcohol fiber, preparation method for masterbatch, and applications thereof
CN106192201B (en) * 2016-07-18 2018-09-14 浙江大学 A kind of graphene fiber non-woven fabrics and preparation method thereof
CN106245138B (en) * 2016-07-27 2019-01-22 南京工程学院 A kind of preparation method of high recovery stress shape memory complex fiber material
CN106948052B (en) * 2017-04-18 2019-08-16 江苏陆亿纺织科技有限公司 A kind of flame-proof electrostatic resistance yarn and its fabric
CN107151829A (en) * 2017-05-16 2017-09-12 南通凯大纺织有限公司 A kind of preparation method of antibacterial uvioresistant automatically cleaning composite-type terylene
CN107164817B (en) * 2017-06-06 2019-03-26 烟台市烯能新材料有限责任公司 A kind of preparation method of graphene-graphene oxide composite nylon fiber
CN107338498B (en) * 2017-08-21 2019-01-25 广东富琳健康产业有限公司 A kind of functional fibre and preparation method thereof for graphene far infrared waist support
CN108193295A (en) * 2018-01-23 2018-06-22 杭州高烯科技有限公司 A kind of high resiliency antistatic UV resistance multifunctional fibre and preparation method thereof
KR101973895B1 (en) * 2018-02-12 2019-04-29 한국과학기술원 Graphene Polymer Composite Fiber structure as thermoelectric materials and Fabrication and manufacturing method thereof
CN108456998B (en) * 2018-03-05 2020-11-17 绍兴厚创新材料科技有限公司 High-strength antibacterial nanofiber membrane and preparation method thereof
CN109811426B (en) * 2019-01-30 2020-05-26 四川大学 Flexible conductive fiber with core-sheath structure and preparation method thereof
CN109750391A (en) * 2019-02-12 2019-05-14 青岛大学 A kind of positive pressure spin processes prepare the system and method for graphene fiber
CN111235676B (en) * 2020-03-19 2020-12-04 宁波市雪狼户外服饰有限公司 Graphene-based pneumonia pathogen protection fabric and preparation method thereof

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05328486A (en) * 1990-12-06 1993-12-10 Agency Of Ind Science & Technol Electroacoustic transducer
JPH0941224A (en) * 1995-08-01 1997-02-10 Tokushu Paper Mfg Co Ltd Production of starch fiber complexed with fine particle
JP4118479B2 (en) * 1999-11-19 2008-07-16 旭化成せんい株式会社 Method for producing polyketone fiber
JP3749502B2 (en) * 2002-05-07 2006-03-01 独立行政法人科学技術振興機構 Biodegradable porous ultrafine hollow fiber and method for producing the same
TW201012749A (en) * 2008-08-19 2010-04-01 Univ Rice William M Methods for preparation of graphene nanoribbons from carbon nanotubes and compositions, thin films and devices derived therefrom
KR101755044B1 (en) * 2009-03-16 2017-07-06 보르벡크 머터리얼스 코포레이션 Polymeric fibers and articles made therefrom
WO2011074125A1 (en) * 2009-12-18 2011-06-23 国立大学法人 北海道大学 Graphene oxide sheet, article containing grapheme-containing substance produced by reducing the graphene oxide sheet, and process for production of the graphene oxide sheet
KR101193970B1 (en) * 2011-03-15 2012-10-24 한양대학교 산학협력단 Graphene fiber and method for preparing the same
KR101195490B1 (en) * 2011-03-15 2012-10-29 한양대학교 산학협력단 Graphene composite fiber and the method for preparing the fiber
CN102352030A (en) * 2011-07-25 2012-02-15 浙江大学 Hyper branched polyglycidyl ether grafted graphene nano composite material and preparation method thereof
CN102534868B (en) * 2011-12-26 2013-09-04 浙江大学 Preparation method for high strength macro graphene conductive fiber
CN102586916B (en) * 2012-01-18 2013-10-23 浙江大学 Preparation method for composite fiber of hyperbranched polymer grafted graphene
CN102664104B (en) * 2012-05-04 2014-07-02 东南大学 Method for preparing one-dimensional graphene/semiconductor nano wire compound photo anode by adopting electric spinning method
CN102690426B (en) * 2012-06-08 2013-11-06 浙江大学 Method for preparing graphene/polymer composite material based on infrared irradiation
CN102828267B (en) * 2012-09-10 2014-05-07 浙江大学 Preparation method of conductive high-strength graphene-reinforced polymer fiber
CN102926020A (en) * 2012-11-14 2013-02-13 浙江大学 Preparation method for polymer-grafted graphene laminated fiber with electrical conductivity and high-strength
CN103541043A (en) * 2013-08-01 2014-01-29 华为技术有限公司 Preparation method of electric graphene composite fiber

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108624980A (en) * 2017-03-24 2018-10-09 中国石化仪征化纤有限责任公司 A kind of conducting PET fiber and preparation method thereof

Also Published As

Publication number Publication date
EP2871268A1 (en) 2015-05-13
JP2015530492A (en) 2015-10-15
EP2871268A4 (en) 2015-08-05
WO2015014124A1 (en) 2015-02-05
CN103541043A (en) 2014-01-29

Similar Documents

Publication Publication Date Title
Lin et al. Carbon nanotube sponges, aerogels, and hierarchical composites: Synthesis, properties, and energy applications
Zhao et al. Highly electrically conductive three-dimensional Ti3C2T x MXene/reduced graphene oxide hybrid aerogels with excellent electromagnetic interference shielding performances
Gong et al. Amino graphene oxide/dopamine modified aramid fibers: Preparation, epoxy nanocomposites and property analysis
Ammar et al. Influence of graphene oxide on mechanical, morphological, barrier, and electrical properties of polymer membranes
Song et al. Highly compressible, anisotropic aerogel with aligned cellulose nanofibers
CN107059251B (en) The preparation method of one-way wet-guide nanofiber multilayer complex films with wetting gradient
Pandey et al. Sulfonated polyimide/acid-functionalized graphene oxide composite polymer electrolyte membranes with improved proton conductivity and water-retention properties
Ji et al. Review of functionalization, structure and properties of graphene/polymer composite fibers
Xing et al. Nanocellulose-graphene composites: A promising nanomaterial for flexible supercapacitors
Cruz-Silva et al. Super-stretchable graphene oxide macroscopic fibers with outstanding knotability fabricated by dry film scrolling
JP6208364B2 (en) Graphene production method and graphene dispersion composition
JP6004507B2 (en) Graphene fiber and method for forming the same
Kang et al. All-solid-state flexible supercapacitors fabricated with bacterial nanocellulose papers, carbon nanotubes, and triblock-copolymer ion gels
Wu et al. Carbonaceous hydrogels and aerogels for supercapacitors
JP2018524482A (en) Graphene fiber nonwoven fabric and method for producing the same
Hooshmand et al. Dry-spun single-filament fibers comprising solely cellulose nanofibers from bioresidue
Harito et al. Polymer nanocomposites having a high filler content: synthesis, structures, properties, and applications
CN103903879B (en) Porous grapheme/ MnO2 composite film and preparation method and application thereof
Cao et al. Ultrathin and flexible CNTs/MXene/cellulose nanofibrils composite paper for electromagnetic interference shielding
Hamedi et al. Highly conducting, strong nanocomposites based on nanocellulose-assisted aqueous dispersions of single-wall carbon nanotubes
Jiang et al. Preparation and characterization of graphene/poly (vinyl alcohol) nanocomposites
Zeng et al. Ultralight and highly elastic graphene/lignin-derived carbon nanocomposite aerogels with ultrahigh electromagnetic interference shielding performance
KR101436500B1 (en) Carbon fiber composites comprising carbon fiber coated carbon nanotube/graphene oxide hybrid and the manufacturing method thereof
CN104072979B (en) A kind of stannic oxide/graphene nano band/polymer composite film and preparation method thereof
Miyauchi et al. Conductive cable fibers with insulating surface prepared by coaxial electrospinning of multiwalled nanotubes and cellulose

Legal Events

Date Code Title Description
AS Assignment

Owner name: HUAWEI TECHNOLOGIES CO., LTD., CHINA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GAO, CHAO;HU, XIAOZHEN;ZHOU, XIAOSONG;AND OTHERS;SIGNING DATES FROM 20141201 TO 20141211;REEL/FRAME:034560/0298

Owner name: ZHEJIANG UNIVERSITY, CHINA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GAO, CHAO;HU, XIAOZHEN;ZHOU, XIAOSONG;AND OTHERS;SIGNING DATES FROM 20141201 TO 20141211;REEL/FRAME:034560/0298

STCB Information on status: application discontinuation

Free format text: EXPRESSLY ABANDONED -- DURING EXAMINATION