US20140004344A1 - Graphene fiber and method for manufacturing same - Google Patents

Graphene fiber and method for manufacturing same Download PDF

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Publication number
US20140004344A1
US20140004344A1 US14/004,829 US201214004829A US2014004344A1 US 20140004344 A1 US20140004344 A1 US 20140004344A1 US 201214004829 A US201214004829 A US 201214004829A US 2014004344 A1 US2014004344 A1 US 2014004344A1
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Prior art keywords
graphene
fiber
graphene fiber
polymer
present
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US14/004,829
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Seon Jeong Kim
Min Kyoon Shin
Shi Hyeong Kim
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Industry University Cooperation Foundation IUCF HYU
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Industry University Cooperation Foundation IUCF HYU
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Assigned to IUCF-HYU (INDUSTRY-UNIVERSITY COOPERATION FOUNDATION HANYANG UNIVERSITY) reassignment IUCF-HYU (INDUSTRY-UNIVERSITY COOPERATION FOUNDATION HANYANG UNIVERSITY) ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KIM, SEON JEONG, KIM, Shi Hyeong, SHIN, Min Kyoon
Publication of US20140004344A1 publication Critical patent/US20140004344A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • 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
    • C01B31/0438—
    • C01B31/0446—
    • 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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • 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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/06—Feeding liquid to the spinning head
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/16—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]

Definitions

  • the present invention relates to a method for producing a graphene fiber and a graphene fiber produced by the method. More specifically, the present invention relates to a porous graphene fiber including graphene whose wrinkled structure is maintained to achieve excellent mechanical and electrochemical properties, and a method for producing the graphene fiber.
  • Graphene is a two-dimensional nanostructure of covalently bonded carbon atoms and exhibits outstanding mechanical, electrical, and thermal properties.
  • Graphene flakes consist of single or several graphene sheets exfoliated from graphite.
  • Graphene flakes have been reconstituted into bulky structures that have a modulus of elasticity exceeding that of flexible graphite while possessing high strength.
  • a major challenge for graphene structures with high strength and toughness is to maintain the inherent active surface of graphene by preventing restacking of graphene tending to form close-packed layer structures.
  • Single-layer graphene or a graphene flake has a wrinkled structure due to high area-to-thickness ratio thereof, but a graphene paper or composite including a large amount of graphene usually has a dense layer structure similar to graphite.
  • the dense layered structure of graphene is an obstacle in achieving maximum mechanical properties owing to the short length of graphene that reduces the van der Waals force and tensile strength between graphene layers (by 1% or less).
  • the dense layered structure of graphene composites limits application thereof to energy and hydrogen storage media. For these reasons, there is a need to improve the porosity, mechanical properties and electrochemical properties of graphene structures.
  • a method for producing a graphene fiber including a) dispersing graphene and a surfactant in a solvent to prepare a dispersion, b) incorporating the dispersion into a polymer solution, wet spinning the resulting solution, followed by drying to produce a composite fiber, and c) annealing the composite fiber or treating the composite fiber with a strong acid to remove the polymer.
  • the graphene is preferably chemically reduced graphene or graphene oxide, more preferably reduced graphene with acid functional groups.
  • the chemically reduced graphene may be prepared by reducing an aqueous dispersion of graphene with hydrazine at 90 to 100° C. for 1 to 24 hours.
  • the annealing is preferably performed at a temperature of 300 to 1000° C.
  • the strong acid used to remove the polymer may be hydrochloric acid, sulfuric acid, a piranha solution consisting of a mixture of sulfuric acid and hydrogen peroxide, or a superacid consisting of a mixture of sulfuric acid and oleum.
  • the strong acid is preferably 30 to 40 wt % hydrochloric acid.
  • the surfactant used to disperse the graphene is preferably selected from sodium dodecyl benzene sulfonate (SDBS), sodium dodecyl sulfonate (SDS), Triton X-100, and cetyltrimethylammonium bromide (CTAB).
  • SDBS sodium dodecyl benzene sulfonate
  • SDS sodium dodecyl sulfonate
  • CTAB cetyltrimethylammonium bromide
  • the surfactant is more preferably sodium dodecyl benzene sulfonate (SDBS).
  • the polymer used in the method of the present invention is preferably selected from polyvinyl alcohol (PVA), poly(methyl methacrylate) (PMMA), and a mixture thereof.
  • the contents of the graphene and the polymer in the graphene composite fiber are from 20 to 90% by weight and from 10 to 80% by weight, respectively. Within these ranges, the wrinkled structure of the graphene can be maintained.
  • the present invention also provides a porous graphene fiber including graphene whose wrinkled structure is maintained even when a polymer is removed from a graphene composite fiber.
  • the porous graphene fiber of the present invention has an electrical conductivity of 10 to 100 S/cm, an electrochemical capacitance of 100 to 300 F/g, and a porosity of 1000 to 2000 m 2 /g.
  • the length of the graphene is preferably from 100 to 1000 nm
  • the diameter of the graphene composite fiber is typically from 30 to 100 ⁇ m, which may be controlled by the diameter of a syringe tip used during wet spinning, and the diameter of the porous graphene fiber after the polymer removal is typically from 15 to 50 ⁇ m.
  • the porous graphene fiber of the present invention may be formed into knot and spring structures due to flexibility thereof, and several strands thereof may also be woven into a fabric.
  • porous graphene fiber of the present invention can be utilized in a supercapacitor or an energy or hydrogen storage medium due to excellent electrical and mechanical properties and high porosity thereof.
  • the graphene fiber of the present invention which includes graphene whose wrinkled structure is maintained, exhibits far superior mechanical and electrochemical properties to conventional graphene papers, graphene composite films, and flexible graphite.
  • the graphene fiber of the present invention can be formed into knot or spring structures due to flexibility thereof and can also be woven into a fabric. Therefore, the graphene fiber of the present invention is applicable to a wide variety of fields.
  • the wrinkled structure of graphene makes the graphene fiber of the present invention porous. This enables utilization of the graphene fiber of the present invention in energy and hydrogen storage media, etc.
  • porous graphene fiber of the present invention can be mass-produced in a simple and economical manner and its length can be extended to tens of meters in a continuous process. Therefore, the porous graphene fiber of the present invention is ideally suited to industrial applications.
  • FIG. 1 is a conceptual diagram showing the procedure for producing a fiber composed of graphene flakes having directivity and wrinkles according to the present invention.
  • FIG. 2 shows SEM images of the surface and cross-sectional morphologies of a graphene fiber having a wrinkled structure according to the present invention.
  • FIG. 3 is a SEM image showing the cross section of a graphene fiber from which PVA was removed by annealing a graphene/PVA fiber at 600° C.
  • FIG. 4 shows cyclic voltammograms of a graphene fiber of the present invention at different scan rates.
  • FIG. 1 is a conceptual diagram showing the procedure for producing a fiber composed of graphene flakes having directivity and wrinkles according to the present invention. According to the method of the present invention, graphene can be prevented from restacking in the individual steps of producing a fiber from a graphene solution in order to maintain a wrinkled structure.
  • Electrostatic repulsive force (van der Waals force)+(force of gravity by graphene)+(centrifugal force)
  • This condition may be varied with increasing time when a large amount of graphene is loaded, and as a result, the graphene may aggregate.
  • a graphene fiber is produced by the following procedure. First, a graphene/DMF solution is prepared. The DMF is exchanged with distilled water by sonication and centrifugation, and the graphene is well dispersed in distilled water with the help of a surfactant to prepare a graphene solution. The graphene solution is incorporated into a coagulation bath containing polyvinyl alcohol (PVA). The graphene solution incorporated into the polymer is changed to a graphene gel-fiber by an assembly process through hydrophobic interaction between the graphene flakes surrounded by the PVA chains replacing the surfactant bonded to the graphene flakes. The graphene gel-fiber is washed with distilled water to remove excess PVA.
  • PVA polyvinyl alcohol
  • the wrinkled structure of the graphene flakes can be maintained because the magnitudes of the hydrostatic forces in the x, y, and z directions are equal. Then, the graphene gel-fiber is suspended vertically and dried in air. As a result, a graphene-based composite fiber having a wrinkled structure is formed.
  • the polymer is removed from the composite fiber, leaving a porous fiber composed of graphene alone.
  • the composite fiber is annealed at 300 to 1000° C. to volatilize the polymer or is treated with an acidic solution to remove the polymer.
  • RCCG was dispersed in dimethylformamide (DMF) in the presence of an appropriate amount of triethylamine to obtain a stable graphene dispersion.
  • DMF dimethylformamide
  • Several grams of RCCG was obtained by reducing an aqueous dispersion of CCG with excess hydrazine at 95° C. over 2 h in accordance with previously reported methods (Li, D., Muller, M. B., Gilje, S., Kaner, R. B. & Wallace, G. G. Processable aqueous dispersions of graphene nanosheets. Nature Nanotech. 3, 101 (2008)).
  • the graphene aggregated in the aqueous solution.
  • the graphene aggregates were acidified with dilute sulfuric acid under vigorous stirring to a pH of 2 or less, and transferred to a sintered funnel. The aggregates were washed with a large amount of Milli-Q water on the funnel until the pH reached about 7. The filtered material was dried under vacuum at 70° C. for 48 h to obtain RCCG as a solid. The dried RCCG powder was dissolved in DMF to prepare a 0.47-0.5 mg/mL RCCG/DMF solution. The length of the graphene flakes was about 400 nm, as measured using a Zetasizer. The particle size and zeta potential remained stable for several months. The dispersion was filtered under vacuum to obtain a paper having a resistance of 30-40 ⁇ /sq.
  • the solvent (DMF) of the graphene flake dispersion was exchanged with distilled water by centrifugation.
  • the G/F aqueous solution was mixed with sodium dodecyl benzene sulfonate (SDBS) by ultrasonication.
  • SDBS sodium dodecyl benzene sulfonate
  • the graphene/PVA was annealed at 600° C. to remove the PVA, leaving behind a porous fiber composed of graphene alone.
  • the diameter of the graphene fiber was 28 ⁇ m.
  • the graphene fiber was sufficiently flexible and thus could be wound on a glass tube having a small diameter of 6.5 mm without mechanical damage, unlike graphene papers tending to be brittle ( FIG. 1B ).
  • Complete knots of the graphene fiber were difficult to form, but the formation of sufficiently strong, flexible, small diameter knots of the graphene fiber was possible ( FIG. 1C ). Difficulty in the formation of complete knots was due to the small length of the graphene flakes and the frictional force of the rough surface of the graphene fiber composed of the graphene flakes ( FIG. 2B ).
  • Several strands of the graphene fiber can also be woven into a fabric.
  • FIG. 2 shows SEM images of the surface and cross-sectional morphologies of the graphene fiber obtained by removing the PVA from the graphene/PVA composite fiber. After annealing at 600° C. for 1 h or treatment with 37% hydrochloric acid for 24 h, the graphene fiber had a rough surface because of the wrinkled graphene flakes.
  • FIG. 2B The wrinkled graphene flakes were aligned along the axis of the fiber ( FIG. 2C ) and were formed into highly porous petals ( FIG. 2D ).
  • the cross section of the graphene fiber can be specifically seen in FIG. 3 , too. This image demonstrates the formation of graphene flakes without serious restacking.
  • FIG. 4 shows cyclic voltammograms of the graphene fiber at different scan rates (solution: 1 M H 2 SO 4 , reference electrode: Ag/AgCl).
  • the electrical conductivity and electrochemical capacitance of the graphene fiber were 10-100 S/cm and 100-200 F/g, respectively. Accordingly, the graphene fiber is expected to find application in supercapacitors.
  • the graphene fiber of the present invention has outstanding mechanical and electrochemical properties and high electrical conductivity.
  • the graphene fiber of the present invention is highly porous due to wrinkled structure thereof. Therefore, the graphene fiber of the present invention can be used as an electrode for a supercapacitor, a fuel cell, or a battery as an energy storage medium.
  • the graphene fiber of the present invention can also be used to develop a hydrogen storage medium.
  • the graphene fiber of the present invention can be formed into knot and spring structures due to flexibility thereof and can also be woven into a fabric.
  • the porous graphene fiber of the present invention can be mass-produced in a simple and economical manner and its length can be extended to tens of meters in a continuous process.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Fibers (AREA)
  • Carbon And Carbon Compounds (AREA)
US14/004,829 2011-03-15 2012-03-09 Graphene fiber and method for manufacturing same Abandoned US20140004344A1 (en)

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KR1020110022832A KR101193970B1 (ko) 2011-03-15 2011-03-15 그라핀 섬유 및 이의 제조 방법
KR10-2011-0022832 2011-03-15
PCT/KR2012/001718 WO2012124934A2 (fr) 2011-03-15 2012-03-09 Fibre de graphène et son procédé de fabrication

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US20130335255A1 (en) * 2012-06-14 2013-12-19 International Business Machines Corporation Graphene based structures and methods for broadband electromagnetic radiation absorption at the microwave and terahertz frequencies
US9174413B2 (en) 2012-06-14 2015-11-03 International Business Machines Corporation Graphene based structures and methods for shielding electromagnetic radiation
US20170120643A1 (en) * 2014-04-08 2017-05-04 Brother Kogyo Kabushiki Kaisha Liquid discharge apparatus
CN107504893A (zh) * 2017-09-06 2017-12-22 南京理工大学 高灵敏度网状石墨烯/弹性体应变传感器及其制备方法
US10145029B2 (en) 2013-04-10 2018-12-04 Huawei Technologies Co., Ltd. Graphene fiber and prepartion method thereof
US10190243B2 (en) 2015-10-20 2019-01-29 Acelon Chemicals and Fiber Corporation Method of preparing of natural graphene cellulose blended meltblown nonwoven fabric
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US20200325024A1 (en) * 2019-04-11 2020-10-15 Cornell University Method for storage or transportation of graphene oxide
US10950392B2 (en) 2017-02-17 2021-03-16 Aict High performance nano/micro composite fiber capable of storing electrical energy and method for fabricating thereof
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US10995428B2 (en) 2016-04-11 2021-05-04 Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) Graphene fiber and method of manufacturing the same
US20210246580A1 (en) * 2016-04-11 2021-08-12 Iucf-Hyu (Industry-Universty Cooperation Foundation Hanyang Universty) Graphene fiber and method of manufacturing the same
CN113470986A (zh) * 2021-07-19 2021-10-01 重庆文理学院 一种柔性线状超级电容器及其制备方法
WO2021262747A1 (fr) * 2020-06-25 2021-12-30 Ciparro Nicholas L Procédés de formation d'une fibre nanocomposite et mélange et fibres nanocomposites associés
CN113860735A (zh) * 2021-10-14 2021-12-31 广东欧文莱陶瓷有限公司 一种耐酸耐碱数码保护釉料
US11339259B2 (en) * 2016-04-12 2022-05-24 Tingying Zeng Facile methods to manufacture intelligent graphene nanomaterials and the use of for super-light machine and vehicles
JP2022531167A (ja) * 2019-04-30 2022-07-06 青島大学 酸化グラフェン繊維の製造方法および得られた繊維

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CN105088415B (zh) * 2015-06-15 2018-01-05 中国科学技术大学 一种湿纺用氧化石墨烯溶液及其制备方法以及一种石墨烯纤维及其制备方法
WO2017011828A1 (fr) 2015-07-16 2017-01-19 Rensselaer Polytechnic Institute Fibre de graphène et son procédé de fabrication
CN105256408A (zh) * 2015-11-29 2016-01-20 南京新月材料科技有限公司 一种氧化石墨烯纤维及其制备方法
KR101801458B1 (ko) * 2016-03-03 2017-12-20 한양대학교 산학협력단 섬유형 전극 및 이를 이용한 슈퍼커패시터
WO2017179900A1 (fr) * 2016-04-11 2017-10-19 한양대학교 산학협력단 Fibre de graphène et son procédé de fabrication
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