WO2018196475A1 - 一种自融合石墨烯纤维及其制备方法 - Google Patents

一种自融合石墨烯纤维及其制备方法 Download PDF

Info

Publication number
WO2018196475A1
WO2018196475A1 PCT/CN2018/077303 CN2018077303W WO2018196475A1 WO 2018196475 A1 WO2018196475 A1 WO 2018196475A1 CN 2018077303 W CN2018077303 W CN 2018077303W WO 2018196475 A1 WO2018196475 A1 WO 2018196475A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
aqueous solution
fusion
fibers
self
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2018/077303
Other languages
English (en)
French (fr)
Inventor
高超
畅丹
李拯
高微微
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.)
Zhejiang University ZJU
Original Assignee
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
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to US16/476,121 priority Critical patent/US11486086B2/en
Publication of WO2018196475A1 publication Critical patent/WO2018196475A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/01—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof
    • D06M11/05—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof with water, e.g. steam; with heavy water
    • 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
    • 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
    • D01D5/04—Dry spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, e.g. by ultrasonic waves, corona discharge, irradiation, electric currents or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/63—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with hydroxylamine or hydrazine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

Definitions

  • the invention relates to graphene fibers, in particular to a self-fusion graphene fiber and a preparation method thereof.
  • Graphene is a type of allotrope of carbon with a single atomic layer thickness, with low density, very high mechanical strength, thermal conductivity and electrical conductivity, as reported by Geim et al. in 2004 (Science, 2004, 306: 666-669) caused widespread concern.
  • Graphene fiber is a one-dimensional macroscopic assembly integrated by graphene sheets. It has light weight, high thermal conductivity and electrical conductivity due to the excellent properties of graphene itself.
  • the current method for obtaining coarser graphene fibers is generally by spinning with a large diameter spinneret (Accounts of chemical research, 2014, 47(4): 1267-1276) or integrating finer graphene fibers into a tow. (Acta Astronautica, 2013, 82(2): 221-224).
  • the invention utilizes the swelling action of the olefin fiber in a solvent to achieve rapid fusion bonding between the fibers, and obtains a self-fusion graphene fiber with an increased diameter.
  • the self-fused graphene fiber has a large diameter, and can maintain the excellent electrical conductivity and the like of the graphene fiber itself before fusion. Since the plurality of graphene fibers are lapped and fused side by side during the preparation process, the surface of the graphene fiber after self-fusion has axial grooves, resulting in a large specific surface area, which is advantageous for further functional modification of the fibers and improvement of the modifier. The amount of load.
  • the self-fusion method does not require the addition of an additional binder, and is simple in operation, time-saving, environmentally friendly, and has high bonding strength.
  • Existing coarser graphene fibers are generally prepared by spinning with a large diameter spinneret or integrating finer graphene fibers into a tow.
  • the internal and external structures of the graphene fiber are often different, and it is difficult to obtain a graphene fiber having excellent properties.
  • the finer graphene fibers are integrated into the tow, the superiority of the fibers itself cannot be sufficiently exhibited due to the weak interaction between the fibers in the tow.
  • the present invention provides a self-fusion graphene fiber having a larger diameter and a method of preparing the same.
  • a self-fusion graphene fiber characterized in that the self-fusion graphene fiber has a diameter of ⁇ 1 ⁇ m, is formed by fusing a plurality of graphene fibers, and the graphene sheet is along an axis.
  • the fiber surface has axial grooves.
  • the self-fusion graphene fiber has a diameter of ⁇ 100 ⁇ m.
  • the self-fusion graphene fiber has a diameter of ⁇ 1000 ⁇ m.
  • a method for preparing a self-fusion graphene fiber comprising the steps of:
  • the graphene oxide fiber is vacuum dried.
  • the self-fused graphene fiber is dried and then reduced to obtain a high-performance self-fusion graphene fiber.
  • the graphene oxide fiber in the step (1) is prepared by dry or wet spinning.
  • the solvent of the spinning solution is water, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone, ethylene glycol, diethylene glycol, Pyridine, ethyl acetate, dioxane, methyl ethyl ketone, isopropanol, and the like.
  • the wet spinning coagulating solution is a methanol solution of sodium hydroxide, an ethanol solution of sodium hydroxide, a methanol solution of potassium hydroxide, an ethanol solution of potassium hydroxide, an aqueous solution of sodium hydroxide, an aqueous solution of sodium sulfate, and sodium chloride.
  • the vacuum drying temperature is from room temperature to 100 ° C for a period of from 1 to 10 hours.
  • the solvent described in the step (2) is: alcohol such as water, methanol, ethanol, isopropanol, ethylene glycol, glycerin or diethylene glycol, formic acid, acetic acid, propionic acid, butyric acid, pentane Organic acids such as acid, oxalic acid, malonic acid, succinic acid, acrylic acid, acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide , an aqueous solution of N-methylpyrrolidone, pyridine, dioxane, sodium chloride, an aqueous solution of calcium chloride, an aqueous solution of sodium nitrate, an aqueous solution of calcium nitrate, an aqueous solution of sodium phosphate, an aqueous solution of potassium chloride, ammonium chloride An aqueous solution, an aqueous acid
  • the soaking time in the solvent is ⁇ 0.1 s.
  • the reduction method is reduction using a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or thermal reduction at 100 to 3000 °C.
  • a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or thermal reduction at 100 to 3000 °C.
  • the invention has the following advantages:
  • the diameter of the graphene fiber can be arbitrarily increased by this preparation method, and the excellent properties of the graphene fiber itself can be maintained.
  • the graphene fiber has a larger diameter after self-fusion, and there is almost no difference in internal and external structure, which can maintain the excellent mechanical properties and electrical and thermal conductivity of the graphene fiber before fusion.
  • the surface of the graphene fiber after self-fusion has an axial groove, resulting in a large specific surface area, which is advantageous for further functional modification of the fiber and increase the loading of the modifier.
  • the graphene fiber does not slip during the stretching process after self-fusion, and is re-soaked in the solvent without dispersing.
  • Fig. 1 and Fig. 2 are scanning electron micrographs of the cross section and the side surface of 10 graphene fibers after self-fusion.
  • Figure 1 shows that the inner and outer structures of the self-fused graphene fibers are relatively uniform, and
  • Figure 2 shows that the self-fusion of the graphene fibers is good.
  • Figure 3 is a schematic illustration of the fusion of fibers at the surface of the solvent.
  • the invention discloses a self-fusion graphene fiber and a preparation method thereof.
  • the fusion of the fibers is achieved by the mutual fusion of the graphene fibers in the swollen state, and the self-fusion graphene fibers having an increased diameter are obtained.
  • the fusion method has a uniform inner-outer structure and a relatively uniform interlayer spacing, and maintains the excellent mechanical properties and electrical and thermal conductivity of the graphene fibers before fusion.
  • the present invention redisperses the graphene oxide fibers obtained by wet-spinning the solution in a solvent, so that the fibers are infiltrated and swollen, so that the graphene sheets in the fibers have a weak degree of freedom, and can be used in the After the connection, the realignment and mutual fusion of the contact layers are realized, and the fibers are bonded by strong ⁇ - ⁇ interaction, and the finally obtained self-bonding graphene fibers maintain the electrical and thermal conductivity of the graphene fibers before bonding. It solves the technical problems of poor fiber performance caused by large difference in internal and external structure of coarse fiber or weak interaction, and has great practical application value.
  • the fiber proposing method of the present invention may be: sandwiching one end of a plurality of fibers with tweezers, and proposing a plurality of fibers together, as shown in FIG.
  • a plurality of graphene fibers are completely fused to form a unitary structure.
  • the fiber surface has a distinct axial groove that can be used for surface loading.
  • the graphene fiber Before the fusion, the graphene fiber has a diameter of 20 ⁇ m and a mechanical strength of 203 MPa; the plurality of graphene fibers have a diameter of 1120 ⁇ m after fusion, the graphene sheet spacing is 0.5 to 0.8 nm, the structure is uniform, the electrical conductivity is 285 S/m, and the mechanical strength is 476 MPa.
  • the fiber obtained in the step (2) is immersed in water for 0.1 s to allow the fiber to be sufficiently wetted and swollen.
  • 100 graphene fibers are completely fused to form a unitary structure.
  • the fiber surface has a distinct axial groove that can be used for surface loading.
  • the pre-fusion graphene fiber has a diameter of 12 ⁇ m and a mechanical strength of 280 MPa; 100 graphene fibers have a diameter of 176 ⁇ m after fusion, a graphene sheet spacing of 0.7 to 1 nm, a uniform structure, and an electrical conductivity of 1.4 ⁇ 10 4 S/m.
  • the strength is 292 MPa.
  • the four graphene fibers are completely fused to form a unitary structure.
  • the fiber surface has a distinct axial groove that can be used for surface loading.
  • the pre-fusion graphene fiber has a diameter of 18 ⁇ m and a mechanical strength of 242 MPa; the four graphene fibers have a diameter of 32 ⁇ m after fusion, the graphene sheet spacing is 0.5 to 0.7 nm, the structure is uniform, the electrical conductivity is 448 S/m, and the mechanical strength is 353 MPa.
  • Steps (1) to (2) are the same as in the third embodiment.
  • the eight graphene fibers are completely fused to form a unitary structure.
  • the fiber surface has a distinct axial groove that can be used for surface loading.
  • the pre-fusion graphene fiber has a diameter of 18 ⁇ m and a mechanical strength of 242 MPa; the 8 graphene fibers have a diameter of 36 ⁇ m after fusion, the graphene sheet spacing is 0.6-0.8 nm, the structure is uniform, the electrical conductivity is 103 S/m, and the mechanical strength is 326 MPa.
  • Steps (1) to (4) are the same as in the first embodiment.
  • a plurality of graphene fibers are completely fused to form a unitary structure.
  • the fiber surface has a distinct axial groove that can be used for surface loading.
  • the graphene fiber Before the fusion, the graphene fiber has a diameter of 20 ⁇ m and a mechanical strength of 203 MPa; the plurality of graphene fibers have a diameter of 923 ⁇ m after fusion, the graphene sheet spacing is 0.8 to 1 nm, the structure is uniform, and the electrical conductivity is 1.9 ⁇ 10 5 S/m.
  • the strength is 289 MPa.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Fibers (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

本发明公开了一种自融合石墨烯纤维及其制备方法。将干燥的氧化石墨烯纤维浸入溶剂中，溶胀后提出搭接在一起，待其干燥后氧化石墨烯纤维实现了相互融合粘结，进一步还原即可得到自融合石墨烯纤维。自融合的整个过程可在1分钟之内快速完成，不须添加额外的粘结剂，操作简单、省时、环保，粘结强度高，能保持石墨烯纤维本身优异的机械强度、电导率等性能，对进一步制备出具有优异性能的石墨烯纤维二维织物或三维网络块体材料有极大的研究及应用价值。

Description

一种自融合石墨烯纤维及其制备方法 技术领域
本发明涉及石墨烯纤维，尤其涉及一种自融合石墨烯纤维及其制备方法。
背景技术
石墨烯是一类具有单原子层厚度的碳的同素异形体，具有低密度、极高的力学强度、热导率和电导率，自2004年Geim等人报道以来(Science,2004,306:666-669)引起了广泛关注。石墨烯纤维是由石墨烯片层集成的一维宏观组装体，由于石墨烯本身的优异性能而具有质轻、高的热导率和电导率等性能。目前得到较粗石墨烯纤维的方法一般是利用大直径的纺丝头进行纺丝(Accounts of chemical research,2014,47(4):1267-1276)或将较细的石墨烯纤维集成为丝束(Acta Astronautica,2013,82(2):221-224)。大直径的纺丝头纺丝时由于工艺的缺陷，往往导致石墨烯纤维内外结构差异较大，不易得到具有优良性能的石墨烯纤维。较细的石墨烯纤维集成为丝束时，由于丝束中纤维之间的相互作用较弱，石墨烯纤维本身的优异性在丝束中无法充分体现。
本发明利用墨烯纤维在溶剂中的溶胀作用实现纤维间的快速融合粘结，得到直径增大的自融合石墨烯纤维。相比于融合前的石墨烯纤维，自融合后的石墨烯纤维直径较大，能保持融合前石墨烯纤维本身优异的导电性等功能性。由于制备过程中多根石墨烯纤维并排搭接、融合，因此自融合后的石墨烯纤维表面具有轴向沟槽，导致大的比表面积，有利于对纤维进一步功能化改性，提高改性剂的负载量。且此自融合方法不须添加额外的粘结剂，操作简单、省时、环保，粘结强度高。
发明内容
现有的较粗的石墨烯基纤维制备方法一般是利用大直径的纺丝头进行纺丝或将较细的石墨烯纤维集成为丝束。大直径的纺丝头纺丝时往往导致石墨烯纤维内外结构差异较大，不易得到具有优良性能的石墨烯纤维。较细的石墨烯纤维集成为丝束时，由于丝束中纤维间的相互作用较弱而使纤维本身的优异性无法充分体现。针对该问题，本发明提供一种具有较大直径的自融合石墨烯纤维及其制备方法。
本发明的目的是通过以下技术方案实现的：一种自融合石墨烯纤维，其特征在于，所述自融合石墨烯纤维直径≥1μm，由多根石墨烯纤维融合而成，石墨烯片沿轴向定向排列，片层间距≤1nm，密度≥0.8g/cm 3。纤维表面具有轴向沟槽。
进一步地，所述自融合石墨烯纤维直径≥100μm。
进一步地，所述自融合石墨烯纤维直径≥1000μm。
一种自融合石墨烯纤维的制备方法，包括以下步骤：
(1)将氧化石墨烯纤维真空干燥。
(2)将干燥后的纤维在溶剂中浸泡，使纤维被充分浸润溶胀。
(3)将2根或2根以上纤维同时从溶剂中提出，在溶剂-空气界面处，纤维由于受到溶剂的表面张力作用而自发融合。
(4)将自融合的石墨烯纤维干燥后，进行还原，得到高性能的自融合石墨烯纤维。
进一步地，所述步骤(1)中的氧化石墨烯纤维通过干法或湿法纺丝制备得到。其中纺丝液的溶剂为水、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、二甲亚砜、N-甲基吡咯烷酮、乙二醇、二甘醇、吡啶、乙酸乙酯、二氧六环、丁酮、异丙醇等。湿法纺丝的凝固液为氢氧化钠的甲醇溶液、氢氧化钠的乙醇溶液、氢氧化钾的甲醇溶液、氢氧化钾的乙醇溶液、氢氧化钠的水溶液、硫酸钠的水溶液、氯化钠的水溶液、氯化钙的水溶液、硝酸钠的水溶液、硝酸钙的水溶液、磷酸钠的水溶液、氯化钾的水溶液、氯化铵的水溶液、氨水、水乙醚、乙醇、乙酸乙酯、丙酮或这些溶液的混合液。
进一步地，所述真空干燥的温度为室温～100℃，时间为1～10h。
进一步地，步骤(2)中所述的溶剂为：水、甲醇、乙醇、异丙醇、乙二醇、丙三醇、二甘醇等醇类、甲酸、醋酸、丙酸、丁酸、戊酸、乙二酸、丙二酸、丁二酸、丙烯酸等有机酸、丙酮、丁酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、二甲亚砜、N-甲基吡咯烷酮、吡啶、二氧六环、氯化钠的水溶液、氯化钙的水溶液、硝酸钠的水溶液、硝酸钙的水溶液、磷酸钠的水溶液、氯化钾的水溶液、氯化铵的水溶液、氢氧化钾的水溶液、氢氧化钠的水溶液或这些溶液的混合液。
进一步地，在溶剂中的浸泡时间≥0.1s。
进一步地，还原方法为使用氢碘酸、水合肼、维他命C、硼氢化钠等化学还原剂进行还原或100～3000℃热还原。
本发明与现有技术相比，具有的优势如下：
(1)利用氧化石墨烯纤维自身的溶胀实现相互融合粘结，方法简单省时，采用的溶剂环保、广泛易得。该融合方法具有很大的应用价值。
(2)利用此制备方法可以任意增大石墨烯纤维的直径，且石墨烯纤维本身的优异性能得以保持。石墨烯纤维自融合后直径增大，内外结构差别几乎不存 在，能保持融合前石墨烯纤维优良的力学性能及导电导热等功能性。
(3)自融合后的石墨烯纤维表面具有轴向沟槽，导致大的比表面积，有利于对纤维进行进一步的功能化改性，提高改性剂的负载量。
(4)粘结强度高。石墨烯纤维自融合后在拉伸过程中不滑脱，重新浸泡在溶剂中不散开。
附图说明
图1、图2分别是10根石墨烯纤维自融合后截面和侧面的扫描电子显微镜照片。图1表明自融合石墨烯纤维的内外结构较为均一，图2表明石墨烯纤维间实现了良好的自融合。
图3为纤维在溶剂表面处融合示意图。
具体实施方式
本发明公开了一种自融合石墨烯纤维及其制备方法。利用石墨烯纤维在溶胀状态下自身的相互融合作用实现纤维的融合，得到直径增大的自融合石墨烯纤维。相比于其他方法得到的较粗的纤维，该融合方法得到的较粗纤维内外结构、片层间距较均一，且保持了融合前石墨烯纤维优异的力学性能及导电导热等功能性。
为实现石墨烯纤维的融合，本发明将溶液湿纺得到的氧化石墨烯纤维重新分散在溶剂中，使纤维被浸润溶胀，从而使纤维中的石墨烯片层具有微弱的自由度，能够在搭接后实现接触处片层的重新排列和相互融合，纤维间依靠强的π-π相互作用而粘合，最终得到的自粘结石墨烯纤维保持了粘结前石墨烯纤维的导电导热等性能，解决了粗纤维内外结构差异较大或相互作用较弱导致的纤维性能较差等技术问题，具有很大的实际应用价值。
本发明所述的纤维提出方法，可以为：用镊子夹住多根纤维的一端，将多根纤维一起提出，如图3所示。
下面通过实施例对本发明进行具体描述，本实施例只用于对本发明做进一步的说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据上述发明的内容做出一些非本质的改变和调整，均属于本发明的保护范围。
实施例1：
(1)使用湿法纺丝制备氧化石墨烯纤维。其中氧化石墨烯纤维的分散液为N,N-二甲基甲酰胺，凝固液为乙酸乙酯。
(2)将氧化石墨烯纤维在室温下真空干燥3h。
(3)将步骤(2)得到的纤维在水中浸泡1min，使纤维被充分浸润溶胀。
(4)将10000左右根纤维(计量法)同时从溶剂中提出，在溶剂-空气界面处，10000根左右纤维由于受到溶剂的表面张力作用而自发融合。
(5)将自融合的氧化石墨烯纤维干燥后，使用水合肼还原。
经过以上步骤，多根石墨烯纤维完全融合，形成整体结构。纤维表面具有明显的轴向沟槽，可用于表面负载。融合前石墨烯纤维直径为20μm，力学强度为203MPa；多根石墨烯纤维融合后直径为1120μm，石墨烯片层间距为0.5～0.8nm，结构均一，电导率为285S/m，力学强度为476MPa。
实施例2：
(1)使用湿法纺丝制备氧化石墨烯纤维。其中氧化石墨烯纤维的分散液为水，凝固液为氯化钙的水溶液。
(2)将氧化石墨烯纤维在60℃下真空干燥1h。
(3)将步骤(2)得到的纤维在水中浸泡0.1s，使纤维被充分浸润溶胀。
(4)将100根纤维同时从溶剂中提出，在溶剂-空气界面处，100根纤维由于受到溶剂的表面张力作用而自发融合。
(5)将自融合的氧化石墨烯纤维干燥后，使用氢碘酸还原。
经过以上步骤，100根石墨烯纤维完全融合，形成整体结构。纤维表面具有明显的轴向沟槽，可用于表面负载。融合前石墨烯纤维直径为12μm，力学强度为280MPa；100根石墨烯纤维融合后直径为176μm，石墨烯片层间距为0.7～1nm，结构均一，电导率为1.4×10 4S/m，力学强度为292MPa。
实施例3：
(1)使用干法纺丝制备氧化石墨烯纤维。
(2)将氧化石墨烯纤维在100℃下真空干燥10h。
(3)将步骤(2)得到的纤维在水和乙醇的混合液(水与乙醇的体积比＝3)中浸泡2h，使纤维被充分浸润溶胀。
(4)将4根纤维同时从溶剂中提出，在溶剂-空气界面处，4根纤维由于受到溶剂的表面张力作用而自发融合。
(5)将自融合的氧化石墨烯纤维干燥后，使用硼氢化钠还原。
经过以上步骤，4根石墨烯纤维完全融合，形成整体结构。纤维表面具有明显的轴向沟槽，可用于表面负载。融合前石墨烯纤维直径为18μm，力学强度为242MPa；4根石墨烯纤维融合后直径为32μm，石墨烯片层间距为0.5～0.7nm，结构均一，电导率为448S/m，力学强度为353MPa。
实施例4：
步骤(1)～(2)与实施例3相同。
(3)将步骤(2)得到的纤维在水和乙醇的混合液(水与乙醇的体积比＝1)中浸泡2h，使纤维被充分浸润溶胀。
(4)将8根纤维同时从溶剂中提出，在溶剂-空气界面处，8根纤维由于受到溶剂的表面张力作用而自发融合。
(5)将自融合的氧化石墨烯纤维干燥后，进行200℃热还原。
经过以上步骤，8根石墨烯纤维完全融合，形成整体结构。纤维表面具有明显的轴向沟槽，可用于表面负载。融合前石墨烯纤维直径为18μm，力学强度为242MPa；8根石墨烯纤维融合后直径为36μm，石墨烯片层间距为0.6～0.8nm，结构均一，电导率为103S/m，力学强度为326MPa。
实施例5：
步骤(1)～(4)与实施例1相同。
(5)将自融合的氧化石墨烯纤维干燥后，进行3000℃热还原。
经过以上步骤，多根石墨烯纤维完全融合，形成整体结构。纤维表面具有明显的轴向沟槽，可用于表面负载。融合前石墨烯纤维直径为20μm，力学强度为203MPa；多根石墨烯纤维融合后直径为923μm，石墨烯片层间距为0.8～1nm，结构均一，电导率为1.9×10 5S/m，力学强度为289MPa。

Claims (9)

  1. 一种自融合石墨烯纤维，其特征在于，所述自融合石墨烯纤维直径≥1μm，由多根石墨烯纤维融合而成，石墨烯片沿轴向定向排列，片层间距≤1nm，密度≥0.8g/cm 3；纤维表面具有轴向沟槽。
  2. 根据权利要求1所述的自融合石墨烯纤维，其特征在于，所述自融合石墨烯纤维直径≥100μm。
  3. 根据权利要求1所述的自融合石墨烯纤维，其特征在于，所述自融合石墨烯纤维直径≥1000μm。
  4. 一种自融合石墨烯纤维的制备方法，其特征在于，包括以下步骤：
    (1)将氧化石墨烯纤维真空干燥；
    (2)将干燥后的纤维在溶剂中浸泡，使纤维被充分浸润溶胀；
    (3)将2根或2根以上纤维同时从溶剂中提出，在溶剂-空气界面处，纤维由于受到溶剂的表面张力作用而自发融合；
    (4)将自融合的纤维干燥后，进行还原，得到自融合石墨烯纤维。
  5. 根据权利要求4所述的方法，其特征在于，所述步骤(1)中的氧化石墨烯纤维通过干法或湿法纺丝制备得到；其中纺丝液的溶剂为水、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、二甲亚砜、N-甲基吡咯烷酮、乙二醇、二甘醇、吡啶、乙酸乙酯、二氧六环、丁酮、异丙醇；湿法纺丝的凝固液为氢氧化钠的甲醇溶液、氢氧化钠的乙醇溶液、氢氧化钾的甲醇溶液、氢氧化钾的乙醇溶液、氢氧化钠的水溶液、硫酸钠的水溶液、氯化钠的水溶液、氯化钙的水溶液、硝酸钠的水溶液、硝酸钙的水溶液、磷酸钠的水溶液、氯化钾的水溶液、氯化铵的水溶液、氨水、水乙醚、乙醇、乙酸乙酯、丙酮或这些溶液的混合液。
  6. 根据权利要求4所述的方法，其特征在于，所述步骤(1)中真空干燥的温度为室温～100℃，时间为1～10h。
  7. 根据权利要求4所述的方法，其特征在于，步骤(2)中所述的溶剂为：水、甲醇、乙醇、异丙醇、乙二醇、丙三醇、二甘醇、甲酸、醋酸、丙酸、丁酸、戊酸、乙二酸、丙二酸、丁二酸、丙烯酸、丙酮、丁酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、二甲亚砜、N-甲基吡咯烷酮、吡啶、二氧六环、氯化钠的水溶液、氯化钙的水溶液、硝酸钠的水溶液、硝酸钙的水溶液、磷酸钠的水溶液、氯化钾的水溶液、氯化铵的水溶液、氢氧化钾的水溶液、氢氧化钠的水溶液或这些溶液的混合液。
  8. 根据权利要求4所述的方法，其特征在于，在溶剂中的浸泡时间≥0.1 s。
  9. 根据权利要求4所述的方法，其特征在于，还原方法为使用化学还原剂进行还 原，或100～3000℃热还原；所述化学还原剂选自氢碘酸、水合肼、维他命C、硼氢化钠。
PCT/CN2018/077303 2017-04-28 2018-02-27 一种自融合石墨烯纤维及其制备方法 Ceased WO2018196475A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/476,121 US11486086B2 (en) 2017-04-28 2018-02-27 Self-fused graphene fiber and method of preparing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710294377.6A CN106948165B (zh) 2017-04-28 2017-04-28 一种自融合石墨烯纤维及其制备方法
CN201710294377.6 2017-04-28

Publications (1)

Publication Number Publication Date
WO2018196475A1 true WO2018196475A1 (zh) 2018-11-01

Family

ID=59477797

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/077303 Ceased WO2018196475A1 (zh) 2017-04-28 2018-02-27 一种自融合石墨烯纤维及其制备方法

Country Status (3)

Country Link
US (1) US11486086B2 (zh)
CN (1) CN106948165B (zh)
WO (1) WO2018196475A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114411285A (zh) * 2022-03-07 2022-04-29 南京工业大学 一种石墨烯/石墨烯量子点垂直纤维及其制备方法与应用

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106948165B (zh) 2017-04-28 2019-06-21 浙江大学 一种自融合石墨烯纤维及其制备方法
JP6952134B2 (ja) 2017-05-27 2021-10-20 ハンヂョウ ガオシー テクノロジー カンパニー リミテッドＨａｎｇｚｈｏｕ Ｇａｏｘｉ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｔｄ． グラフェン粘着に基づく複合材料の製造方法
CN107675488A (zh) * 2017-11-18 2018-02-09 杭州高烯科技有限公司 一种石墨烯‑碳化硅纤维复合材料及其制备方法
CN107869047A (zh) * 2017-11-18 2018-04-03 杭州高烯科技有限公司 一种石墨烯‑氮化硼纤维复合材料及其制备方法
CN107858777A (zh) * 2017-11-18 2018-03-30 杭州高烯科技有限公司 一种石墨烯‑氧化铝纤维复合材料及其制备方法
CN107687090A (zh) * 2017-08-14 2018-02-13 杭州高烯科技有限公司 一种石墨烯交联的碳纤维丝束、织物及其制备方法
CN107815789A (zh) * 2017-11-18 2018-03-20 杭州高烯科技有限公司 一种石墨烯‑石英纤维复合材料及其制备方法
CN107805886A (zh) * 2017-11-18 2018-03-16 杭州高烯科技有限公司 一种石墨烯‑玄武岩纤维复合材料及其制备方法
CN107502995B (zh) * 2017-08-08 2019-08-16 杭州高烯科技有限公司 一种褶皱的石墨烯纤维和石墨烯纤维无纺布及其制备方法
CN109267416A (zh) * 2018-09-21 2019-01-25 杭州高烯科技有限公司 一种自融合的还原石墨烯纤维纸及其制备方法
CN109295796A (zh) * 2018-09-21 2019-02-01 杭州高烯科技有限公司 一种自融合的氧化石墨烯纤维纸及其制备方法
CN112095176A (zh) * 2020-09-22 2020-12-18 杭州高烯科技有限公司 一种石墨烯纤维的制备方法
CN111979609A (zh) * 2020-09-22 2020-11-24 杭州高烯科技有限公司 一种大直径石墨烯纤维的制备方法
CN112127030A (zh) * 2020-09-22 2020-12-25 杭州高烯科技有限公司 一种加捻自融合石墨烯纤维的制备方法
CN115748234B (zh) * 2022-11-21 2024-11-26 浙江大学 一种高强石墨烯材料的制备方法
CN116556076B (zh) * 2023-04-23 2025-02-11 北京科技大学 石墨烯无纺布/聚氨酯导电复合材料、制备方法及应用
CN118996679B (zh) * 2024-09-18 2025-08-26 山西浙大新材料与化工研究院 一种均匀高刚度石墨烯纤维及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105586646A (zh) * 2015-12-27 2016-05-18 盐城增材科技有限公司 一种湿法纺丝方法
CN105671689A (zh) * 2016-01-13 2016-06-15 郑州大学 直丝石墨烯纤维及其作为电抽吸器件的应用
CN106120025A (zh) * 2016-07-02 2016-11-16 苏州大学 一种石墨烯纤维及其制备方法
CN106702535A (zh) * 2015-08-05 2017-05-24 中国科学院苏州纳米技术与纳米仿生研究所 一种石墨烯纤维及其制备方法
CN106948165A (zh) * 2017-04-28 2017-07-14 浙江大学 一种自融合石墨烯纤维及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101599820B1 (ko) * 2013-04-19 2016-03-04 가부시키가이샤 인큐베이션 얼라이언스 탄소 섬유 및 그 제조 방법
US20150329761A1 (en) * 2014-05-14 2015-11-19 Aleksandar GRUJICIC Fiber and nanomaterial composite material and method for making the same
FR3023746B1 (fr) * 2014-07-21 2016-07-29 Univ Paul Sabatier - Toulouse Iii Procede de preparation d'une structure composite stratifiee electriquement conductrice

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106702535A (zh) * 2015-08-05 2017-05-24 中国科学院苏州纳米技术与纳米仿生研究所 一种石墨烯纤维及其制备方法
CN105586646A (zh) * 2015-12-27 2016-05-18 盐城增材科技有限公司 一种湿法纺丝方法
CN105671689A (zh) * 2016-01-13 2016-06-15 郑州大学 直丝石墨烯纤维及其作为电抽吸器件的应用
CN106120025A (zh) * 2016-07-02 2016-11-16 苏州大学 一种石墨烯纤维及其制备方法
CN106948165A (zh) * 2017-04-28 2017-07-14 浙江大学 一种自融合石墨烯纤维及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CAO , J. ET AL.: "Programmable Writing of Graphene Oxide/Reduced Graphene Oxide Fibers for Sensible Networks with in Situ Welded Junctions", ACS NANO, vol. 8, no. 5, 7 April 2014 (2014-04-07), pages 4325 - 4333, XP055528031 *
XIANG,XI: "Structure Regulation and Application of Carbom Nanomaterials, Science-Engineering", CHINA MASTER'S FULL-TEXT DATABASE, no. 2, 15 February 2017 (2017-02-15), ISSN: 1674-0246 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114411285A (zh) * 2022-03-07 2022-04-29 南京工业大学 一种石墨烯/石墨烯量子点垂直纤维及其制备方法与应用

Also Published As

Publication number Publication date
US20200040519A1 (en) 2020-02-06
CN106948165B (zh) 2019-06-21
US11486086B2 (en) 2022-11-01
CN106948165A (zh) 2017-07-14

Similar Documents

Publication Publication Date Title
WO2018196475A1 (zh) 一种自融合石墨烯纤维及其制备方法
CN103603088B (zh) 一种剑鞘型结构的导电纤维及其制备方法
CN104099687B (zh) 一种石墨烯纤维及其制备方法
CN102691136A (zh) 一种同轴静电纺丝制备聚丙烯腈基多孔中空碳纤维的方法
JP2018524482A (ja) グラフェン繊維不織布及びその製造方法
CN105964522B (zh) 一种石墨烯导热膜的制备方法
CN117362743B (zh) 一种耐热冲击的芳纶气凝胶的制备方法和芳纶气凝胶
CN103147355B (zh) 一种生物质纳米纤维导电纸的制备方法
WO2015014124A1 (zh) 一种电石墨烯复合纤维的制备方法
CN115341405A (zh) 多孔基材、多孔电极、碳纤维纸、碳纤维纸的制造方法、多孔基材的制造方法
WO2018219008A1 (zh) 基于石墨烯粘结的复合材料的制备方法
CN106436439A (zh) 一种碳纤维纸的制备方法
CN102534868A (zh) 一种高强度宏观石墨烯导电纤维的制备方法
CN109608794B (zh) Ptfe微孔膜及其制备方法以及复合质子交换膜
CN102586916A (zh) 一种超支化聚合物接枝石墨烯的复合纤维制备方法
CN114150354B (zh) 一种高强度高导电碳纳米管复合薄膜及其制备方法
CN102961976A (zh) 聚四氟乙烯中空纤维多孔膜及其制备方法
CN108939945A (zh) 一种稳定的陶瓷基复合碳膜及其制备方法
CN109250702B (zh) 多孔碳材料及其制备方法和应用
CN106633391A (zh) 一种聚丙烯/玻璃纤维界面横晶结构的诱导方法
CN105858642A (zh) 一种多孔石墨烯材料、其制备方法和应用
CN107687090A (zh) 一种石墨烯交联的碳纤维丝束、织物及其制备方法
CN114409424A (zh) 一种水相常压干燥制备低密度、高强度、大尺寸碳气凝胶复合材料的方法
CN111003703B (zh) 一种结构功能一体化石墨烯材料及其制备方法
CN107675488A (zh) 一种石墨烯‑碳化硅纤维复合材料及其制备方法

Legal Events

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

Ref document number: 18791380

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18791380

Country of ref document: EP

Kind code of ref document: A1