WO2018219008A1 - 基于石墨烯粘结的复合材料的制备方法 - Google Patents

基于石墨烯粘结的复合材料的制备方法 Download PDF

Info

Publication number
WO2018219008A1
WO2018219008A1 PCT/CN2018/078765 CN2018078765W WO2018219008A1 WO 2018219008 A1 WO2018219008 A1 WO 2018219008A1 CN 2018078765 W CN2018078765 W CN 2018078765W WO 2018219008 A1 WO2018219008 A1 WO 2018219008A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
graphene oxide
fiber
coated
fibers
Prior art date
Application number
PCT/CN2018/078765
Other languages
English (en)
French (fr)
Inventor
高超
李拯
张春晓
畅丹
陈琛
高微微
郭燕
韩燚
Original Assignee
杭州高烯科技有限公司
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 claimed from CN201710391093.9A external-priority patent/CN107163861A/zh
Priority claimed from CN201710391092.4A external-priority patent/CN107140619B/zh
Priority claimed from CN201710391843.2A external-priority patent/CN107022312A/zh
Priority claimed from CN201710691600.0A external-priority patent/CN107687090A/zh
Priority claimed from CN201711150773.8A external-priority patent/CN107675488A/zh
Priority claimed from CN201711150763.4A external-priority patent/CN107858777A/zh
Priority claimed from CN201711150778.0A external-priority patent/CN107815789A/zh
Priority claimed from CN201711150786.5A external-priority patent/CN107761249A/zh
Priority claimed from CN201711150776.1A external-priority patent/CN107869047A/zh
Priority claimed from CN201711150791.6A external-priority patent/CN107805886A/zh
Priority to JP2019565907A priority Critical patent/JP6952134B2/ja
Priority to US16/617,531 priority patent/US11542411B2/en
Application filed by 杭州高烯科技有限公司 filed Critical 杭州高烯科技有限公司
Publication of WO2018219008A1 publication Critical patent/WO2018219008A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • 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
    • C01B32/184—Preparation
    • 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
    • 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
    • C01B32/198—Graphene oxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J1/00—Adhesives based on inorganic constituents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • D06M11/73—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 carbon or compounds thereof
    • D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/04—Specific amount of layers or specific thickness
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/24—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/208—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive layer being constituted by at least two or more adjacent or superposed adhesive layers, e.g. multilayer adhesive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials

Definitions

  • the present invention relates to a method of preparing a graphene bonded composite.
  • the present invention utilizes the swelling and fusion of graphene oxide in a solvent to achieve cross-linking bonding of the graphene material itself and materials such as polymers, metals, paper, glass, carbon materials and ceramics. It not only overcomes the shortcomings of traditional adhesive residual formaldehyde, but also has short drying time, high bonding strength and corrosion resistance. It is widely used in aviation, aerospace, automotive, machinery, construction, chemical, light industry, electronics, electrical appliances and daily life. Applications.
  • Solution 1 In order to realize cross-linking of boron nitride fibers, the present invention applies graphene oxide to the surface of boron nitride fibers, and the oxides of graphene oxide and boron nitride fibers form hydrogen bonds and van der Waals forces to achieve uniformity. Firmly coated. Then, the surface oxide layer of boron nitride fiber is swollen in a solvent, and the sheet layer obtains a large degree of freedom. The capillary force of the graphene oxide sheet layer due to solvent volatilization during drying and the ⁇ - ⁇ between the sheets are dried.
  • a graphene-boron nitride fiber composite material including a non-twisted yarn, a non-woven fabric or a chopped strand mat.
  • a method for preparing a graphene-boron nitride fiber composite material comprising the steps of:
  • the boron nitride fiber is surface-coated with a graphene oxide dispersion, and dried to obtain a boron nitride fiber coated with graphene oxide.
  • the graphene-coated boron nitride fiber is placed in a solvent to be surface-swelled, and then the fibers are combined and dried to form the crepe-free yarn, or the fibers are lapped to each other to form the nonwoven. Cloth or chopped strand mat, drying temperature below 100 °C.
  • the concentration of the graphene oxide dispersion in the step (1) is 7 mg/g
  • the dispersing agent is water, N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, and B.
  • the boron nitride fiber is coated a plurality of times using a graphene oxide dispersion, and dried after each coating, and the thickness of the graphene oxide layer after the final drying is 3 ⁇ m.
  • the solvent in the step (2) is water, methanol, ethanol, isopropanol, ethylene glycol, glycerol, diethylene glycol or the like, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, Organic acids such as oxalic acid, malonic acid, succinic acid, acrylic acid, acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, N - aqueous solution of methyl pyrrolidone, pyridine, dioxane, sodium chloride, aqueous solution of calcium chloride, aqueous solution of sodium nitrate, aqueous solution of calcium nitrate, aqueous solution of sodium phosphate, aqueous solution of potassium chloride, aqueous solution of ammonium chloride An aqueous solution of potassium hydroxide, an
  • the reduction method is a reduction using a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 600 °C.
  • a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 600 °C.
  • the prepared graphene-boron nitride fiber composite material graphene is coated on the surface of the boron nitride fiber, and the surface of the boron nitride fiber is connected to the graphene sheet by van der Waals force and hydrogen bonding.
  • the boron nitride fibers are crosslinked by graphene coated on the surface to form a non-twisted yarn, a nonwoven fabric or a chopped strand mat.
  • the cross-linking method can maintain the excellent mechanical properties of the boron nitride fiber, and can improve the conductivity and thermal conductivity of the fiber, thereby further expanding the application of the boron nitride fiber material.
  • Solution 2 In order to realize the cross-linking of the quartz fiber, the present invention applies graphene oxide to the surface of the quartz fiber, and the graphene oxide forms a hydrogen bond and a van der Waals force with the hydroxyl group of the quartz fiber to achieve uniform and firm coating. Then, the surface layer of quartz fiber is swollen in a solvent, and the sheet layer obtains a large degree of freedom. The capillary force of the graphene oxide sheet due to solvent volatilization during drying and the ⁇ - ⁇ force between the sheets And spontaneously stacked tightly, so the quartz fibers cross-link each other to finally obtain a graphene-quartz fiber composite material, and the preparation method comprises the following steps:
  • the quartz fiber was immersed in toluene, heated to 300 ° C for 10 min, and dried.
  • the quartz fiber is surface-coated with a graphene oxide dispersion, and dried to obtain a quartz fiber coated with graphene oxide.
  • the graphene-coated quartz fiber is placed in a solvent to be surface-swelled, and then the fibers are combined and dried to form the crepe-free yarn, or the fibers are lapped to each other to form the nonwoven fabric or Chopped mat, drying temperature below 100 °C.
  • the concentration of the graphene oxide dispersion in the step (2) is 7 mg/g
  • the dispersing agent is water, N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, and B.
  • the quartz fiber is coated a plurality of times using a graphene oxide dispersion, and dried after each coating, and the thickness of the graphene oxide layer after the final drying is 3 ⁇ m.
  • the solvent in the step (3) is water, methanol, ethanol, isopropanol, ethylene glycol, glycerol, diethylene glycol or the like, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, Organic acids such as oxalic acid, malonic acid, succinic acid, acrylic acid, acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, N - aqueous solution of methyl pyrrolidone, pyridine, dioxane, sodium chloride, aqueous solution of calcium chloride, aqueous solution of sodium nitrate, aqueous solution of calcium nitrate, aqueous solution of sodium phosphate, aqueous solution of potassium chloride, aqueous solution of ammonium chloride An aqueous solution of potassium hydroxide, an
  • the reduction method is a reduction using a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 600 °C.
  • a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 600 °C.
  • graphene is coated on the surface of the quartz fiber, and the surface of the quartz fiber is connected to the graphene sheet by van der Waals force and hydrogen bonding.
  • the quartz fibers are crosslinked by graphene coated on the surface to form a non-twisted yarn, a non-woven fabric or a chopped strand mat.
  • the cross-linking method can maintain the excellent mechanical properties of the quartz fiber, and can improve the thermal conductivity, electrical conductivity, and alkali resistance of the quartz fiber, thereby further expanding the application of the quartz fiber material.
  • the silicon carbide fiber is surface-coated with a graphene oxide dispersion, and after drying, a silicon carbide fiber having a surface coated with graphene oxide is obtained.
  • the graphene-coated silicon carbide fiber is placed in a solvent to be surface-swelled, and then the fibers are combined and dried to form the crepe-free yarn, or the fibers are lapped to each other to form the nonwoven fabric. Or chopped strand mat, drying temperature below 100 °C.
  • the silicon carbide fiber contains one or more of titanium, iron, nickel, boron, aluminum, and zirconium, and the cross-sectional shape of the fiber is circular, trilobal, and tri-folded.
  • the cross-sectional shape of the fiber is circular, trilobal, and tri-folded.
  • the concentration of the graphene oxide dispersion in the step (1) is 7 mg/g
  • the dispersing agent is water, N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, and B.
  • the silicon carbide fiber is coated a plurality of times using a graphene oxide dispersion, and dried after each coating, and the thickness of the graphene oxide layer after the final drying is 3 ⁇ m.
  • the solvent in the step (2) is water, methanol, ethanol, isopropanol, ethylene glycol, glycerol, diethylene glycol or the like, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, Organic acids such as oxalic acid, malonic acid, succinic acid, acrylic acid, acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, N - aqueous solution of methyl pyrrolidone, pyridine, dioxane, sodium chloride, aqueous solution of calcium chloride, aqueous solution of sodium nitrate, aqueous solution of calcium nitrate, aqueous solution of sodium phosphate, aqueous solution of potassium chloride, aqueous solution of ammonium chloride An aqueous solution of potassium hydroxide, an
  • the reduction method is a reduction using a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 600 °C.
  • a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 600 °C.
  • graphene is coated on the surface of the silicon carbide fiber, and the surface of the silicon carbide fiber is connected with the graphene sheet by van der Waals force.
  • the silicon carbide fibers are crosslinked by graphene coated on the surface to form a non-twisted yarn, a non-woven fabric or a chopped strand mat.
  • the cross-linking method can maintain the excellent mechanical properties of the SiC fiber, and can improve the conductivity and thermal conductivity of the fiber, thereby further expanding the application of the SiC fiber material.
  • the conductivity of graphene itself can be adjusted, it can adjust the overall dielectric properties of the system after compounding with silicon carbide fiber, which can effectively improve the absorption and reflection ability of electromagnetic waves, and can be widely used in absorbing materials and electromagnetic shielding materials. .
  • the basalt fiber is placed in toluene and heated to 250 ° C, ultrasonically cleaned for 10 to 30 minutes, the surface sizing agent and the oil agent are removed, and dried.
  • the basalt fiber is surface-coated with a graphene oxide dispersion, and dried to obtain a basalt fiber coated with graphene oxide.
  • the graphene-coated basalt fiber is placed in a solvent to be surface-swelled, and then the fibers are combined and dried to form the crepe-free yarn, or the fibers are lapped to each other to form the nonwoven fabric or Chopped mat, drying temperature below 100 degrees Celsius.
  • the concentration of the graphene oxide dispersion in the step (2) is 7 mg/g
  • the dispersing agent is water, N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, and B.
  • the basalt fiber is coated a plurality of times using a graphene oxide dispersion, and dried after each coating, and the thickness of the graphene oxide layer after the final drying is 3 ⁇ m.
  • the solvent in the step (3) is water, methanol, ethanol, isopropanol, ethylene glycol, glycerol, diethylene glycol or the like, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, Organic acids such as oxalic acid, malonic acid, succinic acid, acrylic acid, acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, N - aqueous solution of methyl pyrrolidone, pyridine, dioxane, sodium chloride, aqueous solution of calcium chloride, aqueous solution of sodium nitrate, aqueous solution of calcium nitrate, aqueous solution of sodium phosphate, aqueous solution of potassium chloride, aqueous solution of ammonium chloride An aqueous solution of potassium hydroxide, an
  • the reduction method is a reduction using a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 600 °C.
  • a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 600 °C.
  • the cross-linking method can maintain the excellent mechanical properties of the basalt fiber and improve its electrical conductivity, corrosion resistance and thermal conductivity, thereby further expanding the application of the basalt fiber material.
  • graphene is coated on the surface of basalt fiber, and the surface of the basalt fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the basalt fibers are crosslinked by graphene coated on the surface to form a non-twisted yarn, a non-woven fabric or a chopped strand mat.
  • the cross-linking method can maintain the excellent mechanical properties of the basalt fiber and improve its electrical conductivity, corrosion resistance and thermal conductivity, thereby further expanding the application of the basalt fiber material.
  • the alumina fiber is surface-coated with a graphene oxide dispersion, and dried to obtain an alumina fiber having a surface coated with graphene oxide.
  • the graphene-coated alumina fiber is placed in a solvent to be surface-swelled, and then the fibers are combined and dried to form the crepe-free yarn, or the fibers are lapped to each other to form the nonwoven fabric. Or chopped strand mat, drying temperature below 100 °C.
  • the concentration of the graphene oxide dispersion in the step (1) is 7 mg/g
  • the dispersing agent is water, N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, and B.
  • the alumina fiber is coated a plurality of times using a graphene oxide dispersion, and dried after each coating, and the thickness of the graphene oxide layer after the final drying is 3 ⁇ m.
  • the solvent in the step (2) is water, methanol, ethanol, isopropanol, ethylene glycol, glycerol, diethylene glycol or the like, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, Organic acids such as oxalic acid, malonic acid, succinic acid, acrylic acid, acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, N - aqueous solution of methyl pyrrolidone, pyridine, dioxane, sodium chloride, aqueous solution of calcium chloride, aqueous solution of sodium nitrate, aqueous solution of calcium nitrate, aqueous solution of sodium phosphate, aqueous solution of potassium chloride, aqueous solution of ammonium chloride An aqueous solution of potassium hydroxide, an
  • the reduction method is a reduction using a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 600 °C.
  • a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 600 °C.
  • graphene is coated on the surface of the alumina fiber, and the surface of the alumina fiber is connected to the graphene sheet by van der Waals force and hydrogen bonding.
  • the alumina fibers are crosslinked by graphene coated on the surface to form a crepe-free yarn, a nonwoven fabric or a chopped strand mat.
  • Pure graphene has a uniform surface distribution as an alumina fiber, and has high interfacial adhesion strength, and does not fall off when immersed in a solvent.
  • the cross-linking method can maintain the excellent mechanical properties of the alumina fiber, and can improve the conductivity and thermal conductivity of the fiber, thereby further expanding the application of the alumina fiber material.
  • the present invention applies graphene oxide to the surface of the glass fiber, and the graphene oxide forms a hydrogen bond and a van der Waals force with the hydroxyl group of the glass fiber to achieve uniform and firm coating. Then, the glass fiber surface layer graphene oxide is swollen in a solvent, and the sheet layer obtains a large degree of freedom. The capillary force of the graphene oxide sheet layer due to solvent volatilization during drying and the ⁇ - ⁇ force between the sheets are dried. The particles are spontaneously stacked, so that the glass fibers are cross-linked to each other to finally obtain a graphene-glass fiber composite material, and the preparation method comprises the following steps:
  • the glass fiber is ultrasonically cleaned in acetone to remove surface oil stains and dried.
  • the glass fiber is surface-coated with a graphene oxide dispersion, and dried to obtain a glass fiber coated with graphene oxide.
  • the graphene-coated glass fiber is placed in a solvent to be surface-swelled, and then the fibers are combined and dried to form the crepe-free yarn, or the fibers are lapped to each other to form the nonwoven fabric or Chopped mat, drying temperature below 100 degrees Celsius.
  • the concentration of the graphene oxide dispersion in the step (2) is 7 mg/g
  • the dispersing agent is water, N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, and B.
  • the glass fiber is coated a plurality of times using a graphene oxide dispersion, and dried after each coating, and the thickness of the graphene oxide layer after the final drying is 3 ⁇ m.
  • the solvent in the step (3) is water, methanol, ethanol, isopropanol, ethylene glycol, glycerol, diethylene glycol or the like, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, Organic acids such as oxalic acid, malonic acid, succinic acid, acrylic acid, acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, N - aqueous solution of methyl pyrrolidone, pyridine, dioxane, sodium chloride, aqueous solution of calcium chloride, aqueous solution of sodium nitrate, aqueous solution of calcium nitrate, aqueous solution of sodium phosphate, aqueous solution of potassium chloride, aqueous solution of ammonium chloride An aqueous solution of potassium hydroxide, an
  • the reduction method is a reduction using a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 600 °C.
  • a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 600 °C.
  • graphene is coated on the surface of the glass fiber, and the surface of the glass fiber is connected to the graphene sheet by van der Waals force and hydrogen bonding.
  • the glass fibers are crosslinked by graphene coated on the surface to form a non-twisted yarn, a non-woven fabric or a chopped strand mat.
  • Pure graphene has a uniform surface distribution as a glass fiber, high interfacial adhesion strength, and does not fall off when immersed in a solvent.
  • the cross-linking method can maintain the excellent mechanical properties of the glass fiber, and can improve the thermal conductivity, electrical conductivity, corrosion resistance, etc. of the glass fiber, thereby further expanding the application of the glass fiber material.
  • the sizing agent on the surface of the carbon fiber is removed, and the surface thereof is oxidatively modified.
  • the oxidized modified carbon fiber is surface-coated with a graphene oxide dispersion, and dried to obtain a carbon fiber having a surface coated with graphene oxide.
  • a plurality of graphene-coated carbon fibers are placed in a solvent to be surface-swelled, and then the swollen fibers are bundled into a tow, followed by drying at a temperature lower than 100 ° C to volatilize the solvent.
  • the surface of the carbon fiber has a graphene sheet distributed along the axial direction of the fiber, and the surface of the carbon fiber is connected to the graphene sheet by van der Waals force and hydrogen bonding. At the fabric joint, cross-linking is achieved between the carbon fibers through the graphene sheets.
  • a method for preparing a graphene crosslinked carbon fiber fabric comprises the following steps:
  • the sizing agent on the surface of the carbon fiber is removed, and the surface thereof is oxidatively modified.
  • the oxidized modified carbon fiber is surface-coated with a graphene oxide dispersion, and dried to obtain a carbon fiber having a surface coated with graphene oxide.
  • a plurality of graphene-coated carbon fibers are woven into a fabric, placed in a solvent for surface swelling, fusion, and then dried at a temperature lower than 100 ° C to cause the solvent to volatilize.
  • the method of removing the sizing agent on the surface of the carbon fiber is as follows: the carbon fiber is placed in acetone and refluxed at 57 to 100 ° C for 6 hours or more, and dried.
  • the method for oxidatively modifying the surface of the carbon fiber in the step (1) is: immersing the carbon fiber in a hydrogen peroxide solution (mass fraction of 30%) at 100 to 157 ° C for 0.5 to 3 hours, and then at 83 to 120 ° C.
  • the concentrated nitric acid (70% by mass) is soaked for 6 to 24 hours, and finally washed and dried with water.
  • the surface sizing agent is removed by placing the carbon fibers in acetone at 80 ° C for 72 h. It was immersed in hydrogen peroxide at 110 ° C for 2 h, concentrated in nitric acid at 115 ° C for 12 h, and finally washed with water.
  • the dispersing agent of the graphene oxide dispersion in the step (2) is water, N,N-dimethylformamide, N,N-dimethylacetamide, ethanol, ethylene glycol, N-A Pyrrolidone, tetrahydrofuran, dimethyl sulfoxide, diethylene glycol, pyridine, dioxane, methyl ethyl ketone, isopropanol and the like.
  • the oxidized modified carbon fiber is coated a plurality of times using a graphene oxide dispersion, and dried after each coating, and the drying temperature is about 25 to 50 °C.
  • the solvent in the step (3) is water, methanol, ethanol, isopropanol, ethylene glycol, glycerol, diethylene glycol or the like, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, Organic acids such as oxalic acid, malonic acid, succinic acid, acrylic acid, acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, N - aqueous solution of methyl pyrrolidone, pyridine, dioxane, sodium chloride, aqueous solution of calcium chloride, aqueous solution of sodium nitrate, aqueous solution of calcium nitrate, aqueous solution of sodium phosphate, aqueous solution of potassium chloride, aqueous solution of ammonium chloride An aqueous solution of potassium hydroxide, an
  • the reduction method is a reduction using a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 3000 °C.
  • a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or a thermal reduction at 100 to 3000 °C.
  • the concentration of the graphene oxide dispersion is 7 mg/ml, and the thickness of the graphene oxide on the surface of the carbon fiber after drying is 3 ⁇ m.
  • the carbon fibers in the prepared carbon fiber tow are crosslinked by a graphene sheet distributed along the axial direction of the fiber.
  • the surface of the carbon fiber is connected to the graphene sheet by van der Waals force and hydrogen bonding; in the obtained carbon fiber fabric, the surface of the carbon fiber has a graphene sheet distributed along the axial direction of the fiber, and the surface of the carbon fiber and the graphene sheet pass van der Waals force and Hydrogen bond connection.
  • cross-linking is achieved between the carbon fibers through the graphene sheets.
  • the cross-linking method can maintain the excellent mechanical properties, electrical conductivity, corrosion resistance, etc. of the carbon fiber, and can improve the thermal conductivity of the carbon fiber, thereby further expanding the application of the carbon fiber material.
  • a graphene oxide having an average size of more than 50 ⁇ m is formulated into an aqueous solution of graphene oxide having a concentration of 1 to 20 mg/mL, and the solution is formed into a film and then naturally dried to obtain a graphene oxide film.
  • the dried graphene oxide composite film is placed in a hot pressing chamber of a hot press, heated to a temperature of 0.1 to 5 ° C / min to 200 ° C, and then hot pressed, repeating the following hot pressing process 8-10 Time: maintain the pressure 20MPa, maintain 1h; gradually release the pressure to 0MPa, vacuum the hot pressure chamber for 5min to a vacuum of -100 ⁇ 10KPa; then increase the temperature by 300 ° C at a rate of 0.1 ⁇ 5 ° C / min, 0.5 h, Then hot pressing, repeat the following hot pressing process 4-6 times: maintain the pressure 60MPa, maintain 1h, gradually release the pressure to 0MPa, vacuum the hot pressure chamber for 5min to a vacuum of -100 ⁇ 10KPa; after the hot pressing process is natural Cool down.
  • the graphene oxide film after the hot pressing in step 4 is heated to a temperature of 1800 to 3000 ° C at an inert gas atmosphere at a rate of 1 to 20 ° C / min for further hot pressing, and the holding pressure is 0.5 to 8 h; the pressure is 60 MPa. After cooling, a thick film of graphene with high thermal conductivity is obtained.
  • the thickness of the graphene oxide film prepared in the step 1 is 1 to 30 ⁇ m.
  • the film forming method in the step 1 is selected from the group consisting of a suction filtration method, a doctor blade method, a spin coating method, a spray coating method, and a dip coating method.
  • the graphene oxide film prepared in the step 1 has a carbon to oxygen ratio of 1.8 to 2.1.
  • the liquid used in the spraying of the step 2 is: deionized water, an aqueous solution of graphene oxide having a concentration of 1 to 10 mg/mL, or other solution containing deionized water.
  • the thickness of the prepared graphene thick film is greater than 50 ⁇ m, the porosity is 5-40%; the graphene sheet layer wrinkle density is controlled at 50-500 mm/mm 2 , and the graphene sheet has few defects, and its ID/TG ⁇ 0.02,
  • the thermal conductivity is 1000-2000 W/mK.
  • the graphene thick film has no delamination, and the interlayer spacing of any two adjacent graphene sheets is less than 20 nm.
  • the beneficial effects are as follows: the invention swells the surface of the graphene oxide film to bond the plurality of graphene oxide films together, and after drying, the graphene oxide film can achieve self-bonding through the force at the bonding interface.
  • the preparation of the thick graphene oxide film is achieved by further low-temperature hot pressing to make the adhesion between the graphene oxide films more compact.
  • the low-temperature heating pre-reduction and high-temperature hot-pressing treatment repair the structural defects of the graphene film, control the fold density of the graphene sheet, improve the orientation of the graphene sheet, and make the graphene film form the highest three-dimensional graphite.
  • the structure ensures the smooth conduction of the heat conduction path of the graphene, and a thick film of graphene with high thermal conductivity can be obtained.
  • the high thermal conductivity graphene thick film has flexibility, can be bent, and has high thermal conductivity.
  • a graphene oxide binder comprising a solvent and graphene oxide dispersed in a solvent, the graphene oxide having a concentration of 4 mg/ml or more, a C/O ratio of 3:1 or less, graphite oxide
  • the monolayer rate is greater than 80%.
  • the graphene oxide sheet has a size of 1 um to 100 um, the amount of graphene oxide sheets having a size of less than 5 um is not more than 10%, and the amount of graphene oxide sheets having a size larger than 30 um is not less than 60%.
  • the solvent is water, DMF.
  • a bonding method based on graphene material is: firstly, the surface of the bonding material is subjected to hydrophilic treatment, and then the graphene oxide adhesive is uniformly coated between the plurality of materials to be bonded, and is dried. Thereafter, bonding is performed between the materials to be bonded by graphene oxide.
  • the material to be bonded includes a polymer, a metal, a paper and a material such as glass, a carbon material, a ceramic, and the like, and a bond between the above different materials.
  • the invention firstly proposes a novel environmentally friendly graphene oxide adhesive, which not only overcomes the shortcomings of the conventional adhesive residual formaldehyde, but also has good adhesion, in aviation, aerospace, automobile, machinery, construction, chemical industry, light industry, electronics. , electrical appliances and daily life and other fields have been widely used. Compared with the prior art, it has the following beneficial effects:
  • the bonding interface is stable and can withstand high temperature, acid and alkali corrosion.
  • Scheme 10 A method for achieving material bonding by using graphene, which is: firstly, a graphene oxide solution is uniformly coated between a plurality of materials to be bonded, and after being dried, it is reduced, and then it is to be adhered. The bonding between the bonding materials is achieved by graphene.
  • the graphene oxide solution the graphene oxide sheet has a size of 1 um to 100 um, a graphene oxide sheet having a size of less than 5 um is less than or equal to 10%, and a graphene oxide sheet having a size larger than 30 um is not less than 65%;
  • the monolayer rate is greater than 80%; the concentration of graphene oxide is greater than or equal to 4 mg/mL.
  • the reduced graphene has a C/O greater than 4:1.
  • the solvent is water, ethanol, N,N-dimethylformamide (DMF).
  • the material to be bonded includes a polymer, a metal, a paper and a glass, a carbon material, a ceramic, and the like, and a bonding between the different materials.
  • the reduction method is chemical reduction using hydriodic acid or hydrazine hydrate vapor at 80 to 100 °C.
  • the reduction method is a thermal reduction by slowly raising the temperature to a temperature of 100 to 500 ° C at a heating rate of 1 ° C / min under a pressurized or vacuum state.
  • the present invention is the first to propose a method for achieving 100% graphene bonding at the material interface.
  • the strategy first establishes effective bonding at the material interface through high-polarity graphene oxide, and then applies controlled reduction to obtain a graphene bonding layer, and effectively avoids the occurrence of debonding and foaming during the reduction process.
  • the present invention has the following beneficial effects:
  • the method of use is simple, and the bonding portion has characteristics such as electrical conduction and heat conduction.
  • the bonding interface is stable and can withstand high temperature, moisture, acid and alkali corrosion.
  • Figure 1 is a schematic illustration of a boron nitride fiber nonwoven fabric crosslinked by graphene of the present invention.
  • FIG. 2 is a schematic view of a boron nitride fiber non-twisted fiber crosslinked by graphene of the present invention.
  • 3a, b are scanning electron micrographs of the carbon fiber before and after coating, and c is a cross-sectional view of the two crosslinked carbon fibers.
  • Figure 4 is a graph showing the bonding properties of different concentrations of binder (graphene oxide).
  • Figure 5 is a graph showing the bonding properties of different concentrations of binder (reduced graphene oxide).
  • Figure 6 is a schematic view of a continuous coating apparatus
  • Figure 7 is a SEM cross-sectional view of a thick graphene film bonded using deionized water
  • Fig. 8 is a SEM cross-sectional view showing a thick graphene film bonded using an aqueous graphene oxide solution.
  • the percentages referred to in the following examples are all percentages.
  • “single layer of graphene oxide accounts for 81.5% of the total amount of graphene oxide”, meaning that among 1000 sheets of graphene oxide, single The number of layer graphene oxide is 815 sheets; "the amount of graphene oxide sheets having a size of less than 5 um is 7 ⁇ 3%", which means that the number of graphene oxide sheets having a size of less than 5 ⁇ m in 100 sheets of graphene oxide is 7 ⁇ 3 tablets.
  • C/O is a technical term commonly used in the art, and indicates the atomic ratio of C and O.
  • the amount of the graphene oxide sheet having a size of less than 5 ⁇ m is 7 ⁇ 3%, the amount of the graphene oxide sheet having a size larger than 30 ⁇ m is 65 ⁇ 4%, and the remaining portion is between 5 and 30 ⁇ m;
  • the overall C/O ratio is 2.5:1, and the single-layer graphene oxide accounts for 81.5% of the total amount of graphene oxide.
  • the aqueous graphene oxide solution was placed at a concentration of 2-20 mg/ml, and the two slides were bonded.
  • the bonding method was as follows: first, the slide was subjected to hydrophilic treatment, and then the graphene oxide was bonded. The agent was evenly coated between two slides, and after drying, the two slides were bonded by graphene oxide.
  • the amount of graphene oxide sheets having a size of less than 5 ⁇ m is 5 ⁇ 3%, the amount of graphene oxide sheets having a size larger than 30 ⁇ m is 60 ⁇ 5%, and the remaining portions are between 5-30 ⁇ m;
  • the layer graphene oxide accounts for 95.8% of the total amount of graphene oxide.
  • the aqueous graphene oxide solution was placed at a concentration of 8 mg/ml and bonded to two glass slides by first hydrophilically treating the slide, and then uniformly coating the graphene oxide adhesive. Covered between two slides, after drying, the two slides were bonded by graphene oxide.
  • the size distribution of the graphene oxide used is shown in Table 1; the overall C/O ratio is 2.5:1, and the single-layer graphene oxide content is 91.6%.
  • the aqueous graphene oxide solution was placed at a concentration of 4 mg/ml and bonded to two glass slides by first hydrophilically treating the slide, and then uniformly coating the graphene oxide adhesive. Covered between two slides, after drying, the two slides were bonded by graphene oxide.
  • the bonding effects under different size distributions are shown in Table 1. As can be seen from the table, the amount of graphene oxide sheets having a size of less than 5 ⁇ m should be not more than 10%, and the amount of graphene oxide sheets having a size larger than 30 ⁇ m should be not less than 60%.
  • the graphene bonding solution is uniformly coated on the surface of the polyethylene terephthalate (PET) material, and the bonding is achieved after drying.
  • the tested bond strength was 0.11 MPa.
  • a graphene oxide having a C/O ratio equal to 1.7:1 and a single layer ratio of 88.9% is controlled to be 50-80 um; a graphene oxide dispersion having a concentration of 18 mg/ml is disposed, and the dispersed phase is water. This was used as a graphene bonding solution.
  • the amount of the graphene oxide sheet having a size of less than 5 ⁇ m is 8 ⁇ 1%, the amount of the graphene oxide sheet having a size larger than 30 ⁇ m is 70 ⁇ 3%, and the remaining portion is between 5 and 30 ⁇ m;
  • the overall C/O ratio is 2:1, and the single-layer graphene oxide accounts for 98.8% of the total amount of graphene oxide.
  • the aqueous graphene oxide solution was placed at a concentration of 2-20 mg/ml, and the two slides were bonded.
  • the bonding method was as follows: first, the slide was subjected to hydrophilic treatment, and then the graphene oxide was bonded. The agent was evenly coated between two slides. After drying, it was chemically reduced at 95 ° C with hydrazine hydrate vapor. The reduced graphene C/O was about 6:1, and two slides passed. Graphene achieves bonding.
  • the size distribution of the graphene oxide used is shown in Table 2; the overall C/O ratio is 2:1, and the single-layer graphene oxide content is 95.8%.
  • the aqueous graphene oxide solution was placed at a concentration of 4 mg/ml and bonded to two glass slides by first hydrophilically treating the slide, and then uniformly coating the graphene oxide adhesive. Covered between two slides, after being dried, chemically reduced with hydriodic acid vapor at 90 ° C. The reduced graphene C/O is about 5:1, and two slides pass through graphene. Achieve bonding.
  • the bonding effect under different size distributions is shown in Table 2. As can be seen from the table, the amount of graphene oxide sheets having a size of less than 5 ⁇ m should be less than or equal to 10%, and the amount of graphene oxide sheets having a size larger than 30 ⁇ m should be not less than 65%.
  • the size of graphene oxide used is 30-80 um, the C/O range is 2:1 to 3:1, and the single-layer graphene oxide accounts for 84.1% of the total amount of graphene oxide.
  • the aqueous graphene oxide solution was placed at a concentration of 8 mg/ml and bonded to two sheets of ITO by first hydrophilically treating the ITO, and then uniformly coating the graphene oxide adhesive on the two sheets.
  • the graphene oxide having a single layer ratio of 81.4% is taken, the amount of graphene oxide sheets having a size of less than 5 ⁇ m is 6%, the amount of graphene oxide sheets having a size larger than 30 ⁇ m is 87%, and the remaining portion is 5-30 ⁇ m.
  • a graphene oxide dispersion having a concentration of 4 mg/ml was disposed, and the dispersed phase was water, which was used as a graphene bonding solution.
  • the graphene oxide having a single layer ratio of 96.3% is taken, the amount of graphene oxide sheets having a size smaller than 5 ⁇ m is 3%, the amount of graphene oxide sheets having a size larger than 30 ⁇ m is 91%, and the remaining portion is 5-30 ⁇ m.
  • a graphene oxide dispersion having a concentration of 16 mg/ml was disposed, and the dispersed phase was water, which was used as a graphene bonding solution.
  • the graphene oxide having a single layer ratio of 97.2% was controlled to have a size of 50 to 80 ⁇ m; a graphene oxide dispersion having a concentration of 12 mg/ml was disposed, and the dispersed phase was DMF, which was used as a graphene bonding solution.
  • the graphene oxide having a single layer ratio of 95.4% was controlled to have a size of 50 to 80 ⁇ m; a graphene oxide dispersion having a concentration of 18 mg/ml was disposed, and the dispersed phase was water, which was used as a graphene bonding solution.
  • the density, tensile strength, electrical conductivity and thermal conductivity of the obtained carbon fiber tow are smaller, and the crosslinking effect is obtained. The worse.
  • Step (1) is the same as Example 3-1.
  • the surface of the carbon fiber is repeatedly coated and dried (drying temperature is 25 ° C) by a continuous coating apparatus using an aqueous dispersion of graphene oxide at a concentration of 7 mg/ml (the size of the graphene oxide sheet is 40 to 50 ⁇ m), and the cycle is repeated. The number of times was 20, and carbon fibers having a surface coated with graphene oxide were obtained. Among them, the graphene oxide coating has a thickness of about 3.8 ⁇ m and is uniformly distributed along the axial direction of the fiber.
  • the surface of the carbon fiber is repeatedly coated and dried (the drying temperature is 40 ° C) by a continuous coating apparatus using an aqueous dispersion of graphene oxide having a concentration of 7 mg/ml (the size of the graphene oxide sheet is 40 to 50 ⁇ m). The number of times was 15 times, and carbon fibers having a surface coated with graphene oxide were obtained. Among them, the graphene oxide coating has a thickness of about 3 ⁇ m and is uniformly distributed along the axial direction of the fiber.
  • the carbon fiber coated with graphene oxide is woven into a 50 ⁇ 50 woven fabric (the weaving method is plain weave), and then taken out in the pool for 3 minutes, taken out, dried at 60 ° C, and the water volatilizes to make the carbon fiber in the woven fabric.
  • the graphene oxide sheets on the surface layer at the contact node are fused to each other to crosslink the carbon fibers to each other to obtain a graphene-crosslinked carbon fiber woven fabric.
  • the carbon fibers at the contact nodes of the woven fabric are completely crosslinked by the graphene in which the sheets are stacked on each other.
  • the tensile strength was 4.1 GPa
  • the electrical conductivity was 0.4 ⁇ 10 5 S/m
  • the thermal conductivity was 36 W/mK.
  • the surface of the carbon fiber is repeatedly coated and dried (the drying temperature is 50 ° C) by a continuous coating apparatus using an aqueous dispersion of graphene oxide at a concentration of 7 mg/ml (the size of the graphene oxide sheet is 40 to 50 ⁇ m). The number of times was 15 times, and carbon fibers having a surface coated with graphene oxide were obtained. Among them, the graphene oxide coating has a thickness of about 3 ⁇ m and is uniformly distributed along the axial direction of the fiber.
  • the carbon fiber coated with graphene oxide is cut into short fibers and dispersed in an aqueous solution, followed by suction filtration, drying at 60 ° C, and water volatilization so that the graphene oxide sheets on the surface layer of the carbon fiber contact nodes in the nonwoven fabric are mutually
  • the fusion is performed to crosslink the carbon fibers to each other to obtain a graphene-crosslinked carbon fiber nonwoven fabric.
  • the carbon fibers at the contact nodes of the nonwoven fabric are completely crosslinked by the graphene in which the sheets are stacked on each other.
  • the tensile strength was 600 MPa
  • the electrical conductivity was 0.6 ⁇ 10 5 S/m
  • the thermal conductivity was 42 W/mK.
  • Example 3-1 it was found by comparing Examples 3-1 to 3-4 that in the carbon fiber tow obtained in Examples 3-1 and 3-2, the graphene sheet layer dispersion was more uniform than in the other examples, indicating that the implementation was carried out.
  • the carbon fiber modified by the oxidation modification scheme of Example 3-1 has a better affinity with the active group on the surface of the graphene oxide.
  • the surface of the boron nitride fiber was repeatedly coated and dried using an aqueous dispersion of graphene oxide, and the number of cycles was 15 times, and boron nitride fibers having a surface coated with graphene oxide were obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated boron nitride fiber obtained in the step (3) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 °C.
  • graphene is coated on the surface of the boron nitride fiber, and the surface of the boron nitride fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the boron nitride fibers are crosslinked by graphene coated on the surface, and the composite fibers are randomly overlapped to form a non-woven fabric structure having an areal density of 90.9 g/m 2 and a breaking strength of 1.98 GPa, soaked in water at 25 ° C. After 24 h, the breaking strength retention rate was 86%, the electrical conductivity was 2.3 ⁇ 10 4 S/m, and the thermal conductivity was 29 W/mK.
  • the graphene oxide concentration and the coating thickness are the best results obtained through trial and error. It can be seen from Table 4 that when the concentration of graphene oxide is 7 mg/ml under the same number of coatings, the thickness of the graphene oxide coating on the surface of the boron nitride fiber is 3 ⁇ m, and the obtained boron nitride fiber nonwoven fabric is obtained. The breaking strength, electrical conductivity and thermal conductivity are the highest, the waterproofing ability is the best, and the crosslinking effect is the best.
  • the waterproof solution ability is reduced.
  • the surface of the boron nitride fiber is repeatedly coated and dried using a dispersion of N,N-dimethylformamide of graphene oxide, and the number of cycles is 13 times, and a boron nitride fiber coated with graphene oxide is obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated boron nitride fiber obtained in the step (1) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 °C.
  • graphene is coated on the surface of the boron nitride fiber, and the surface of the boron nitride fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the boron nitride fibers are crosslinked by graphene coated on the surface, and the composite fibers are randomly overlapped to form a non-woven fabric structure having an areal density of 91.1 g/m 2 and a breaking strength of 1.94 GPa, soaked in water at 25 ° C. 24h after the break strength retention ratio was 84%, a conductivity of 1.7 ⁇ 10 4 S / m, a thermal conductivity of 26W / mK.
  • the surface of the boron nitride fiber was repeatedly coated and dried using an ethanol dispersion of graphene oxide, and the number of cycles was 16 times, and a boron nitride fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated boron nitride fiber obtained in the step (3) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 °C.
  • graphene is coated on the surface of the boron nitride fiber, and the surface of the boron nitride fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the boron nitride fibers are crosslinked by graphene coated on the surface, and the composite fibers are randomly overlapped to form a non-woven fabric structure having an areal density of 91.7 g/m 2 and a breaking strength of 1.99 GPa, soaked in water at 25 ° C. After 24 hours, the breaking strength retention rate was 88%, the electrical conductivity was 2.7 ⁇ 10 4 S/m, and the thermal conductivity was 30 W/mK.
  • the surface of the parallel-arranged boron nitride fibers was repeatedly coated and dried using an ethylene glycol dispersion of graphene oxide, and the number of cycles was 12, and a boron nitride fiber filament having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated boron nitride fiber filament obtained in the step (1) is placed in ethylene glycol to be surface-swelled, and then the fibers are combined and dried to form the Untwisted yarn, drying temperature below 100 ° C, volatilization of ethylene glycol.
  • graphene is coated on the surface of the boron nitride fiber, and the surface of the boron nitride fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the boron nitride fibers are crosslinked by graphene coated on the surface, and the composite fibers are arranged in parallel to form a non-twisted fiber structure, and the breaking strength is 2.09 GPa, and the breaking strength retention rate is 85% after soaking in 25 ° C water for 24 hours.
  • the electrical conductivity was 2.4 ⁇ 10 4 S/m, and the thermal conductivity was 26 W/mK.
  • the surface of the parallel-arranged boron nitride fibers was repeatedly coated and dried using an aqueous dispersion of graphene oxide, and the number of cycles was 15 times, and boron nitride fibers having a surface coated with graphene oxide were obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated boron nitride fiber obtained in the step (1) is placed in ethylene glycol to be surface-swelled, and then the fibers are combined and dried to form the crepe-free yarn, and the drying temperature is lower than 100 ° C. To volatilize ethylene glycol.
  • graphene is coated on the surface of the boron nitride fiber, and the surface of the boron nitride fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the boron nitride fibers are crosslinked by graphene coated on the surface, and the composite fibers are arranged in parallel to form a non-twisted fiber structure, and the breaking strength is 2.14 GPa, and the breaking strength retention rate is 85% after being immersed in water at 25 ° C for 24 hours.
  • the electrical conductivity was 3.1 ⁇ 10 4 S/m, and the thermal conductivity was 28 W/mK.
  • quartz fiber is immersed in toluene, heated to 300 ° C for 10 min, and dried;
  • the surface of the quartz fiber obtained in the step (1) was repeatedly coated and dried using an aqueous dispersion of graphene oxide, and the number of cycles was 15 times, and a quartz fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated quartz fiber obtained in the step (2) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 °C.
  • graphene is coated on the surface of the quartz fiber, and the surface of the quartz fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the graphene oxide concentration and the coating thickness are the best results obtained through trial and error. It can be seen from Table 5 that when the concentration of graphene oxide is 7 mg/ml under the same number of coatings, the thickness of the graphene oxide coating on the surface of the quartz fiber is 3 ⁇ m, and the obtained quartz fiber nonwoven fabric has strong breaking strength and electrical conductivity. The rate and thermal conductivity are the highest, and the crosslinking effect is the best. The smaller the concentration of graphene oxide, the smaller the thickness of graphene oxide on the surface of the quartz fiber, and the smaller the breaking strength, electrical conductivity, and thermal conductivity of the obtained quartz fiber nonwoven fabric, the worse the crosslinking effect and alkali resistance.
  • quartz fiber is immersed in toluene, heated to 300 ° C for 10 min, and dried;
  • the surface of the quartz fiber obtained in the step (1) is repeatedly coated and dried using an N,N-dimethylformamide dispersion of graphene oxide, and the number of cycles is 13 times, and the surface is coated with graphene oxide. Quartz fiber.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated quartz fiber obtained in the step (2) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 °C.
  • graphene is coated on the surface of the quartz fiber, and the surface of the quartz fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the strength retention rate of the immersion 12h was 87%, the conductivity was 5.1 ⁇ 10 4 S/m, and the thermal conductivity was 25W/mK.
  • quartz fiber is immersed in toluene, heated to 300 ° C for 10 min, and dried;
  • the surface of the quartz fiber obtained in the step (1) was repeatedly coated and dried using an ethanol dispersion of graphene oxide, and the number of cycles was 16 times, and a quartz fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated quartz fiber obtained in the step (2) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 °C.
  • graphene is coated on the surface of the quartz fiber, and the surface of the quartz fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the strength retention rate in the 12h immersion was 82%, the conductivity was 3.9 ⁇ 10 4 S/m, and the thermal conductivity was 22W/mK.
  • the parallel arranged quartz fibers are immersed in toluene, heated to 300 ° C for 10 min, and dried;
  • the surface of the quartz fiber obtained in the step (1) was repeatedly coated and dried using an ethylene glycol dispersion of graphene oxide, and the number of cycles was 12, and a long-fiber of quartz fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated quartz fiber filament obtained in the step (2) is placed in ethylene glycol to be surface-swelled, and then the fibers are combined and dried to form the non-twisted yarn, and the drying temperature is lower than 100 ° C. To volatilize ethylene glycol.
  • graphene is coated on the surface of the quartz fiber, and the surface of the quartz fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the rate was 6.8 ⁇ 10 4 S/m, and the thermal conductivity was 29 W/mK.
  • the parallel arranged quartz fibers are immersed in toluene, heated to 300 ° C for 10 min, and dried;
  • the surface of the quartz fiber obtained in the step (1) was repeatedly coated and dried using an aqueous dispersion of graphene oxide, and the number of cycles was 15 times, and a quartz fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated quartz fiber obtained in the step (2) is placed in ethylene glycol to be surface-swelled, and then the fibers are combined and dried to form the non-twisted yarn, and the drying temperature is lower than 100 ° C. Ethylene glycol is evaporated.
  • the surface of the silicon carbide fiber having a circular cross section was repeatedly coated and dried using an aqueous dispersion of graphene oxide, and the number of cycles was 15 times, and a silicon carbide fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated silicon carbide fiber obtained in the step (3) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 °C.
  • graphene is coated on the surface of the silicon carbide fiber, and the surface of the silicon carbide fiber is connected with the graphene sheet by van der Waals force.
  • the SiC fibers are crosslinked by graphene coated on the surface, and the composite fibers are randomly overlapped to form a non-woven fabric structure having an areal density of 111 g/m 2 , a breaking strength of 2.91 GPa and a conductivity of 2.8 ⁇ 10 4 .
  • S/m, thermal conductivity is 22W/mK.
  • the graphene oxide concentration and the coating thickness are the best results obtained through trial and error. It can be seen from Table 6 that, when the concentration of graphene oxide is 7 mg/ml under the same number of coatings, the thickness of the graphene oxide coating on the surface of the silicon carbide fiber is 3 ⁇ m, and the breaking strength of the obtained silicon carbide fiber nonwoven fabric is obtained. The conductivity and thermal conductivity are the highest, and the crosslinking effect is the best. The smaller the concentration of graphene oxide, the smaller the thickness of graphene oxide on the surface of the silicon carbide fiber, and the smaller the breaking strength, electrical conductivity, and thermal conductivity of the obtained silicon carbide fiber nonwoven fabric, the worse the crosslinking effect.
  • the surface of the iron-containing silicon carbide fiber having a circular cross section was repeatedly coated and dried using an N,N-dimethylformamide dispersion of graphene oxide, and the number of cycles was 13 times, and the surface was coated with graphite oxide.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated silicon carbide fiber obtained in the step (1) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 °C.
  • graphene is coated on the surface of the silicon carbide fiber, and the surface of the silicon carbide fiber is connected with the graphene sheet by van der Waals force.
  • the SiC fibers are crosslinked by graphene coated on the surface, and the composite fibers are randomly overlapped to form a non-woven fabric structure with an areal density of 112.6 g/m 2 , a breaking strength of 2.89 GPa and a conductivity of 2.5 ⁇ 10. 4 S/m, thermal conductivity 23W/mK.
  • the surface of the titanium-containing silicon carbide fiber having a trilobal cross section was repeatedly coated and dried using an ethanol dispersion of graphene oxide, and the number of cycles was 16 times, and a silicon carbide fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated silicon carbide fiber obtained in the step (3) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 °C.
  • graphene is coated on the surface of the silicon carbide fiber, and the surface of the silicon carbide fiber is connected with the graphene sheet by van der Waals force.
  • the SiC fibers are crosslinked by graphene coated on the surface, and the composite fibers are randomly overlapped to form a non-woven fabric structure with an areal density of 113.5 g/m 2 , a breaking strength of 2.93 GPa and a conductivity of 3.5 ⁇ 10. 4 S/m, thermal conductivity is 24W/mK.
  • the surface of the parallelized silicon carbide fiber having a circular cross section is repeatedly coated and dried using an ethylene glycol dispersion of graphene oxide, and the number of cycles is 12 times, and the length of the silicon carbide fiber coated with graphene oxide is obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated SiC fiber filament obtained by the step (1) is placed in ethylene glycol to be surface-swelled, and then the fibers are combined and dried to form the crepe-free yarn, and the drying temperature is lower than 100. °C, volatilize ethylene glycol.
  • graphene is coated on the surface of the silicon carbide fiber, and the surface of the silicon carbide fiber is connected with the graphene sheet by van der Waals force.
  • the silicon carbide fibers are crosslinked by graphene coated on the surface, and the composite fibers are arranged in parallel to form a non-twisted fiber structure, the breaking strength is 2.92 GPa, the electrical conductivity is 5.7 ⁇ 10 4 S/m, and the thermal conductivity is 27 W/ mK.
  • the surface of the parallel-shaped hollow aluminum-containing silicon carbide fibers was repeatedly coated and dried using an aqueous dispersion of graphene oxide, and the number of cycles was 15 times, and a silicon carbide fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated silicon carbide fiber obtained in the step (1) is placed in ethylene glycol to be surface-swelled, and then the fibers are combined and dried to form the non-twisted yarn, and the drying temperature is lower than 100 ° C. Evaporate the glycol.
  • graphene is coated on the surface of the silicon carbide fiber, and the surface of the silicon carbide fiber is connected with the graphene sheet by van der Waals force.
  • the silicon carbide fibers are crosslinked by graphene coated on the surface, and the composite fibers are arranged in parallel to form a non-twisted fiber structure, the breaking strength is 2.86 GPa, the electrical conductivity is 4.8 ⁇ 10 4 S/m, and the thermal conductivity is 27 W/mK. .
  • the basalt fiber is heated to 250 ° C in toluene, ultrasonically cleaned for 10 min, the surface sizing agent and the oil agent are removed, and dried;
  • the surface of the basalt fiber obtained in the step (1) was repeatedly coated and dried using an aqueous dispersion of graphene oxide, and the number of cycles was 15 times, and basalt fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated basalt fiber obtained in the step (2) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 degrees Celsius.
  • graphene is coated on the surface of the basalt fiber, and the surface of the basalt fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the basalt fibers are crosslinked by graphene coated on the surface, and the composite fibers are randomly overlapped to form a non-woven fabric structure having an areal density of 86.1 g/m 2 , a breaking strength of 3.24 GPa and a pH of 12 in the lye.
  • the immersion 6h strength retention rate was 89%, the electrical conductivity was 1.6 ⁇ 10 4 S/m, and the thermal conductivity was 29 W/mK.
  • the graphene oxide concentration and the coating thickness are the best results obtained through trial and error. It can be seen from Table 7 that when the concentration of graphene oxide is 7 mg/ml under the same number of coatings, the thickness of the graphene oxide coating on the surface of the basalt fiber is 3 ⁇ m, and the fracture strength and conductivity of the obtained basalt fiber nonwoven fabric are obtained. The rate and thermal conductivity are the highest, and the crosslinking effect is the best. The smaller the concentration of graphene oxide, the smaller the thickness of graphene oxide on the surface of basalt fiber, and the smaller the breaking strength, electrical conductivity and thermal conductivity of the obtained basalt fiber nonwoven fabric, the worse the crosslinking effect.
  • the basalt fiber is heated to 250 ° C in toluene, ultrasonically cleaned for 10 min, the surface sizing agent and the oil agent are removed, and dried;
  • the surface of the basalt fiber obtained in the step (1) is repeatedly coated and dried using an N,N-dimethylformamide dispersion of graphene oxide, and the number of cycles is 13 times, and the surface is coated with graphene oxide.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated basalt fiber obtained in the step (2) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 degrees Celsius.
  • graphene is coated on the surface of the basalt fiber, and the surface of the basalt fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the basalt fibers are crosslinked by graphene coated on the surface, and the composite fibers are randomly overlapped to form a non-woven fabric structure with an areal density of 85.2 g/m 2 , a breaking strength of 3.21 GPa and a pH of 12 in the lye.
  • the immersion 6h strength retention rate was 87%, the electrical conductivity was 1.3 ⁇ 10 4 S/m, and the thermal conductivity was 28 W/mK.
  • the basalt fiber is heated to 250 ° C in toluene, ultrasonically cleaned for 10 min, the surface sizing agent and the oil agent are removed, and dried;
  • the surface of the basalt fiber obtained in the step (1) was repeatedly coated and dried using an ethanol dispersion of graphene oxide, and the number of cycles was 16 times to obtain a basalt fiber having a surface coated with graphene oxide.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated basalt fiber obtained in the step (2) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 degrees Celsius.
  • graphene is coated on the surface of the basalt fiber, and the surface of the basalt fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the basalt fibers are crosslinked by graphene coated on the surface, and the composite fibers are randomly overlapped to form a non-woven fabric structure with an areal density of 84.6 g/m 2 , a breaking strength of 3.23 GPa, and a pH of 12 in the lye.
  • the immersion 6h strength retention rate was 85%, the electrical conductivity was 2.1 ⁇ 10 4 S/m, and the thermal conductivity was 27 W/mK.
  • the parallel basalt long fibers are placed in toluene and heated to 250 ° C, ultrasonically cleaned for 20 min, the surface sizing agent and oil agent are removed, and dried;
  • the surface of the basalt fiber obtained in the step (1) was repeatedly coated and dried using an ethylene glycol dispersion of graphene oxide, and the number of cycles was 12, and a basalt fiber long fiber coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated basalt fiber filament obtained in the step (2) is placed in ethylene glycol to be surface-swelled, and then the fibers are combined and dried to form the crepe-free yarn, and the drying temperature is lower than 100 degrees Celsius. To volatilize ethylene glycol.
  • graphene is coated on the surface of the basalt fiber, and the surface of the basalt fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the parallel basalt long fibers are placed in toluene and heated to 250 ° C, ultrasonically cleaned for 20 min, the surface sizing agent and oil agent are removed, and dried;
  • the surface of the basalt fiber obtained in the step (1) was repeatedly coated and dried using an aqueous dispersion of graphene oxide, and the number of cycles was 15 times, and basalt fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated basalt fiber obtained in the step (2) is placed in ethylene glycol to be surface-swelled, and then the fibers are combined and dried to form the non-twisted yarn, and the drying temperature is lower than 100 degrees Celsius. Ethylene glycol is evaporated.
  • graphene is coated on the surface of the basalt fiber, and the surface of the basalt fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the surface of the alumina fiber was repeatedly coated and dried using an aqueous dispersion of graphene oxide, and the number of cycles was 15 times, and an alumina fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated alumina fiber obtained in the step (3) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 °C.
  • graphene is coated on the surface of the alumina fiber, and the surface of the alumina fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the alumina fibers are crosslinked by graphene coated on the surface, and the composite fibers are randomly overlapped to form a non-woven fabric structure having an areal density of 96.5 g/m 2 , a breaking strength of 2.23 GPa and a conductivity of 3.7 ⁇ 10. 4 S/m, thermal conductivity is 24W/mK.
  • the graphene oxide concentration and the coating thickness are the best results obtained through trial and error. It can be seen from Table 8 that, when the concentration of graphene oxide is 7 mg/ml under the same number of coatings, the thickness of the graphene oxide coating on the surface of the alumina fiber is 3 ⁇ m, and the breaking strength of the obtained alumina fiber nonwoven fabric is obtained. The conductivity and thermal conductivity are the highest, and the crosslinking effect is the best. The smaller the concentration of graphene oxide, the smaller the thickness of graphene oxide on the surface of alumina fiber, and the smaller the breaking strength, electrical conductivity and thermal conductivity of the obtained alumina fiber nonwoven fabric, the worse the crosslinking effect and alkali resistance. .
  • the surface of the alumina fiber was repeatedly coated and dried using a dispersion of N,N-dimethylformamide of graphene oxide, and the number of cycles was 13 times, and an alumina fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated alumina fiber obtained in the step (1) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 °C.
  • graphene is coated on the surface of the alumina fiber, and the surface of the alumina fiber is connected to the graphene sheet by van der Waals force and hydrogen bonding.
  • the alumina fibers are crosslinked by graphene coated on the surface, and the composite fibers are randomly overlapped to form a non-woven fabric structure having an areal density of 95.6 g/m 2 , a breaking strength of 2.3 GPa and a conductivity of 4.5 ⁇ 10. 4 S/m, thermal conductivity is 25W/mK.
  • the surface of the alumina fiber was repeatedly coated and dried using an ethanol dispersion of graphene oxide, and the number of cycles was 16 times, and an alumina fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated alumina fiber obtained in the step (3) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 °C.
  • graphene is coated on the surface of the alumina fiber, and the surface of the alumina fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the alumina fibers are crosslinked by graphene coated on the surface, and the composite fibers are randomly overlapped to form a non-woven fabric structure having an areal density of 95.7 g/m 2 , a breaking strength of 2.24 GPa and a conductivity of 4.1 ⁇ 10. 4 S/m, thermal conductivity 23W/mK.
  • the surface of the parallel-arranged alumina fibers was repeatedly coated and dried using an ethylene glycol dispersion of graphene oxide, and the number of cycles was 12, and alumina fibers having a surface coated with graphene oxide were obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated alumina fiber filament obtained in the step (1) is placed in ethylene glycol to be surface-swelled, and then the fibers are combined and dried to form the crepe-free yarn, and the drying temperature is lower than 100. °C, volatilize ethylene glycol.
  • graphene is coated on the surface of the alumina fiber, and the surface of the alumina fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the alumina fibers are crosslinked by graphene coated on the surface, and the composite fibers are arranged in parallel to form a non-twisted fiber structure, the breaking strength is 2.42 GPa, the electrical conductivity is 7.2 ⁇ 10 4 S/m, and the thermal conductivity is 27 W/ mK.
  • the surface of the parallel-arranged alumina fibers was repeatedly coated and dried using an aqueous dispersion of graphene oxide, and the number of cycles was 15 times, and alumina fibers having a surface coated with graphene oxide were obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated alumina fiber obtained in the step (1) is placed in ethylene glycol to be surface-swelled, and then the fibers are combined and dried to form the non-twisted yarn, and the drying temperature is lower than 100 ° C. Evaporate the glycol.
  • graphene is coated on the surface of the alumina fiber, and the surface of the alumina fiber is connected with the graphene sheet by van der Waals force and hydrogen bonding.
  • the alumina fibers are crosslinked by graphene coated on the surface, and the composite fibers are arranged in parallel to form a non-twisted fiber structure with a breaking strength of 2.52 GPa, a conductivity of 7.6 ⁇ 10 4 S/m, and a thermal conductivity of 28 W/mK. .
  • the surface of the glass fiber obtained in the step (1) was repeatedly coated and dried using an aqueous dispersion of graphene oxide, and the number of cycles was 15 times to obtain a glass fiber having a surface coated with graphene oxide.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated glass fiber obtained in the step (2) is placed in water to be surface-swelled, and then the fibers are lapped to each other and dried to form a nonwoven fabric, and the drying temperature is lower than 100 degrees Celsius.
  • the graphene oxide concentration and the coating thickness are the best results obtained through trial and error. It can be seen from Table 9 that when the concentration of graphene oxide is 7 mg/ml under the same number of coatings, the thickness of the graphene oxide coating on the surface of the glass fiber is 3 ⁇ m, and the obtained glass fiber nonwoven fabric has strong breaking strength and electrical conductivity. The rate and thermal conductivity are the highest, and the crosslinking effect is the best. The smaller the concentration of graphene oxide, the smaller the thickness of graphene oxide on the surface of the glass fiber, and the smaller the breaking strength, electrical conductivity, and thermal conductivity of the obtained glass fiber nonwoven fabric, the worse the crosslinking effect.
  • the surface of the glass fiber obtained in the step (1) is repeatedly coated and dried using an N,N-dimethylformamide dispersion of graphene oxide, and the number of cycles is 13 times, and the surface is coated with graphene oxide.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated glass fiber obtained in the step (2) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 degrees Celsius.
  • the nonwoven fabric structure was formed to have an areal density of 93.1 g/m 2 , a breaking strength of 136 N, a conductivity of 6.1 ⁇ 10 4 S/m, and a thermal conductivity of 26 W/mK.
  • the surface of the glass fiber obtained in the step (1) was repeatedly coated and dried using an ethanol dispersion of graphene oxide, and the number of cycles was 16 times to obtain a glass fiber having a surface coated with graphene oxide.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated glass fiber obtained in the step (2) is placed in water to be surface-swelled, and then the fibers are lapped to each other to form a nonwoven fabric, and the drying temperature is lower than 100 degrees Celsius.
  • the nonwoven fabric structure was formed to have an areal density of 94.6 g/m 2 , a breaking strength of 139 N, a conductivity of 5.7 ⁇ 10 4 S/m, and a thermal conductivity of 23 W/mK.
  • the surface of the glass fiber obtained in the step (1) was repeatedly coated and dried using an ethylene glycol dispersion of graphene oxide, and the number of cycles was 12, and a glass fiber long fiber having a surface coated with graphene oxide was obtained.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated glass fiber filament obtained in the step (2) is placed in ethylene glycol to be surface-swelled, and then the fibers are combined and dried to form the crepe-free yarn, and the drying temperature is lower than 100 degrees Celsius. To volatilize ethylene glycol.
  • the fiber structure has a breaking strength of 2.1 GPa, a conductivity of 7.3 ⁇ 10 4 S/m, and a thermal conductivity of 27 W/mK.
  • the surface of the glass fiber obtained in the step (1) was repeatedly coated and dried using an aqueous dispersion of graphene oxide, and the number of cycles was 15 times to obtain a glass fiber having a surface coated with graphene oxide.
  • the graphene oxide layer has a thickness of 3 ⁇ m;
  • the graphene-coated glass fiber obtained in the step (2) is placed in ethylene glycol to be surface-swelled, and then the fibers are combined and dried to form the non-twisted yarn, and the drying temperature is lower than 100 degrees Celsius. Ethylene glycol is evaporated.
  • the fiber structure has a breaking strength of 2.17 GPa, a conductivity of 5.9 ⁇ 10 4 S/m, and a thermal conductivity of 25 W/mK.
  • a graphene oxide having an average size of more than 50 ⁇ m is formulated into an aqueous solution of graphene oxide having a concentration of 7 mg/mL, and a graphene oxide solution having a thickness of 5 mm is deposited by a doctor blade method to form a film, and then air-dried to obtain a graphene oxide film.
  • Two graphene oxide films having a size of 8 cm*8 cm are compounded by liquid coating, specifically: uniformly coating a surface of the graphene oxide film with a concentration of 4 mg/mL of graphene oxide aqueous solution, and then A plurality of graphene oxide films are bonded together in the thickness direction.
  • step 4 The film after hot pressing in step 4 was heated to 2800 ° C at a rate of 5 ° C / min under an inert gas atmosphere for further hot pressing, and the holding pressure was maintained for 2 hours; the pressure was 60 MPa. After cooling, a graphene film having high thermal conductivity is obtained.
  • the graphene oxide film is fused by the force of the adhesion to form an overall structure.
  • a highly thermally conductive graphene composite film is finally obtained.
  • the graphene composite film bonded by coating the graphene oxide solution can also fill the gap because the graphene oxide can be filled therein, so that the defects are less and the structure is more compact and complete.
  • the graphene thick film has no delamination, and the interlayer spacing of any two adjacent graphene sheets is less than 20 nm.
  • a graphene oxide having an average size of more than 50 ⁇ m is formulated into an aqueous solution of graphene oxide having a concentration of 7 mg/mL, and a graphene oxide solution having a thickness of 5 mm is deposited by a doctor blade method to form a film, and then air-dried to obtain a graphene oxide film.
  • the dried graphene oxide composite film is placed in a hot pressing chamber of a hot press, heated at a rate of 2 ° C/min to 200 ° C, and then hot pressed, and the following hot pressing process is repeated 10 times: maintaining pressure 20MPa, maintain 1h; gradually release the pressure to 0MPa, vacuum the hot pressure chamber for 5min to a vacuum of -50KPa; then heat the temperature at 2 °C / min 300 ° C, heat for 0.5h, then hot press, repeat the following heat
  • the pressing process is 5 times: maintaining the pressure of 60 MPa for 1 h, gradually releasing the pressure to 0 MPa, vacuuming the hot pressing chamber for 5 min to a vacuum of -50 KPa, and naturally cooling after the hot pressing process ends.
  • the graphene oxide composite film which was hot-pressed in the step 4 was heated to 2800 ° C at a rate of 5 ° C/min under an inert gas atmosphere for further hot pressing, and the holding pressure was maintained for 2 hours; the pressure was 60 MPa. After cooling, a thick film of graphene with high thermal conductivity is obtained.
  • the graphene oxide film is fused by the force of the adhesion to form an overall structure.
  • a highly heat-conductive graphene composite thick film is finally obtained.
  • the graphene composite thick film bonded by coating the graphene oxide solution can also fill the gap because of the graphene oxide, so that the structure is less encrypted and more complete.
  • the graphene thick film has no delamination, and the interlayer spacing of any two adjacent graphene sheets is less than 20 nm.
  • the thermal conductivity is 1448.9 W/mK.
  • the graphene thick film has no delamination, and the interlayer spacing of any two adjacent graphene sheets is less than 20 nm, and the thermal conductivity is 1495.8 W/mK.
  • Graphene oxide with a high degree of oxidation of an average size of more than 50 ⁇ m and graphene oxide of a low degree of oxidation are respectively prepared into a 7 mg/mL aqueous solution of graphene oxide, and a graphene solution having a thickness of 5 mm is deposited by a doctor blade method. The film is naturally dried to obtain a graphene oxide film having a high degree of oxidation and a graphene oxide film having a low degree of oxidation.
  • the dried graphene oxide composite film is placed in a hot pressing chamber of a hot press, heated at a rate of 2 ° C/min to 200 ° C, and then hot pressed, and the following hot pressing process is repeated 10 times: maintaining pressure 20MPa, maintain 1h; gradually release the pressure to 0MPa, vacuum the hot pressure chamber for 5min to a vacuum of -50KPa; then heat the temperature at 2 °C / min 300 ° C, heat for 0.5h, then hot press, repeat the following heat
  • the pressing process is 5 times: maintaining the pressure of 60 MPa for 1 h, gradually releasing the pressure to 0 MPa, vacuuming the hot pressing chamber for 5 min to a vacuum of -50 KPa, and naturally cooling after the hot pressing process ends.
  • the graphene oxide composite film which was hot-pressed in the step 4 was heated to 2800 ° C at a rate of 5 ° C/min under an inert gas atmosphere for further hot pressing, and the holding pressure was maintained for 2 hours; the pressure was 60 MPa. After cooling, a thick film of graphene with high thermal conductivity is obtained.
  • the graphene oxide film is fused by the force of the adhesion to form an overall structure.
  • a highly heat-conductive graphene composite thick film is finally obtained. Since the graphene oxide with high oxidation degree has more functional groups, the hydrogen oxide and van der Waals force at the interface are more effective after the high oxidation degree graphene oxide film is uniformly coated with a layer of water. The bonding effect is better and the structure is more compact.
  • the thermal conductivity is 1466.9 W/mK, and the graphene thick film has no delamination, and the interlayer spacing of any two adjacent graphene sheets is less than 20 nm.
  • a graphene oxide having an average size of more than 50 ⁇ m is separately prepared into a 7 mg/mL aqueous solution of graphene oxide, and a graphene oxide film having a thickness of 5 mm and 2.5 mm is separately deposited by a doctor blade method, and dried naturally after being formed into a film. Two thicknesses of graphene oxide film.
  • the dried graphene oxide composite film is placed in a hot pressing chamber of a hot press, heated at a rate of 2 ° C/min to 200 ° C, and then hot pressed, and the following hot pressing process is repeated 10 times: maintaining pressure 20MPa, maintain 1h; gradually release the pressure to 0MPa, vacuum the hot pressure chamber for 5min to a vacuum of -50KPa; then heat the temperature at 2 °C / min 300 ° C, heat for 0.5h, then hot press, repeat the following heat
  • the pressing process is 5 times: maintaining the pressure of 60 MPa for 1 h, gradually releasing the pressure to 0 MPa, vacuuming the hot pressing chamber for 5 min to a vacuum of -50 KPa, and naturally cooling after the hot pressing process ends.
  • the graphene oxide composite film which was hot-pressed in the step 4 was heated to 2800 ° C at a rate of 5 ° C/min under an inert gas atmosphere for further hot pressing, and the holding pressure was maintained for 2 hours; the pressure was 60 MPa. After cooling, a thick film of graphene with high thermal conductivity is obtained.
  • the graphene oxide film is fused by the force of the adhesion to form an overall structure.
  • high-temperature heat treatment repairs defects, and finally a highly thermally conductive graphene thick film is obtained.
  • the thickness of the sample E was 135 ⁇ m
  • the pleat density of the graphene sheet was 121 mm/mm 2
  • the defects of the graphene sheet were extremely small
  • the ID/TG 0.009
  • the porosity was 12.7%
  • the density was 1.92 g/cm 3
  • the thermal conductivity is 1518.4 W/mK
  • the graphene thick film has no delamination.
  • a graphene oxide having an average size of more than 50 ⁇ m is formulated into an aqueous solution of graphene oxide having a concentration of 7 mg/mL, and a graphene oxide solution having a thickness of 5 mm is deposited by a doctor blade method to form a film, and then air-dried to obtain a graphene oxide film.
  • a hundred sheets of a graphene oxide film having a size of 4 cm*4 cm are composited, specifically: uniformly coating a layer of a graphene oxide solution having a concentration of 4 mg/mL on the surface of the graphene oxide film, and then applying a plurality of sheets The graphene oxide film is bonded together in the thickness direction.
  • the dried graphene oxide composite film is placed in a hot pressing chamber of a hot press, heated at a rate of 2 ° C/min to 200 ° C, and then hot pressed, and the following hot pressing process is repeated 10 times: maintaining pressure 20MPa, maintain 1h; gradually release the pressure to 0MPa, vacuum the hot pressure chamber for 5min to a vacuum of -100 ⁇ 10KPa; then heat up to 300°C at a rate of 2°C/min, keep warm for 0.5h, then heat-press, repeat The following hot pressing process is 5 times: maintaining the pressure of 60 MPa for 1 h, gradually releasing the pressure to 0 MPa, vacuuming the hot pressing chamber for 5 min to a vacuum of -100 to 10 KPa, and naturally cooling after the hot pressing process.
  • the graphene oxide composite film which was hot pressed in the step 4 was heated to 2500 ° C at a rate of 5 ° C/min under an inert gas atmosphere for further hot pressing, and the holding pressure was maintained for 2 hours; the pressure was 60 MPa. After cooling, a thick film of graphene with high thermal conductivity is obtained.
  • the graphene oxide film is fused by the force of the adhesion and the filling gap of the graphene oxide in the liquid is applied to form an integral structure.
  • a highly heat-conductive graphene composite thick film is finally obtained.
  • a graphene oxide having an average size of more than 100 ⁇ m is formulated into an aqueous solution of graphene oxide having a concentration of 1 mg/mL, and the solution is formed into a film and then naturally dried to obtain a graphene oxide film.
  • the thickness of the graphene oxide film was 15 ⁇ m, and the carbon oxide ratio of the graphene oxide film was 1.8.
  • the dried graphene oxide composite film is placed in a hot press chamber of a hot press, heated to a temperature of 0.1 ° C/min to 200 ° C, and then hot pressed, and the following hot pressing process is repeated 8 times: maintaining pressure 20MPa, maintain 1h; gradually release the pressure to 0MPa, vacuum the hot pressure chamber for 5min to a vacuum of -100KPa; then heat the temperature at 0.1 °C / min 300 ° C, heat for 0.5h, then hot press, repeat the following heat
  • the pressing process is 4 times: maintaining the pressure of 60 MPa for 1 h, gradually releasing the pressure to 0 MPa, vacuuming the hot pressing chamber for 5 min to a vacuum of -100 KPa, and naturally cooling after the hot pressing process.
  • the graphene oxide film which was hot-pressed in the step 4 was heated to 1800 ° C at a rate of 1 ° C/min under an inert gas atmosphere for further hot pressing, and the holding pressure was maintained for 8 hours; the pressure was 60 MPa. After cooling and pressing, a thick film of graphene with high thermal conductivity is obtained.
  • the graphene thick film has no delamination, and the interlayer spacing of any two adjacent graphene sheets is less than 20 nm.
  • a graphene oxide having an average size of more than 50 ⁇ m is formulated into an aqueous solution of graphene oxide having a concentration of 20 mg/mL, and the solution is formed into a film and then air-dried to obtain a graphene oxide film having a thickness of 50 ⁇ m and a carbon-oxygen ratio of 2.1.
  • the dried graphene oxide composite film is placed in a hot pressing chamber of a hot press, heated to a temperature of 5 ° C/min to 200 ° C, and then hot pressed, and the following hot pressing process is repeated 10 times: maintaining pressure 20MPa, maintain 1h; gradually release the pressure to 0MPa, vacuum the hot pressure chamber for 5min to a vacuum of -10KPa; then heat the temperature at 5 °C / min 300 ° C, heat for 0.5h, then hot press, repeat the following heat
  • the pressing process is 6 times: maintaining the pressure of 60 MPa for 1 h, gradually releasing the pressure to 0 MPa, vacuuming the hot pressing chamber for 5 min to a vacuum of -10 KPa, and naturally cooling after the hot pressing process.
  • the graphene oxide film which was hot pressed in the step 4 was heated to 3000 ° C at a rate of 20 ° C / min under an inert gas atmosphere for further hot pressing, and the holding pressure was maintained for 0.5 h; the pressure was 10 MPa. After cooling and pressing, a thick film of graphene with high thermal conductivity is obtained.
  • the graphene thick film has no delamination, and the interlayer spacing of any two adjacent graphene sheets is less than 20 nm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Textile Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本发明利用氧化石墨烯在溶剂中的溶胀和融合作用，实现对石墨烯材料本身以及高分子、金属、纸、玻璃、碳材料和陶瓷等材料的交联粘结。不但克服传统粘接剂残留甲醛的缺点，而且干燥时间短，粘接强度高，耐腐蚀，在航空、航天、汽车、机械、建筑、化工、轻工、电子、电器以及日常生活等领域得到广泛的应用。

Description

基于石墨烯粘结的复合材料的制备方法 技术领域
本发明涉及石墨烯粘结的复合材料的制备方法。
背景技术
随着社会的进步和科学技术的发展，人们的环保意思识和可持续发展观念日益增强，由溶剂型粘接剂向环保型水基粘接剂转变，已成为当前粘接剂发展的必然趋势。传统的粘接剂例如白乳胶、淀粉胶黏剂存在着易霉变、耐水性和耐湿性比较差和干燥速度慢等缺点；水玻璃存在着耐碱性和耐水性差；具腐蚀性、强刺激性，可致人体灼伤；酚醛树脂胶黏剂存在着脆性大，剥离强度低，不适于作结构胶粘剂使用的缺点；应用较多的脲醛树脂胶黏剂甲醛释放量高、污染环境、危害健康的缺点。
发明内容
针对现有技术的不足，本发明利用氧化石墨烯在溶剂中的溶胀和融合作用，实现对石墨烯材料本身以及高分子、金属、纸、玻璃、碳材料和陶瓷等材料的交联粘结。不但克服传统粘接剂残留甲醛的缺点，而且干燥时间短，粘接强度高，耐腐蚀，在航空、航天、汽车、机械、建筑、化工、轻工、电子、电器以及日常生活等领域得到广泛的应用。
本发明包括以下技术方案：
方案一：为实现氮化硼纤维的交联，本发明将氧化石墨烯涂覆到氮化硼纤维表面，氧化石墨烯与氮化硼纤维表面的氧化硼形成氢键和范德华力作用，实现均匀牢固涂覆。而后使氮化硼纤维表层氧化石墨烯在溶剂中溶胀，片层获得较大的自由度，干燥时氧化石墨烯片层由于受到溶剂挥发所致的毛细作用力和片层之间的π-π作用力而自发紧密堆叠，因此氮化硼纤维相互交联，如图1,2所示，最终得到石墨烯-氮化硼纤维复合材料，包括无捻纱，无纺布或短切毡等。
石墨烯-氮化硼纤维复合材料的制备方法，包括以下步骤：
(1)使用氧化石墨烯分散液对氮化硼纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的氮化硼纤维。
(2)将涂覆氧化石墨烯的氮化硼纤维置于溶剂中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，或将纤维相互搭接经干燥后形成所述无纺布或短切毡，干燥温度低于100℃。
(3)还原后得到石墨烯-氮化硼纤维复合材料。
进一步地，所述步骤(1)中氧化石墨烯分散液的浓度为7mg/g，分散剂为水、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙醇、乙二醇、N-甲基吡咯烷酮、四氢呋喃、二甲亚砜、二甘醇、吡啶、二氧六环、丁酮、异丙醇等。
进一步地，所述步骤(1)中使用氧化石墨烯分散液对氮化硼纤维进行多次涂覆，每次涂覆后干燥，最终干燥后的氧化石墨烯层厚度为3μm。
进一步地，所述步骤(2)中溶剂为水、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，所述步骤(3)中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100～600℃热还原。
所制备得到的石墨烯-氮化硼纤维复合材料中，石墨烯包覆在氮化硼纤维表面，氮化硼纤维表面与石墨烯片通过范德华力和氢键连接。氮化硼纤维之间通过包覆在表面的石墨烯实现交联，形成无捻纱，无纺布或短切毡。有益效果在于：
(1)纯石墨烯作为氮化硼纤维表面分布均匀，界面附着强度高，浸泡在溶剂中不脱落。
(2)纯石墨烯作为氮化硼纤维的交联剂交联强度高。利用氧化石墨烯在溶剂中的溶胀融合作用实现氮化硼纤维的交联，方法简单、省时，采用的溶剂环保，交联效果好，相比其他交联方法具有很大的应用价值。
利用此交联方法可以保持氮化硼纤维优异的力学性能，并且可以提升纤维的导电性、导热性等，从而进一步扩展氮化硼纤维材料的应用。
方案二：为实现石英纤维的交联，本发明将氧化石墨烯涂覆到石英纤维表面，氧化石墨烯与石英纤维的羟基形成氢键和范德华力作用，实现均匀牢固涂覆。而后使石英纤维表层氧化石墨烯在溶剂中溶胀，片层获得较大的自由度，干燥时氧化石墨烯片层由于受到溶剂挥发所致的毛细作用力和片层之间的π-π作用力而自发紧密堆叠，因此石英纤维相互交联，最终得到石墨烯-石英纤维复合材料，制备方法包括以下步骤：
(1)将石英纤维置于甲苯中浸泡，加热至300℃保持10min，烘干。
(2)使用氧化石墨烯分散液对石英纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的石英纤维。
(3)将涂覆氧化石墨烯的石英纤维置于溶剂中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，或将纤维相互搭接经干燥后形成所述无纺布或短切毡，干燥温度低于100℃。
(4)还原后得到石墨烯-石英纤维复合材料。
进一步地，所述步骤(2)中氧化石墨烯分散液的浓度为7mg/g，分散剂为水、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙醇、乙二醇、N-甲基吡咯烷酮、四氢呋喃、二甲亚砜、二甘醇、吡啶、二氧六环、丁酮、异丙醇等。
进一步地，所述步骤(2)中使用氧化石墨烯分散液对石英纤维进行多次涂覆，每次涂覆后干燥，最终干燥后的氧化石墨烯层厚度为3μm。
进一步地，所述步骤(3)中溶剂为水、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，所述步骤(4)中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100～600℃热还原。
所制备得到的石墨烯-石英纤维复合材料中，石墨烯包覆在石英纤维表面，石英纤维表面与石墨烯片通过范德华力和氢键连接。石英纤维之间通过包覆在表面的石墨烯实现交联，形成无捻纱，无纺布或短切毡。有益效果在于：
(1)纯石墨烯作为石英纤维表面分布均匀，界面附着强度高，浸泡在溶剂中不脱落。
(2)纯石墨烯作为石英纤维的交联剂交联强度高。利用氧化石墨烯在溶剂中的溶胀融合作用实现石英纤维的交联，方法简单、省时，采用的溶剂环保，交联效果好，相比其他交联方法具有很大的应用价值。
利用此交联方法可以保持石英纤维优异的力学性能，且能提高石英纤维的导热性，导电性，耐碱性等，从而进一步扩展石英纤维材料的应用。
方案三：为实现碳化硅纤维的交联，本发明将氧化石墨烯涂覆到碳化硅纤维表面，氧化石墨烯与碳化硅表面形成范德华力作用，实现均匀牢固涂覆。而后使碳化硅纤维表层氧化石墨烯在溶剂中溶胀，片层获得较大的自由度，干燥时氧化石墨烯片层由于受到溶剂挥发所致的毛细作用力和片层之间的π-π作用力而自发紧密堆叠，因此碳化硅纤维相互交联，最终得到石墨烯-碳化硅纤维复合材料，制备方法包括以下步骤：
(1)使用氧化石墨烯分散液对碳化硅纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的碳化硅纤维。
(2)将涂覆氧化石墨烯的碳化硅纤维置于溶剂中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，或将纤维相互搭接经干燥后形成所述无纺布或短切毡，干燥温度低于100℃。
(3)还原后得到石墨烯-碳化硅纤维复合材料。
进一步地，所述步骤(1)中碳化硅纤维含有钛、铁、镍、硼、铝、锆元素中的一种或多种，纤维截面形状为圆形、三叶形、三折叶形、六叶形、条形、十字形、中空形中的一种。
进一步地，所述步骤(1)中氧化石墨烯分散液的浓度为7mg/g，分散剂为水、N,N-二甲 基甲酰胺、N,N-二甲基乙酰胺、乙醇、乙二醇、N-甲基吡咯烷酮、四氢呋喃、二甲亚砜、二甘醇、吡啶、二氧六环、丁酮、异丙醇等。
进一步地，所述步骤(1)中使用氧化石墨烯分散液对碳化硅纤维进行多次涂覆，每次涂覆后干燥，最终干燥后的氧化石墨烯层厚度为3μm。
进一步地，所述步骤(2)中溶剂为水、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，所述步骤(3)中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100～600℃热还原。
制备得到的石墨烯-碳化硅纤维复合材料中，石墨烯包覆在碳化硅纤维表面，碳化硅纤维表面与石墨烯片通过范德华力连接。碳化硅纤维之间通过包覆在表面的石墨烯实现交联，形成无捻纱，无纺布或短切毡。有益效果在于：
(1)纯石墨烯作为碳化硅纤维表面分布均匀，界面附着强度高，浸泡在溶剂中不脱落。
(2)纯石墨烯作为碳化硅纤维的交联剂交联强度高。利用氧化石墨烯在溶剂中的溶胀融合作用实现碳化硅纤维的交联，方法简单、省时，采用的溶剂环保，交联效果好，相比其他交联方法具有很大的应用价值。
利用此交联方法可以保持碳化硅纤维优异的力学性能，并且可以提升纤维的导电性、导热性等，从而进一步扩展碳化硅纤维材料的应用。此外，由于石墨烯本身电导率可调节，与碳化硅纤维复合后可调节体系整体的介电性能，可有效提升对电磁波的吸收和反射能力，可在吸波材料和电磁屏蔽材料中得到广泛应用。
方案四：为实现玄武岩纤维的交联，本发明将氧化石墨烯涂覆到玄武岩纤维表面，氧化石墨烯与玄武岩纤维的羟基形成氢键和范德华力作用，实现均匀牢固涂覆。而后使玄武岩纤维表层氧化石墨烯在溶剂中溶胀，片层获得较大的自由度，干燥时氧化石墨烯片层由于受到溶剂挥发所致的毛细作用力和片层之间的π-π作用力而自发紧密堆叠，因此玄武岩纤维相互交联，最终得到石墨烯-玄武岩纤维复合材料制备方法，包括以下步骤：
(1)将玄武岩纤维置于甲苯中加热至250℃，超声清洗10～30min，除去表面浸润剂和油剂，烘干。
(2)使用氧化石墨烯分散液对玄武岩纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的玄武岩纤维。
(3)将涂覆氧化石墨烯的玄武岩纤维置于溶剂中进行表面溶胀，然后将纤维合并经干燥 后形成所述无捻纱，或将纤维相互搭接经干燥后形成所述无纺布或短切毡，干燥温度低于100摄氏度。
(4)还原后得到石墨烯-玄武岩纤维复合材料。
进一步地，所述步骤(2)中氧化石墨烯分散液的浓度为7mg/g，分散剂为水、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙醇、乙二醇、N-甲基吡咯烷酮、四氢呋喃、二甲亚砜、二甘醇、吡啶、二氧六环、丁酮、异丙醇等。
进一步地，所述步骤(2)中使用氧化石墨烯分散液对玄武岩纤维进行多次涂覆，每次涂覆后干燥，最终干燥后的氧化石墨烯层厚度为3μm。
进一步地，所述步骤(3)中溶剂为水、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，所述步骤(4)中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100～600℃热还原。
本发明的有益效果在于：
(1)纯石墨烯作为玄武岩纤维表面分布均匀，界面附着强度高，浸泡在溶剂中不脱落。
(2)纯石墨烯作为玄武岩纤维的交联剂交联强度高。利用氧化石墨烯在溶剂中的溶胀融合作用实现玄武岩纤维的交联，方法简单、省时，采用的溶剂环保，交联效果好，相比其他交联方法具有很大的应用价值。
利用此交联方法可以保持玄武岩纤维优异的力学性能，并提高其导电性，耐腐蚀性，导热性，从而进一步扩展玄武岩纤维材料的应用。
制备得到的石墨烯-玄武岩纤维复合材料中，石墨烯包覆在玄武岩纤维表面，玄武岩纤维表面与石墨烯片通过范德华力和氢键连接。玄武岩纤维之间通过包覆在表面的石墨烯实现交联，形成无捻纱，无纺布或短切毡。有益效果在于：
(1)纯石墨烯作为玄武岩纤维表面分布均匀，界面附着强度高，浸泡在溶剂中不脱落。
(2)纯石墨烯作为玄武岩纤维的交联剂交联强度高。利用氧化石墨烯在溶剂中的溶胀融合作用实现玄武岩纤维的交联，方法简单、省时，采用的溶剂环保，交联效果好，相比其他交联方法具有很大的应用价值。
利用此交联方法可以保持玄武岩纤维优异的力学性能，并提高其导电性，耐腐蚀性，导热性，从而进一步扩展玄武岩纤维材料的应用。
方案五：为实现氧化铝纤维的交联，本发明将氧化石墨烯涂覆到氧化铝纤维表面，氧化 石墨烯与氧化铝纤维的羟基形成氢键和范德华力作用，实现均匀牢固涂覆。而后使氧化铝纤维表层氧化石墨烯在溶剂中溶胀，片层获得较大的自由度，干燥时氧化石墨烯片层由于受到溶剂挥发所致的毛细作用力和片层之间的π-π作用力而自发紧密堆叠，因此氧化铝纤维相互交联，最终得到石墨烯-氧化铝纤维复合材料，制备方法包括以下步骤：
(1)使用氧化石墨烯分散液对氧化铝纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的氧化铝纤维。
(2)将涂覆氧化石墨烯的氧化铝纤维置于溶剂中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，或将纤维相互搭接经干燥后形成所述无纺布或短切毡，干燥温度低于100℃。
(3)还原后得到石墨烯-氧化铝纤维复合材料。
进一步地，所述步骤(1)中氧化石墨烯分散液的浓度为7mg/g，分散剂为水、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙醇、乙二醇、N-甲基吡咯烷酮、四氢呋喃、二甲亚砜、二甘醇、吡啶、二氧六环、丁酮、异丙醇等。
进一步地，所述步骤(1)中使用氧化石墨烯分散液对氧化铝纤维进行多次涂覆，每次涂覆后干燥，最终干燥后的氧化石墨烯层厚度为3μm。
进一步地，所述步骤(2)中溶剂为水、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，所述步骤(3)中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100～600℃热还原。
制备得到的石墨烯-氧化铝纤维复合材料中，石墨烯包覆在氧化铝纤维表面，氧化铝纤维表面与石墨烯片通过范德华力和氢键连接。氧化铝纤维之间通过包覆在表面的石墨烯实现交联，形成无捻纱，无纺布或短切毡。有益效果在于：
(1)纯石墨烯作为氧化铝纤维表面分布均匀，界面附着强度高，浸泡在溶剂中不脱落。
(2)纯石墨烯作为氧化铝纤维的交联剂交联强度高。利用氧化石墨烯在溶剂中的溶胀融合作用实现氧化铝纤维的交联，方法简单、省时，采用的溶剂环保，交联效果好，相比其他交联方法具有很大的应用价值。
利用此交联方法可以保持氧化铝纤维优异的力学性能，并且可以提升纤维的导电性、导热性等，从而进一步扩展氧化铝纤维材料的应用。
方案六：为实现玻璃纤维的交联，本发明将氧化石墨烯涂覆到玻璃纤维表面，氧化石墨 烯与玻璃纤维的羟基形成氢键和范德华力作用，实现均匀牢固涂覆。而后使玻璃纤维表层氧化石墨烯在溶剂中溶胀，片层获得较大的自由度，干燥时氧化石墨烯片层由于受到溶剂挥发所致的毛细作用力和片层之间的π-π作用力而自发紧密堆叠，因此玻璃纤维相互交联，最终得到石墨烯-玻璃纤维复合材料，制备方法包括以下步骤：
(1)将玻璃纤维置于丙酮中超声清洗，除去表面油渍，烘干。
(2)使用氧化石墨烯分散液对玻璃纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的玻璃纤维。
(3)将涂覆氧化石墨烯的玻璃纤维置于溶剂中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，或将纤维相互搭接经干燥后形成所述无纺布或短切毡，干燥温度低于100摄氏度。
(4)还原后得到石墨烯-玻璃纤维复合材料。
进一步地，所述步骤(2)中氧化石墨烯分散液的浓度为7mg/g，分散剂为水、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙醇、乙二醇、N-甲基吡咯烷酮、四氢呋喃、二甲亚砜、二甘醇、吡啶、二氧六环、丁酮、异丙醇等。
进一步地，所述步骤(2)中使用氧化石墨烯分散液对玻璃纤维进行多次涂覆，每次涂覆后干燥，最终干燥后的氧化石墨烯层厚度为3μm。
进一步地，所述步骤(3)中溶剂为水、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，所述步骤(4)中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100～600℃热还原。
制备得到的石墨烯-玻璃纤维复合材料中，石墨烯包覆在玻璃纤维表面，玻璃纤维表面与石墨烯片通过范德华力和氢键连接。玻璃纤维之间通过包覆在表面的石墨烯实现交联，形成无捻纱，无纺布或短切毡。有益效果在于：
(1)纯石墨烯作为玻璃纤维表面分布均匀，界面附着强度高，浸泡在溶剂中不脱落。
(2)纯石墨烯作为玻璃纤维的交联剂交联强度高。利用氧化石墨烯在溶剂中的溶胀融合作用实现玻璃纤维的交联，方法简单、省时，采用的溶剂环保，交联效果好，相比其他交联方法具有很大的应用价值。
利用此交联方法可以保持玻璃纤维优异的力学性能，且能提高玻璃纤维的导热性，导电性，耐腐蚀性等，从而进一步扩展玻璃纤维材料的应用。
方案七：为实现碳纤维的交联，本发明将氧化石墨烯作为上浆剂涂覆到单根碳纤维上，氧化石墨烯在范德华力及氢键的作用下，沿纤维轴向贴附在纤维表面，即沿纤维轴向分布，如图3b所示。而后使碳纤维表层氧化石墨烯在溶剂中溶胀，片层获得较大的自由度，干燥时氧化石墨烯片层由于受到溶剂挥发所致的毛细作用力和片层之间的π-π作用力而自发紧密堆叠，因此碳纤维相互交联，如图3c所示，最终得到石墨烯交联的碳纤维丝束，制备方法包括以下步骤：
(1)去除碳纤维表面的上浆剂，并对其表面进行氧化改性。
(2)使用氧化石墨烯分散液对氧化改性后的碳纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的碳纤维。
(3)将多根涂覆氧化石墨烯的碳纤维置于溶剂中进行表面溶胀，然后将溶胀后的纤维并成丝束，随后在低于100℃的温度下干燥，使得溶剂挥发。
(4)还原后得到石墨烯交联的碳纤维丝束。
所述碳纤维表面具有沿纤维轴向分布的石墨烯片，所述碳纤维表面与石墨烯片通过范德华力和氢键连接。织物节点处，碳纤维之间通过石墨烯片实现交联。
一种石墨烯交联的碳纤维织物的制备方法，包括以下步骤：
(1)去除碳纤维表面的上浆剂，并对其表面进行氧化改性。
(2)使用氧化石墨烯分散液对氧化改性后的碳纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的碳纤维。
(3)将多根涂覆氧化石墨烯的碳纤维编织成织物，置于溶剂中进行表面溶胀、融合，随后在低于100℃的温度下干燥，使得溶剂挥发。
(4)还原后得到石墨烯交联的碳纤维织物。
进一步地，所述步骤(1)中去除碳纤维表面上浆剂的方法为：将碳纤维置于丙酮中以57～100℃回流6h以上，烘干。所述步骤(1)中对碳纤维表面进行氧化改性的方法为：将碳纤维置于100～157℃的过氧化氢溶液(质量分数为30％)中浸泡0.5～3h、然后在83～120℃的浓硝酸(质量分数为70％)中浸泡6～24h，最后用水清洗烘干。优选为：将碳纤维置于丙酮中以80℃回流72h除去表面上浆剂。再先后在过氧化氢中110℃浸泡2h、浓硝酸中115℃浸泡12h，最后用水清洗烘干。
进一步地，所述步骤(2)中氧化石墨烯分散液的分散剂为水、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙醇、乙二醇、N-甲基吡咯烷酮、四氢呋喃、二甲亚砜、二甘醇、吡啶、二氧六环、丁酮、异丙醇等。
进一步地，所述步骤(2)中，使用氧化石墨烯分散液对氧化改性后的碳纤维进行多次涂覆，每次涂覆后干燥，干燥温度约为25～50℃。
进一步地，所述步骤(3)中溶剂为水、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，所述步骤(4)中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。
进一步地，所述步骤2中采用氧化石墨烯分散液的浓度为7mg/ml，干燥后碳纤维表面的氧化石墨烯厚度为3μm。
所制备得到的碳纤维丝束中的碳纤维之间通过沿纤维轴向分布的石墨烯片实现交联。所述碳纤维表面与石墨烯片通过范德华力和氢键连接；所得到的碳纤维织物中，所述碳纤维表面具有沿纤维轴向分布的石墨烯片，所述碳纤维表面与石墨烯片通过范德华力和氢键连接。织物节点处，碳纤维之间通过石墨烯片实现交联。现有技术相比，具有的优势如下：
(1)纯石墨烯作为碳纤维的上浆剂在纤维表面分布均匀，界面附着强度高，浸泡在溶剂中不脱落。
(2)纯石墨烯作为碳纤维的交联剂交联强度高。利用氧化石墨烯在溶剂中的溶胀融合作用实现碳纤维的交联，方法简单、省时，采用的溶剂环保，交联效果好。该交联方法具有很大的应用价值。
利用此交联方法可以保持碳纤维优异的力学性能、导电性、耐腐蚀性等，且能提高碳纤维的导热性，从而进一步扩展碳纤维材料的应用。
方案八：为实现氧化石墨烯膜的粘结，本发明将氧化石墨烯膜表面均匀喷涂一层水或者稀的氧化石墨烯溶液，表面溶胀后将多张氧化石墨烯膜粘接在一起，从而使氧化石墨烯薄膜之间通过氢键和范德华力作用，能够在膜粘接的界面处实现自粘结，氧化石墨烯膜之间融合为一体，膜与膜之间的界面几乎消失。通过进一步低温热压，高温热压退火还原，使得石墨烯膜褶皱极少，石墨烯片层上缺陷几乎全部修复，形成完美的三维石墨结构，相互接触的石墨烯片层之间有一定的融合，最终得到厚度大于50μm的高导热石墨烯厚膜，制备方法包含如下步骤：
(1)将平均尺寸大于50μm的氧化石墨烯配制成浓度为1～20mg/mL氧化石墨烯水溶液，溶液成膜后自然晾干，得到氧化石墨烯膜。
(2)多张氧化石墨烯膜进行复合，具体为：在氧化石墨烯膜表面进行均匀喷涂液体，使之表面溶胀，然后将多张氧化石墨烯膜沿厚度方向粘接在一起。
(3)将粘接后的氧化石墨烯复合膜放置在烘箱烘干，烘箱的温度低于40℃。
(4)将烘干后的氧化石墨烯复合膜置于热压机的热压腔中，以0.1～5℃/min的速率升 温到200℃后进行热压，重复以下热压过程8-10次：维持压力20MPa，维持1h；逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-100～10KPa；然后再以0.1～5℃/min的速率升温300℃，保温0.5h，然后进行热压，重复以下热压过程4-6次：维持压力60MPa，维持1h，逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-100～10KPa；热压过程结束后自然降温。
(5)将步骤4热压后的氧化石墨烯膜在惰性气体氛围下以1～20℃/min的速率升温到1800～3000℃进行进一步热压，保温保压0.5～8h；压力为60MPa。降温后，得到高导热的石墨烯厚膜。
进一步地，所述步骤1制备的氧化石墨烯膜的厚度为1～30μm。
进一步地，所述步骤1中的成膜方法选自抽滤法、刮膜法、旋涂法、喷涂法和浸涂法等。
进一步地，所述的步骤1制备的氧化石墨烯膜的碳氧比1.8～2.1。
进一步地，所述的步骤2喷涂所使用的液体为：去离子水，浓度为1～10mg/mL的氧化石墨烯水溶液，或其它含有去离子水的溶液。
所制备的石墨烯厚膜的厚度大于50μm，孔隙率为5～40％；石墨烯片层褶皱密度控制在50-500mm/mm 2,且石墨烯片的缺陷少，其ID/TG＜0.02，面向热导率为1000～2000W/mK。石墨烯厚膜无分层现象，任意两个相邻的石墨烯片的片层间距小于20nm。有益效果在于：本发明通过将氧化石墨烯膜表面溶胀后，使得多张氧化石墨烯膜粘接在一起，待其干燥后氧化石墨烯膜可通过粘接界面处的作用力实现自粘结，通过进一步低温热压使得氧化石墨烯膜之间粘结更加紧实，实现氧化石墨烯厚膜的制备。最终经过低温加热预还原，再高温热压处理的方式，修复石墨烯膜结构缺陷，控制了石墨烯片层褶皱密度，提高了石墨烯片的取向程度，使得石墨烯膜最高程度的形成三维石墨结构，保证了石墨烯导热通路的畅通，可得到高导热的石墨烯厚膜。该高导热的石墨烯厚膜具有柔性，可弯折，导热性能高。
方案九：一种氧化石墨烯粘接剂，包括溶剂，以及分散于溶剂中的氧化石墨烯，所述氧化石墨烯的浓度大于等于4mg/ml，C/O比小于等于3:1，氧化石墨烯单层率大于80％。氧化石墨烯片层尺寸为1um～100um，尺寸小于5um的氧化石墨烯片的量不多于10％，且尺寸大于30um的氧化石墨烯片的量不少于60％。
进一步地，溶剂为水、DMF。
一种基于石墨烯材料的粘结方法，该方法为：首先对粘结材料表面进行亲水处理，之后将氧化石墨烯粘接剂均匀涂覆在多个待粘接材料之间，待其干燥后，待粘接材料之间通过氧化石墨烯实现粘接。
进一步地，待粘接材料包括高分子、金属、纸和玻璃、碳材料、陶瓷等材料，以及上述不同种材料之间的粘结。
本发明首次提出一种新型环保的氧化石墨烯粘接剂，不但克服传统粘接剂残留甲醛的缺 点，而且粘接性好，在航空、航天、汽车、机械、建筑、化工、轻工、电子、电器以及日常生活等领域得到广泛的应用。与现有技术相比，具有以下有益效果：
(1)在氧化石墨烯粘接剂合成的工艺路线中，未加入任何含有高分子物质，无污染，利于环保。
(2)采用氧化石墨烯粘接剂进行粘接，直接涂覆，待其干燥后即实现粘接，使用简便，可实现连续化生产。
(3)粘接界面稳定，可耐受高温、酸碱腐蚀等。
方案十：一种利用石墨烯实现材料粘接的方法，该方法为：首先将氧化石墨烯溶液均匀涂覆在多个待粘接材料之间，待其干燥后进行还原，即可在待粘接材料之间通过石墨烯实现粘接。所述氧化石墨烯溶液中，氧化石墨烯片层尺寸为1um～100um，尺寸小于5um的氧化石墨烯片少于等于10％，且尺寸大于30um的氧化石墨烯片不少于65％；氧化石墨烯单层率大于80％；氧化石墨烯的浓度大于等于4mg/mL。
进一步地，还原后的石墨烯的C/O大于4:1。
进一步地，所述溶剂为水、乙醇、N,N-二甲基甲酰胺(DMF)。
进一步地，待粘接材料包括高分子、金属、纸和玻璃、碳材料、陶瓷等材料，以及上述不同种材料之间的粘接。
进一步地，所述还原方法为在80-100℃下利用氢碘酸或水合肼蒸汽进行化学还原。
进一步地，所述还原方法为在加压或真空状态下按1℃/min升温速率缓慢升温至100-500℃热还原。
本发明首次提出一种在材料界面处实现100％石墨烯粘接的方法。该策略首先通过高极性的氧化石墨烯在材料界面处建立有效粘接，继而施加可控还原，得到石墨烯粘接层，并且有效避免了还原过程中脱粘、起泡等现象的发生。与现有技术相比，本发明具有以下有益效果：
(1)在粘接过程中，未加入任何含有高分子物质，无污染，利于环保。
(2)使用方法简单，且粘接处具有导电导热等特性。
(3)粘接界面稳定，可耐受高温、湿气、酸碱腐蚀等。
附图说明
图1是经本发明石墨烯交联的氮化硼纤维无纺布的示意图。
图2是经本发明石墨烯交联的氮化硼纤维无捻纤的示意图。
图3a,b分别是单根碳纤维涂覆前、后的扫描电子显微镜照片，c为两根交联后的碳纤维的截面图。
图4为不同浓度粘结剂(氧化石墨烯)的粘结性能图。
图5为不同浓度粘结剂(还原后的氧化石墨烯)的粘结性能图。
图6为连续涂覆设备的示意图；
图7为使用去离子水粘接成的石墨烯厚膜的SEM截面图；
图8为使用氧化石墨烯水溶液粘接成的石墨烯厚膜的SEM截面图。
具体实施方式
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。
没有明确指定的情况下，以下实施例涉及的百分数均为数量百分比，例如，“单层氧化石墨烯占在氧化石墨烯总量的81.5％”，意为，1000片的氧化石墨烯中，单层氧化石墨烯的数量为815片；“尺寸小于5um的氧化石墨烯片的量为7±3％”，意为，100片的氧化石墨烯中，尺寸小于5um的氧化石墨烯片的数量为7±3片。另外，C/O为本领域常用技术术语，表示C、O的原子个数比。
实施例1-1
本实施例研究了不同浓度下的氧化石墨烯粘结剂的粘结性能，其条件如下：
采用的氧化石墨烯溶液中，尺寸小于5um的氧化石墨烯片的量为7±3％，尺寸大于30um的氧化石墨烯片的量为65±4％，其余部分尺寸为5-30um之间；整体的C/O比2.5:1，单层氧化石墨烯占在氧化石墨烯总量的81.5％。
分别按照2-20mg/ml的浓度配置氧化石墨烯水溶液，并将其对两片载玻片实现粘结，粘结方法为：首先对载玻片进行亲水处理，之后将氧化石墨烯粘接剂均匀涂覆在两片载玻片之间，待其干燥后，两片载玻片通过氧化石墨烯实现粘接。
不同浓度下的粘接效果如图4所示。从图中可以看出，氧化石墨烯浓度在4mg/ml以上，具有较好的粘接效果。
实施例1-2
本实施例研究了不同C/O比(1:3、1:2、1:1、2:1、3:1、4:1、5:1)的氧化石墨烯粘结剂的粘结性能，其条件如下：
采用的氧化石墨烯中，尺寸小于5um的氧化石墨烯片的量为5±3％，尺寸大于30um的氧化石墨烯片的量为60±5％，其余部分尺寸为5-30um之间；单层氧化石墨烯占在氧化石墨烯总量的95.8％。按照8mg/ml的浓度配置氧化石墨烯水溶液，并将其对两片载玻片实现粘结，粘结方法为：首先对载玻片进行亲水处理，之后将氧化石墨烯粘接剂均匀涂覆在两片载玻片之间，待其干燥后，两片载玻片通过氧化石墨烯实现粘接。
通过对6个粘结试样进行粘结性能测试，发现C/O小于等于3:1情况下，具有较好的粘结效果，而C/O为4:1、5:1的两个粘结试样粘结效果不佳。
实施例1-3
本实施例研究了不同尺寸分布的氧化石墨烯粘结剂的粘结性能，其条件如下：
采用的氧化石墨烯中，尺寸分布如表1所示；整体的C/O比2.5:1，单层氧化石墨烯含量为91.6％。按照4mg/ml的浓度配置氧化石墨烯水溶液，并将其对两片载玻片实现粘结，粘结方法为：首先对载玻片进行亲水处理，之后将氧化石墨烯粘接剂均匀涂覆在两片载玻片之间，待其干燥后，两片载玻片通过氧化石墨烯实现粘接。
不同尺寸分布下的粘接效果如表1所示。从表中可以看出，尺寸小于5um的氧化石墨烯片的量应不多于10％，且尺寸大于30um的氧化石墨烯片的量应不小于60％。
表1
Figure PCTCN2018078765-appb-000001
实施例1-4：
(1)取C/O比等于3:1、单层率为81.4％的氧化石墨烯，尺寸小于5um的氧化石墨烯片的量为6％，尺寸大于30um的氧化石墨烯片的量为71％，其余部分尺寸为5-30um之间；配置浓度为4mg/ml的氧化石墨烯分散液，分散相为水，将其作为石墨烯粘接溶液。
(2)将石墨烯粘接溶液均匀涂覆在聚对苯二甲酸乙二醇酯(PET)材料表面，待其干燥后即实现粘接。经测试粘接强度达0.11MPa。
实施例1-5：
(1)取C/O比等于2.3:1的氧化石墨烯，尺寸小于5um的氧化石墨烯片的量为10％，尺寸大于30um的氧化石墨烯片的量为87％，其余部分尺寸为5-30um之间；配置浓度为16mg/ml的氧化石墨烯分散液，分散相为水，将其作为石墨烯粘接溶液。
(2)将石墨烯粘接溶液均匀涂覆在聚酰亚胺(PI)材料表面，待其干燥后即实现粘接。经测试粘接强度达0.36MPa。
实施例1-6
(1)取C/O比等于0.5:1、单层率为96.8％的氧化石墨烯，尺寸小于5um的氧化石墨烯片的量为3％，尺寸大于30um的氧化石墨烯片的量为94％，其余部分尺寸为5-30um之间；配置浓度为18mg/ml的氧化石墨烯分散液，分散相为DMF，将其作为石墨烯粘接溶液。
(2)将石墨烯粘接溶液均匀涂覆在玻璃材料表面，待其干燥后即实现粘接。经测试粘接 强度达0.0.45MPa。
实施例1-7
(1)取C/O比等于1.7:1、单层率为88.9％的氧化石墨烯，尺寸均控制在50～80um；配置浓度为18mg/ml的氧化石墨烯分散液，分散相为水，将其作为石墨烯粘接溶液。
(2)将石墨烯粘接溶液均匀涂覆在纸材料表面，待其干燥后即实现粘接。经测试粘接强度达0.62MPa。
实施例1-8
(1)取C/O比等于3:1、单层率为97.5％的氧化石墨烯，尺寸小于5um的氧化石墨烯片的量为4％，尺寸大于30um的氧化石墨烯片的量为91％，其余部分尺寸为5-30um之间；配置浓度为18mg/ml的氧化石墨烯分散液，分散相为水，将其作为石墨烯粘接溶液。
(2)将石墨烯粘接溶液均匀涂覆在陶瓷材料表面，待其干燥后即实现粘接。经测试粘接强度达0.22MPa。
实施例2-1
本实施例研究了不同浓度的氧化石墨烯溶液对最终石墨烯粘结性能的影响，具体如下：
采用的氧化石墨烯溶液中，尺寸小于5um的氧化石墨烯片的量为8±1％，尺寸大于30um的氧化石墨烯片的量为70±3％，其余部分尺寸为5-30um之间；整体的C/O比2:1，单层氧化石墨烯占在氧化石墨烯总量的98.8％。
分别按照2-20mg/ml的浓度配置氧化石墨烯水溶液，并将其对两片载玻片实现粘结，粘结方法为：首先对载玻片进行亲水处理，之后将氧化石墨烯粘接剂均匀涂覆在两片载玻片之间，待其干燥后在95℃下利用水合肼蒸气进行化学还原，还原后的石墨烯的C/O为6:1左右，两片载玻片通过石墨烯实现粘接。
不同浓度下的粘接效果如图5所示。从图中可以看出，氧化石墨烯浓度在4mg/ml以上，具有较好的粘接效果。
实施例2-2
本实施例研究了不同尺寸分布的氧化石墨烯对最终石墨烯粘结性能的影响，具体如下：
采用的氧化石墨烯中，尺寸分布如表2所示；整体的C/O比2:1，单层氧化石墨烯含量为95.8％。按照4mg/ml的浓度配置氧化石墨烯水溶液，并将其对两片载玻片实现粘结，粘结方法为：首先对载玻片进行亲水处理，之后将氧化石墨烯粘接剂均匀涂覆在两片载玻片之间，待其干燥后在90℃下利用氢碘酸蒸汽进行化学还原，还原后的石墨烯的C/O为5:1左右，两片载玻片通过石墨烯实现粘接。
不同尺寸分布下的粘接效果如表2所示。从表中可以看出，尺寸小于5um的氧化石墨烯片的量应少于等于10％，且尺寸大于30um的氧化石墨烯片的量应不小于65％。
表2
Figure PCTCN2018078765-appb-000002
实施例2-3
本实施例研究了不同还原程度的石墨烯(不同C/O值)对最终粘结性能的影响，具体如下：
采用的氧化石墨烯尺寸在30～80um，C/O变化范围为2:1～3:1，单层氧化石墨烯占在氧化石墨烯总量的84.1％。按照8mg/ml的浓度配置氧化石墨烯水溶液，并将其对两片ITO实现粘结，粘结方法为：首先对ITO进行亲水处理，之后将氧化石墨烯粘接剂均匀涂覆在两片ITO之间，待其干燥后在真空状态下按1℃/min升温速率缓慢升温至300℃进行热还原，或者水合肼蒸气化学还原，通过对氧化石墨烯C/O的选择以及还原方法的控制，使还原后的石墨烯的C/O比分别为3.5:1、4:1、5:1：6:1；
一方面，通过对4个粘结试样进行粘结性能测试，发现随着C/O比的升高(还原程度的增加)，粘结效果有所下降，然而，由于石墨烯片的尺寸分布，以及单层率等优势，使得其始终保持较好的粘结效果；另一方面，对两个粘结后的ITO的导电性进行测试，测试结果表明，随着C/O比的升高，粘接层的导电性显著提升，在C/O比为4:1时，即达到了ITO本身的导电性能。
通过以上实施例可知，本领域技术人员利用本发明的粘结方法，可根据对实际粘结效果以及导电率的要求，对碳氧比以及尺寸分布、氧化石墨烯前躯体浓度进行调整，以实现完好粘结。例如，对导电率要求高的，需要还原后的石墨烯具备高碳氧比，此时，即可通过提高大尺寸石墨烯片的含量、或提高氧化石墨烯前躯体浓度来实现粘结。
实施例2-4
(1)取单层率为81.4％的氧化石墨烯，尺寸小于5um的氧化石墨烯片的量为6％，尺寸大于30um的氧化石墨烯片的量为87％，其余部分尺寸为5-30um之间；配置浓度为4mg/ml的氧化石墨烯分散液，分散相为水，将其作为石墨烯粘接溶液。
(2)将石墨烯粘接溶液均匀涂覆在聚苯胺材料表面，待其干燥后即实现粘接。经测试粘接强度达0.11MPa。
(3)经氢碘酸溶液90℃还原处理30分钟后，测得其C/O为4:1，经测试在粘接处粘接强度达0.04MPa，且具有优异的导电性，并可耐酸、耐碱和耐盐。
实施例2-5
(1)取单层率为96.3％的氧化石墨烯，尺寸小于5um的氧化石墨烯片的量为3％，尺寸大于30um的氧化石墨烯片的量为91％，其余部分尺寸为5-30um之间；配置浓度为16mg/ml的氧化石墨烯分散液，分散相为水，将其作为石墨烯粘接溶液。
(2)将石墨烯粘接溶液均匀涂覆在铁片表面，待其干燥后即实现粘接。经测试粘接强度达0.36MPa。
(3)经水合肼溶液70℃还原处理20分钟后，测得其C/O为4:1，经测试在粘接处粘接强度达0.04MPa，且具有导电性，并可耐酸、耐碱和耐盐。
实施例2-6
(1)取单层率为97.2％的氧化石墨烯，尺寸均控制在50～80um；配置浓度为12mg/ml的氧化石墨烯分散液，分散相为DMF，将其作为石墨烯粘接溶液。
(2)将石墨烯粘接溶液均匀涂覆在导电玻璃材料表面，待其干燥后即实现粘接。经测试粘接强度达0.11MPa。
(3)按1℃/min升温速率缓慢升温至200℃热还原处理20分钟后，测得其C/O为4:1，经测试在粘接处粘接强度达0.03MPa，且具有导电性，并可耐酸、耐碱和耐盐。
实施例2-7
(1)取单层率为95.4％的氧化石墨烯，尺寸均控制在50～80um；配置浓度为18mg/ml的氧化石墨烯分散液，分散相为水，将其作为石墨烯粘接溶液。
(2)将石墨烯粘接溶液均匀涂覆在导电陶瓷材料表面，待其干燥后即实现粘接。经测试粘接强度达0.22MPa。
(3)经氢碘酸溶液80℃还原处理60分钟后，测得其C/O为5:1，经测试在粘接处粘接强度达0.02MPa，且具有导电性，并可耐酸、耐碱和耐盐。
实施例3-1：
(1)将商业化碳纤维T800H置于丙酮中以80℃回流72h除去表面上浆剂。再先后在过氧化氢中110℃浸泡2h、浓硝酸中115℃浸泡12h，最后用水清洗烘干，得到表面氧化改性的碳纤维。
(2)通过如图6所示的连续涂覆设备，使用氧化石墨烯水分散液(氧化石墨烯片大小为40～50μm，浓度如表3所示)对碳纤维表面进行反复涂覆干燥(干燥温度为40℃)，循环次数为15次，得到表面涂覆有氧化石墨烯的碳纤维。
(3)将30根涂覆有氧化石墨烯的碳纤维通过水槽浸润溶胀，同时从水中提出，纤维由 于受到水的表面张力作用而自发相互靠近成丝束。随后将丝束室温干燥，水挥发使得碳纤维表层的氧化石墨烯片相互融合，从而使碳纤维间相互交联。
(4)将氧化石墨烯交联的碳纤维丝束进行3000℃热还原，得到高性能的石墨烯交联碳纤维丝束。
经过以上步骤，30根碳纤维丝束轴向完全由片层相互堆叠的石墨烯交联。丝束密度为1.7g/cm 3，拉伸强度为4.9GPa，电导率为0.8×10 5S/m，导热率为43W/mK。
表3
Figure PCTCN2018078765-appb-000003
由表3可以看出，涂覆相同次数下，氧化石墨烯的浓度为7mg/ml时，氧化石墨烯涂层在碳纤维表面的厚度为3μm，沿纤维轴向均匀分布，得到的碳纤维丝束的密度、拉伸强度、导电率、导热率最高，交联效果最好。氧化石墨烯的浓度越小，氧化石墨烯在碳纤维表面的厚度越小，得到的碳纤维丝束的密度、拉伸强度、导电率、导热率越小，交联效果越差。氧化石墨烯的浓度越高，氧化石墨烯在碳纤维表面厚度越大，厚度沿纤维轴向分布不均匀，得到的碳纤维丝束的密度、拉伸强度、导电率、导热率越小，交联效果越差。
实施例3-2：
步骤(1)与实施例3-1相同。
(2)通过连续涂覆设备，使用浓度为7mg/ml的氧化石墨烯水分散液(氧化石墨烯片大小为40～50μm)对碳纤维表面进行反复涂覆干燥(干燥温度为25℃)，循环次数为20次，得到表面涂覆有氧化石墨烯的碳纤维。其中，氧化石墨烯涂层的厚度约为3.8μm，沿纤维轴向均匀分布。
(3)将1000根左右(计量法)涂覆有氧化石墨烯的碳纤维通过水槽浸润溶胀，同时从水中提出，纤维由于受到水的表面张力作用而自发相互靠近成丝束。随后将丝束室温干燥，水挥发使得碳纤维表层的氧化石墨烯片相互融合，从而使碳纤维间相互交联。
(4)将氧化石墨烯交联的碳纤维丝束进行氢碘酸还原，得到石墨烯交联的碳纤维丝束。
经过以上步骤，1000根碳纤维丝束轴向完全由片层相互堆叠的石墨烯交联。丝束密度为1.4g/cm 3，拉伸强度为3.9GPa，电导率为6.0×10 4S/m，导热率为18W/mK。
实施例3-3：
(1)将商业化碳纤维T800H置于丙酮中以57℃回流72h除去表面上浆剂。再先后在过氧化氢中108℃浸泡2h、浓硝酸中115℃浸泡12h，最后用水清洗烘干，得到表面氧化改性的碳纤维。
(2)通过连续涂覆设备，使用浓度为7mg/ml的氧化石墨烯水分散液(氧化石墨烯片大小为40～50μm)对碳纤维表面进行反复涂覆干燥(干燥温度为40℃)，循环次数为15次，得到表面涂覆有氧化石墨烯的碳纤维。其中，氧化石墨烯涂层的厚度约为3μm，沿纤维轴向均匀分布。
(3)将涂覆有氧化石墨烯的碳纤维编织成50×50的编织布(编织方法为平纹编织)，随后在水池中浸泡3min后取出，60℃烘干，水挥发使得编织布中碳纤维的接触节点处表层的氧化石墨烯片相互融合，从而使碳纤维间相互交联，得到氧化石墨烯交联的碳纤维编织布。
(4)将氧化石墨烯交联的碳纤维布进行3000℃热还原，得到高性能的石墨烯交联碳纤维编织布。
经过以上步骤，编织布的接触节点处碳纤维完全由片层相互堆叠的石墨烯交联。拉伸强度为4.1GPa，电导率为0.4×10 5S/m，热导率为36W/mK。
实施例3-4：
(1)将商业化碳纤维T800H置于丙酮中以100℃回流6h除去表面上浆剂。再先后在过氧化氢中108℃浸泡2h、浓硝酸中115℃浸泡12h，最后用水清洗烘干，得到表面氧化改性的碳纤维。
(2)通过连续涂覆设备，使用浓度为7mg/ml的氧化石墨烯水分散液(氧化石墨烯片大小为40～50μm)对碳纤维表面进行反复涂覆干燥(干燥温度为50℃)，循环次数为15次，得到表面涂覆有氧化石墨烯的碳纤维。其中，氧化石墨烯涂层的厚度约为3μm，沿纤维轴向均匀分布。
(3)将涂覆有氧化石墨烯的碳纤维切成短纤并分散于水溶液中，随后抽滤，60℃烘干，水挥发使得无纺布中碳纤维的接触节点处表层的氧化石墨烯片相互融合，从而使碳纤维间相互交联，得到氧化石墨烯交联的碳纤维无纺布。
(4)将氧化石墨烯交联的碳纤维布进行3000℃热还原，得到高性能的石墨烯交联碳纤维无纺布。
经过以上步骤，无纺布的接触节点处碳纤维完全由片层相互堆叠的石墨烯交联。拉伸强度为600MPa，电导率为0.6×10 5S/m，热导率为42W/mK。
此外，通过比较实施例3-1～3-4发现，实施例3-1和3-2获得的碳纤维丝束中，相比于其他实施例，石墨烯片层分散更为均一，这说明实施例3-1的氧化改性方案改性的碳纤维与氧化石墨烯表面的活性基团具有更好的亲和性。
实施例4-1：
(1)使用氧化石墨烯的水分散液对氮化硼纤维表面进行反复涂覆干燥，循环次数为15次，得到表面涂覆有氧化石墨烯的氮化硼纤维。氧化石墨烯层厚度为3μm；
(2)将步骤(3)得到的涂覆氧化石墨烯的氮化硼纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100℃。
(3)将步骤(2)得到的氧化石墨烯交联氮化硼纤维置于含有水合肼的封闭釜中，80℃下还原12小时。
经以上步骤，石墨烯包覆在氮化硼纤维表面，氮化硼纤维表面与石墨烯片通过范德华力和氢键连接。氮化硼纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为90.9g/m 2,断裂强度为1.98GPa，在25℃水中浸泡24h后断裂强度保持率为86％，导电率为2.3×10 4S/m，导热率为29W/mK。
表4
Figure PCTCN2018078765-appb-000004
此外，氧化石墨烯浓度和涂层厚度是经反复试验得到的最优结果。由表4可以看出，涂覆相同次数下，氧化石墨烯的浓度为7mg/ml时，氧化石墨烯涂层在氮化硼纤维表面的厚度为3μm，得到的氮化硼纤维无纺布的断裂强度、导电率、导热率最高，防水解能力最好，交联效果最好。氧化石墨烯的浓度越小，氧化石墨烯在氮化硼纤维表面的厚度越小，得到的氮化硼纤维无纺布的断裂强度、导电率、导热率越小，交联效果和耐水性越差。氧化石墨烯的浓度越高，氧化石墨烯在氮化硼纤维表面厚度越大，厚度分布不均匀，交联强度下降，得到的氮化硼纤维无纺布的断裂强度、导电率、导热率降低，防水解能力降低。
实施例4-2：
(1)使用氧化石墨烯的N,N-二甲基甲酰胺分散液对氮化硼纤维表面进行反复涂覆干燥，循环次数为13次，得到表面涂覆有氧化石墨烯的氮化硼纤维。氧化石墨烯层厚度为3μm；
(2)将步骤(1)得到的涂覆氧化石墨烯的氮化硼纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100℃。
(3)将步骤(2)得到的氧化石墨烯交联氮化硼纤维置于含有水合肼的封闭釜中，80℃下还原12小时。
经以上步骤，石墨烯包覆在氮化硼纤维表面，氮化硼纤维表面与石墨烯片通过范德华力和氢键连接。氮化硼纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为91.1g/m 2,断裂强度为1.94GPa，在25℃水中浸泡24h后断裂强度保持率为84％，导电率为1.7×10 4S/m，导热率为26W/mK。
实施例4-3：
(1)使用氧化石墨烯的乙醇分散液对氮化硼纤维表面进行反复涂覆干燥，循环次数为16次，得到表面涂覆有氧化石墨烯的氮化硼纤维。氧化石墨烯层厚度为3μm；
(2)将步骤(3)得到的涂覆氧化石墨烯的氮化硼纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100℃。
(3)将步骤(2)得到的氧化石墨烯交联氮化硼纤维置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在氮化硼纤维表面，氮化硼纤维表面与石墨烯片通过范德华力和氢键连接。氮化硼纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为91.7g/m 2,断裂强度为1.99GPa，在25℃水中浸泡24h后断裂强度保持率为88％，导电率为2.7×10 4S/m，导热率为30W/mK。
实施例4-4：
(1)使用氧化石墨烯的乙二醇分散液对平行排列的氮化硼纤维表面进行反复涂覆干燥，循环次数为12次，得到表面涂覆有氧化石墨烯的氮化硼纤维长纤。氧化石墨烯层厚度为3μm；(2)将步骤(1)得到的涂覆氧化石墨烯的氮化硼纤维长纤置于乙二醇中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，干燥温度低于100℃，使乙二醇挥发。
(3)将步骤(2)得到的氧化石墨烯交联氮化硼纤维长纤置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在氮化硼纤维表面，氮化硼纤维表面与石墨烯片通过范德华力和氢键连接。氮化硼纤维之间通过包覆在表面的石墨烯实现交联，复合纤维平行排列形成无捻纤结构，断裂强度为2.09GPa，在25℃水中浸泡24h后断裂强度保持率为85％，在导电率为2.4×10 4S/m，导热率为26W/mK。
实施例4-5：
(1)使用氧化石墨烯的水分散液对平行排列的氮化硼纤维表面进行反复涂覆干燥，循环次数为15次，得到表面涂覆有氧化石墨烯的氮化硼纤维。氧化石墨烯层厚度为3μm；
(2)将步骤(1)得到的涂覆氧化石墨烯的氮化硼纤维置于乙二醇中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，干燥温度低于100℃，使乙二醇挥发。
(3)将步骤(2)得到的氧化石墨烯交联氮化硼纤维长纤置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在氮化硼纤维表面，氮化硼纤维表面与石墨烯片通过范德华力和氢键连接。氮化硼纤维之间通过包覆在表面的石墨烯实现交联，复合纤维平行排列形成无捻纤结构，断裂强度为2.14GPa，在25℃水中浸泡24h后断裂强度保持率为85％，在导电率为3.1×10 4S/m，导热率为28W/mK。
实施例5-1：
(1)将石英纤维置于甲苯中浸泡，加热至300℃保持10min，烘干；
(2)使用氧化石墨烯的水分散液对步骤(1)得到的石英纤维表面进行反复涂覆干燥，循环次数为15次，得到表面涂覆有氧化石墨烯的石英纤维。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的石英纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100℃。
(4)将步骤(3)得到的氧化石墨烯交联石英纤维置于含有水合肼的封闭釜中，80℃下还原12小时。
经以上步骤，石墨烯包覆在石英纤维表面，石英纤维表面与石墨烯片通过范德华力和氢键连接。石英纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为87.1g/m 2,断裂强度为2.2GPa，在PH＝12的碱液中浸泡12h强度保持率在89％，导电率为4.9×10 4S/m，导热率为23W/mK。
表5
Figure PCTCN2018078765-appb-000005
此外，氧化石墨烯浓度和涂层厚度是经反复试验得到的最优结果。由表5可以看出，涂覆相同次数下，氧化石墨烯的浓度为7mg/ml时，氧化石墨烯涂层在石英纤维表面的厚度为3μm，得到的石英纤维无纺布的断裂强力、导电率、导热率最高，交联效果最好。氧化石墨烯的浓度越小，氧化石墨烯在石英纤维表面的厚度越小，得到的石英纤维无纺布的断裂强力、导电率、导热率越小，交联效果和耐碱性越差。氧化石墨烯的浓度越高，氧化石墨烯在石英 纤维表面厚度越大，厚度分布不均匀，交联强度下降，得到的石英纤维无纺布的断裂强力、导电率、导热率降低。
实施例5-2：
(1)将石英纤维置于甲苯中浸泡，加热至300℃保持10min，烘干；
(2)使用氧化石墨烯的N,N-二甲基甲酰胺分散液对步骤(1)得到的石英纤维表面进行反复涂覆干燥，循环次数为13次，得到表面涂覆有氧化石墨烯的石英纤维。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的石英纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100℃。
(4)将步骤(3)得到的氧化石墨烯交联石英纤维置于含有水合肼的封闭釜中，80℃下还原12小时。
经以上步骤，石墨烯包覆在石英纤维表面，石英纤维表面与石墨烯片通过范德华力和氢键连接。石英纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为88.3g/m 2,断裂强度为2.1GPa，在PH＝12的碱液中浸泡12h强度保持率在87％，导电率为5.1×10 4S/m，导热率为25W/mK。
实施例5-3：
(1)将石英纤维置于甲苯中浸泡，加热至300℃保持10min，烘干；
(2)使用氧化石墨烯的乙醇分散液对步骤(1)得到的石英纤维表面进行反复涂覆干燥，循环次数为16次，得到表面涂覆有氧化石墨烯的石英纤维。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的石英纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100℃。
(4)将步骤(3)得到的氧化石墨烯交联石英纤维置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在石英纤维表面，石英纤维表面与石墨烯片通过范德华力和氢键连接。石英纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为86.4g/m 2,断裂强度为2.3GPa，在PH＝12的碱液中浸泡12h强度保持率在82％，导电率为3.9×10 4S/m，导热率为22W/mK。
实施例5-4：
(1)将平行排列的石英纤维置于甲苯中浸泡，加热至300℃保持10min，烘干；
(2)使用氧化石墨烯的乙二醇分散液对步骤(1)得到的石英纤维表面进行反复涂覆干燥，循环次数为12次，得到表面涂覆有氧化石墨烯的石英纤维长纤。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的石英纤维长纤置于乙二醇中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，干燥温度低于100℃，使乙二醇挥发。
(4)将步骤(3)得到的氧化石墨烯交联石英纤维长纤置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在石英纤维表面，石英纤维表面与石墨烯片通过范德华力和氢键连接。石英纤维之间通过包覆在表面的石墨烯实现交联，复合纤维平行排列形成无捻纤结构，断裂强度为2.7GPa，在PH＝12的碱液中浸泡12h强度保持率在84％，导电率为6.8×10 4S/m，导热率为29W/mK。
实施例5-5：
(1)将平行排列的石英纤维置于甲苯中浸泡，加热至300℃保持10min，烘干；
(2)使用氧化石墨烯的水分散液对步骤(1)得到的石英纤维表面进行反复涂覆干燥，循环次数为15次，得到表面涂覆有氧化石墨烯的石英纤维。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的石英纤维置于乙二醇中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，干燥温度低于100℃，使乙二醇挥发。
(4)将步骤(3)得到的氧化石墨烯交联石英纤维长纤置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在石英纤维表面，石英纤维表面与石墨烯片通过范德华力和氢键连接。石英纤维之间通过包覆在表面的石墨烯实现交联，复合纤维平行排列形成无捻纤结构，断裂强度为2.8GPa，在PH＝12的碱液中浸泡12h强度保持率在82％，导电率为6.3×10 4S/m，导热率为27W/mK。
实施例6-1：
(1)使用氧化石墨烯的水分散液对截面呈圆形的碳化硅纤维表面进行反复涂覆干燥，循环次数为15次，得到表面涂覆有氧化石墨烯的碳化硅纤维。氧化石墨烯层厚度为3μm；
(2)将步骤(3)得到的涂覆氧化石墨烯的碳化硅纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100℃。
(3)将步骤(2)得到的氧化石墨烯交联碳化硅纤维置于含有水合肼的封闭釜中，80℃下还原12小时。
经以上步骤，石墨烯包覆在碳化硅纤维表面，碳化硅纤维表面与石墨烯片通过范德华力连接。碳化硅纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为111g/m 2,断裂强度为2.91GPa，导电率为2.8×10 4S/m，导热率为22W/mK。
表6
Figure PCTCN2018078765-appb-000006
Figure PCTCN2018078765-appb-000007
此外，氧化石墨烯浓度和涂层厚度是经反复试验得到的最优结果。由表6可以看出，涂覆相同次数下，氧化石墨烯的浓度为7mg/ml时，氧化石墨烯涂层在碳化硅纤维表面的厚度为3μm，得到的碳化硅纤维无纺布的断裂强度、导电率、导热率最高，交联效果最好。氧化石墨烯的浓度越小，氧化石墨烯在碳化硅纤维表面的厚度越小，得到的碳化硅纤维无纺布的断裂强度、导电率、导热率越小，交联效果越差。氧化石墨烯的浓度越高，氧化石墨烯在碳化硅纤维表面厚度越大，厚度分布不均匀，交联强度下降，得到的碳化硅纤维无纺布的断裂强度、导电率、导热率降低。
实施例6-2：
(1)使用氧化石墨烯的N,N-二甲基甲酰胺分散液对截面呈圆形的含铁碳化硅纤维表面进行反复涂覆干燥，循环次数为13次，得到表面涂覆有氧化石墨烯的碳化硅纤维。氧化石墨烯层厚度为3μm；
(2)将步骤(1)得到的涂覆氧化石墨烯的碳化硅纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100℃。
(3)将步骤(2)得到的氧化石墨烯交联碳化硅纤维置于含有水合肼的封闭釜中，80℃下还原12小时。
经以上步骤，石墨烯包覆在碳化硅纤维表面，碳化硅纤维表面与石墨烯片通过范德华力连接。碳化硅纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为112.6g/m 2,断裂强度为2.89GPa，导电率为2.5×10 4S/m，导热率为23W/mK。
实施例6-3：
(1)使用氧化石墨烯的乙醇分散液对截面呈三叶形的含钛碳化硅纤维表面进行反复涂覆干燥，循环次数为16次，得到表面涂覆有氧化石墨烯的碳化硅纤维。氧化石墨烯层厚度为3μm；
(2)将步骤(3)得到的涂覆氧化石墨烯的碳化硅纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100℃。
(3)将步骤(2)得到的氧化石墨烯交联碳化硅纤维置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在碳化硅纤维表面，碳化硅纤维表面与石墨烯片通过范德华力连接。碳化硅纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为113.5g/m 2,断裂强度为2.93GPa，导电率为3.5×10 4S/m，导热率为24W/mK。
实施例6-4：
(1)使用氧化石墨烯的乙二醇分散液对截面呈圆形的平行排列碳化硅纤维表面进行反复 涂覆干燥，循环次数为12次，得到表面涂覆有氧化石墨烯的碳化硅纤维长纤。氧化石墨烯层厚度为3μm；
(2)将步骤(1)得到的涂覆氧化石墨烯的碳化硅纤维长纤置于乙二醇中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，干燥温度低于100℃，使乙二醇挥发。
(3)将步骤(2)得到的氧化石墨烯交联碳化硅纤维长纤置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在碳化硅纤维表面，碳化硅纤维表面与石墨烯片通过范德华力连接。碳化硅纤维之间通过包覆在表面的石墨烯实现交联，复合纤维平行排列形成无捻纤结构，断裂强度为2.92GPa，在导电率为5.7×10 4S/m，导热率为27W/mK。
实施例6-5：
(1)使用氧化石墨烯的水分散液对平行排列的中空形含铝碳化硅纤维表面进行反复涂覆干燥，循环次数为15次，得到表面涂覆有氧化石墨烯的碳化硅纤维。氧化石墨烯层厚度为3μm；
(2)将步骤(1)得到的涂覆氧化石墨烯的碳化硅纤维置于乙二醇中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，干燥温度低于100℃，使乙二醇挥发。
(3)将步骤(2)得到的氧化石墨烯交联碳化硅纤维长纤置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在碳化硅纤维表面，碳化硅纤维表面与石墨烯片通过范德华力连接。碳化硅纤维之间通过包覆在表面的石墨烯实现交联，复合纤维平行排列形成无捻纤结构，断裂强度为2.86GPa，导电率为4.8×10 4S/m，导热率为27W/mK。
实施例7-1：
(1)将玄武岩纤维置于甲苯中加热至250℃，超声清洗10min，除去表面浸润剂和油剂，烘干；
(2)使用氧化石墨烯的水分散液对步骤(1)得到的玄武岩纤维表面进行反复涂覆干燥，循环次数为15次，得到表面涂覆有氧化石墨烯的玄武岩纤维。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的玄武岩纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100摄氏度。
(4)将步骤(3)得到的氧化石墨烯交联玄武岩纤维置于含有水合肼的封闭釜中，80℃下还原12小时。
经以上步骤，石墨烯包覆在玄武岩纤维表面，玄武岩纤维表面与石墨烯片通过范德华力和氢键连接。玄武岩纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为86.1g/m 2,断裂强度为3.24GPa，PH＝12的碱液中浸泡6h强度保持率为89％，导电率为1.6×10 4S/m，导热率为29W/mK。
表7
Figure PCTCN2018078765-appb-000008
此外，氧化石墨烯浓度和涂层厚度是经反复试验得到的最优结果。由表7可以看出，涂覆相同次数下，氧化石墨烯的浓度为7mg/ml时，氧化石墨烯涂层在玄武岩纤维表面的厚度为3μm，得到的玄武岩纤维无纺布的断裂强度、导电率、导热率最高，交联效果最好。氧化石墨烯的浓度越小，氧化石墨烯在玄武岩纤维表面的厚度越小，得到的玄武岩纤维无纺布的断裂强度、导电率、导热率越小，交联效果越差。氧化石墨烯的浓度越高，氧化石墨烯在玄武岩纤维表面厚度越大，厚度分布不均匀，交联强度下降，得到的玄武岩纤维无纺布的断裂强度、导电率、导热率降低。
实施例7-2：
(1)将玄武岩纤维置于甲苯中加热至250℃，超声清洗10min，除去表面浸润剂和油剂，烘干；
(2)使用氧化石墨烯的N,N-二甲基甲酰胺分散液对步骤(1)得到的玄武岩纤维表面进行反复涂覆干燥，循环次数为13次，得到表面涂覆有氧化石墨烯的玄武岩纤维。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的玄武岩纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100摄氏度。
(4)将步骤(3)得到的氧化石墨烯交联玄武岩纤维置于含有水合肼的封闭釜中，80℃下还原12小时。
经以上步骤，石墨烯包覆在玄武岩纤维表面，玄武岩纤维表面与石墨烯片通过范德华力和氢键连接。玄武岩纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为85.2g/m 2,断裂强度为3.21GPa，PH＝12的碱液中浸泡6h强度保持率为87％，导电率为1.3×10 4S/m，导热率为28W/mK。
实施例7-3：
(1)将玄武岩纤维置于甲苯中加热至250℃，超声清洗10min，除去表面浸润剂和油剂，烘干；
(2)使用氧化石墨烯的乙醇分散液对步骤(1)得到的玄武岩纤维表面进行反复涂覆干燥，循环次数为16次，得到表面涂覆有氧化石墨烯的玄武岩纤维。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的玄武岩纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100摄氏度。
(4)将步骤(3)得到的氧化石墨烯交联玄武岩纤维置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在玄武岩纤维表面，玄武岩纤维表面与石墨烯片通过范德华力和氢键连接。玄武岩纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为84.6g/m 2,断裂强度为3.23GPa，PH＝12的碱液中浸泡6h强度保持率为85％，导电率为2.1×10 4S/m，导热率为27W/mK。
实施例7-4：
(1)将平行排列的玄武岩长纤维置于甲苯中加热至250℃，超声清洗20min，除去表面浸润剂和油剂，烘干；
(2)使用氧化石墨烯的乙二醇分散液对步骤(1)得到的玄武岩纤维表面进行反复涂覆干燥，循环次数为12次，得到表面涂覆有氧化石墨烯的玄武岩纤维长纤。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的玄武岩纤维长纤置于乙二醇中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，干燥温度低于100摄氏度，使乙二醇挥发。
(4)将步骤(3)得到的氧化石墨烯交联玄武岩纤维长纤置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在玄武岩纤维表面，玄武岩纤维表面与石墨烯片通过范德华力和氢键连接。玄武岩纤维之间通过包覆在表面的石墨烯实现交联，复合纤维平行排列形成无捻纤结构，断裂强度为3.42GPa，PH＝12的碱液中浸泡6h强度保持率为85％，导电率为3.9×10 4S/m，导热率为31W/mK。
实施例7-5：
(1)将平行排列的玄武岩长纤维置于甲苯中加热至250℃，超声清洗20min，除去表面浸润剂和油剂，烘干；
(2)使用氧化石墨烯的水分散液对步骤(1)得到的玄武岩纤维表面进行反复涂覆干燥，循环次数为15次，得到表面涂覆有氧化石墨烯的玄武岩纤维。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的玄武岩纤维置于乙二醇中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，干燥温度低于100摄氏度，使乙二醇挥发。
(4)将步骤(3)得到的氧化石墨烯交联玄武岩纤维长纤置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在玄武岩纤维表面，玄武岩纤维表面与石墨烯片通过范德华力和氢键连接。玄武岩纤维之间通过包覆在表面的石墨烯实现交联，复合纤维平行排列形成无捻纤结构，断裂强度为3.45GPa，PH＝12的碱液中浸泡6h强度保持率为84％，导电率为4.4×10 4S/m，导热率为26W/mK。
实施例8-1：
(1)使用氧化石墨烯的水分散液对氧化铝纤维表面进行反复涂覆干燥，循环次数为15次，得到表面涂覆有氧化石墨烯的氧化铝纤维。氧化石墨烯层厚度为3μm；
(2)将步骤(3)得到的涂覆氧化石墨烯的氧化铝纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100℃。
(3)将步骤(2)得到的氧化石墨烯交联氧化铝纤维置于含有水合肼的封闭釜中，80℃下还原12小时。
经以上步骤，石墨烯包覆在氧化铝纤维表面，氧化铝纤维表面与石墨烯片通过范德华力和氢键连接。氧化铝纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为96.5g/m 2,断裂强度为2.23GPa，导电率为3.7×10 4S/m，导热率为24W/mK。
表8
Figure PCTCN2018078765-appb-000009
此外，氧化石墨烯浓度和涂层厚度是经反复试验得到的最优结果。由表8可以看出，涂覆相同次数下，氧化石墨烯的浓度为7mg/ml时，氧化石墨烯涂层在氧化铝纤维表面的厚度为3μm，得到的氧化铝纤维无纺布的断裂强度、导电率、导热率最高，交联效果最好。氧化石墨烯的浓度越小，氧化石墨烯在氧化铝纤维表面的厚度越小，得到的氧化铝纤维无纺布的断裂强度、导电率、导热率越小，交联效果和耐碱性越差。氧化石墨烯的浓度越高，氧化石墨烯在氧化铝纤维表面厚度越大，厚度分布不均匀，交联强度下降，得到的氧化铝纤维无纺布的断裂强度、导电率、导热率降低。
实施例8-2：
(1)使用氧化石墨烯的N,N-二甲基甲酰胺分散液对氧化铝纤维表面进行反复涂覆干燥，循环次数为13次，得到表面涂覆有氧化石墨烯的氧化铝纤维。氧化石墨烯层厚度为3μm；
(2)将步骤(1)得到的涂覆氧化石墨烯的氧化铝纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100℃。
(3)将步骤(2)得到的氧化石墨烯交联氧化铝纤维置于含有水合肼的封闭釜中，80℃下还原12小时。
经以上步骤石墨烯包覆在氧化铝纤维表面，氧化铝纤维表面与石墨烯片通过范德华力和氢键连接。氧化铝纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为95.6g/m 2,断裂强度为2.3GPa，导电率为4.5×10 4S/m，导热率为25W/mK。
实施例8-3：
(1)使用氧化石墨烯的乙醇分散液对氧化铝纤维表面进行反复涂覆干燥，循环次数为16次，得到表面涂覆有氧化石墨烯的氧化铝纤维。氧化石墨烯层厚度为3μm；
(2)将步骤(3)得到的涂覆氧化石墨烯的氧化铝纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100℃。
(3)将步骤(2)得到的氧化石墨烯交联氧化铝纤维置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在氧化铝纤维表面，氧化铝纤维表面与石墨烯片通过范德华力和氢键连接。氧化铝纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为95.7g/m 2,断裂强度为2.24GPa，导电率为4.1×10 4S/m，导热率为23W/mK。
实施例8-4：
(1)使用氧化石墨烯的乙二醇分散液对平行排列的氧化铝纤维表面进行反复涂覆干燥，循环次数为12次，得到表面涂覆有氧化石墨烯的氧化铝纤维长纤。氧化石墨烯层厚度为3μm；
(2)将步骤(1)得到的涂覆氧化石墨烯的氧化铝纤维长纤置于乙二醇中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，干燥温度低于100℃，使乙二醇挥发。
(3)将步骤(2)得到的氧化石墨烯交联氧化铝纤维长纤置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在氧化铝纤维表面，氧化铝纤维表面与石墨烯片通过范德华力和氢键连接。氧化铝纤维之间通过包覆在表面的石墨烯实现交联，复合纤维平行排列形成无捻纤结构，断裂强度为2.42GPa，在导电率为7.2×10 4S/m，导热率为27W/mK。
实施例8-5：
(1)使用氧化石墨烯的水分散液对平行排列的氧化铝纤维表面进行反复涂覆干燥，循环次数为15次，得到表面涂覆有氧化石墨烯的氧化铝纤维。氧化石墨烯层厚度为3μm；
(2)将步骤(1)得到的涂覆氧化石墨烯的氧化铝纤维置于乙二醇中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，干燥温度低于100℃，使乙二醇挥发。
(3)将步骤(2)得到的氧化石墨烯交联氧化铝纤维长纤置于含有氢碘酸的封闭釜中， 90℃下还原18小时。
经以上步骤，石墨烯包覆在氧化铝纤维表面，氧化铝纤维表面与石墨烯片通过范德华力和氢键连接。氧化铝纤维之间通过包覆在表面的石墨烯实现交联，复合纤维平行排列形成无捻纤结构，断裂强度为2.52GPa，导电率为7.6×10 4S/m，导热率为28W/mK。
实施例9-1：
(1)将玻璃纤维置于丙酮中超声清洗，除去表面油渍，烘干；
(2)使用氧化石墨烯的水分散液对步骤(1)得到的玻璃纤维表面进行反复涂覆干燥，循环次数为15次，得到表面涂覆有氧化石墨烯的玻璃纤维。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的玻璃纤维置于水中进行表面溶胀，然后将纤维相互搭接，经干燥后形成无纺布，干燥温度低于100摄氏度。
(4)将步骤(3)得到的氧化石墨烯交联玻璃纤维置于含有水合肼的封闭釜中，80℃下还原12小时。
经以上步骤，石墨烯包覆在玻璃纤维表面，玻璃纤维表面与石墨烯片通过范德华力和氢键连接，玻璃纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为92.4g/m 2,断裂强力为134N，导电率为6.5×10 4S/m，导热率为26W/mK。
表9
Figure PCTCN2018078765-appb-000010
此外，氧化石墨烯浓度和涂层厚度是经反复试验得到的最优结果。由表9可以看出，涂覆相同次数下，氧化石墨烯的浓度为7mg/ml时，氧化石墨烯涂层在玻璃纤维表面的厚度为3μm，得到的玻璃纤维无纺布的断裂强力、导电率、导热率最高，交联效果最好。氧化石墨烯的浓度越小，氧化石墨烯在玻璃纤维表面的厚度越小，得到的玻璃纤维无纺布的断裂强力、导电率、导热率越小，交联效果越差。氧化石墨烯的浓度越高，氧化石墨烯在玻璃纤维表面厚度越大，厚度分布不均匀，交联强度下降，得到的玻璃纤维无纺布的断裂强力、导电率、导热率降低。
实施例9-2：
(1)将玻璃纤维置于丙酮中超声清洗，除去表面油渍，烘干；
(2)使用氧化石墨烯的N,N-二甲基甲酰胺分散液对步骤(1)得到的玻璃纤维表面进行反复涂覆干燥，循环次数为13次，得到表面涂覆有氧化石墨烯的玻璃纤维。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的玻璃纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100摄氏度。
(4)将步骤(3)得到的氧化石墨烯交联玻璃纤维置于含有水合肼的封闭釜中，80℃下还原12小时。
经以上步骤，石墨烯包覆在玻璃纤维表面，玻璃纤维表面与石墨烯片通过范德华力和氢键连接，玻璃纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为93.1g/m 2,断裂强力为136N，导电率为6.1×10 4S/m，导热率为26W/mK。
实施例9-3：
(1)将玻璃纤维置于丙酮中超声清洗，除去表面油渍，烘干；
(2)使用氧化石墨烯的乙醇分散液对步骤(1)得到的玻璃纤维表面进行反复涂覆干燥，循环次数为16次，得到表面涂覆有氧化石墨烯的玻璃纤维。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的玻璃纤维置于水中进行表面溶胀，然后将纤维相互搭接经干燥后形成无纺布，干燥温度低于100摄氏度。
(4)将步骤(3)得到的氧化石墨烯交联玻璃纤维置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在玻璃纤维表面，玻璃纤维表面与石墨烯片通过范德华力和氢键连接，玻璃纤维之间通过包覆在表面的石墨烯实现交联，复合纤维无序交叠形成无纺布结构，面密度为94.6g/m 2,断裂强力为139N，导电率为5.7×10 4S/m，导热率为23W/mK。
实施例9-4：
(1)将平行排列的玻璃长纤维置于丙酮中超声清洗，除去表面油渍，烘干；
(2)使用氧化石墨烯的乙二醇分散液对步骤(1)得到的玻璃纤维表面进行反复涂覆干燥，循环次数为12次，得到表面涂覆有氧化石墨烯的玻璃纤维长纤。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的玻璃纤维长纤置于乙二醇中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，干燥温度低于100摄氏度，使乙二醇挥发。
(4)将步骤(3)得到的氧化石墨烯交联玻璃纤维长纤置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在玻璃纤维表面，玻璃纤维表面与石墨烯片通过范德华力和氢键连接，玻璃纤维之间通过包覆在表面的石墨烯实现交联，复合纤维平行排列形成无捻纤结构，断裂强度为2.1GPa，导电率为7.3×10 4S/m，导热率为27W/mK。
实施例9-5：
(1)将平行排列的玻璃长纤维置于丙酮中超声清洗，除去表面油渍，烘干；
(2)使用氧化石墨烯的水分散液对步骤(1)得到的玻璃纤维表面进行反复涂覆干燥，循环次数为15次，得到表面涂覆有氧化石墨烯的玻璃纤维。氧化石墨烯层厚度为3μm；
(3)将步骤(2)得到的涂覆氧化石墨烯的玻璃纤维置于乙二醇中进行表面溶胀，然后将纤维合并经干燥后形成所述无捻纱，干燥温度低于100摄氏度，使乙二醇挥发。
(4)将步骤(3)得到的氧化石墨烯交联玻璃纤维长纤置于含有氢碘酸的封闭釜中，90℃下还原18小时。
经以上步骤，石墨烯包覆在玻璃纤维表面，玻璃纤维表面与石墨烯片通过范德华力和氢键连接，玻璃纤维之间通过包覆在表面的石墨烯实现交联，复合纤维平行排列形成无捻纤结构，断裂强度为2.17GPa，导电率为5.9×10 4S/m，导热率为25W/mK。
实施例10-1：
(1)将平均尺寸大于50μm的氧化石墨烯配制成浓度为7mg/mL氧化石墨烯水溶液，用刮膜法，铺厚度为5mm的氧化石墨烯溶液成膜后自然晾干得到氧化石墨烯膜。
(2)将两张尺寸为8cm*8cm的氧化石墨烯膜用液体涂覆进行复合，具体为：在氧化石墨烯膜表面进行均匀涂覆一层浓度为4mg/mL的氧化石墨烯水溶液，然后将多张氧化石墨烯膜沿厚度方向粘接在一起。
(3)将粘接后的氧化石墨烯复合膜放置在烘箱烘干，烘箱的温度为40℃。
(4)将烘干后的氧化石墨烯复合和原石墨烯膜分别置于热压机的热压腔中，以2℃/min的速率升温到200℃后进行热压，重复以下热压过程10次：维持压力20MPa，维持1h；逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-50KPa；然后再以2℃/min的速率升温300℃，保温0.5h，然后进行热压，重复以下热压过程5次：维持压力60MPa，维持1h，逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-50KPa；热压过程结束后自然降温。
(5)将步骤4热压后的膜在惰性气体氛围下以5℃/min的速率升温到2800℃进行进一步热压，保温保压2h；压力为60MPa。降温后，得到高导热的石墨烯膜。
经过以上步骤，氧化石墨烯膜通过粘处的作用力融合，形成整体结构。通过进一步低温热压，高温热压退火还原，最终得到高导热的石墨烯复合膜。而通过涂覆氧化石墨烯溶液粘接成的石墨烯复合膜，因其中的氧化石墨烯还可以填充缝隙处，故缺陷更少，结构更加密实完整。经测试，原石墨烯膜的厚度为26μm，石墨烯片层褶皱密度为92mm/mm 2,且石墨烯片的缺陷极少，其ID/TG＝0.004，孔隙率为8.6％，密度为2.01g/cm 3，面向导热率为1613.2W/mK；通过上述处理后，石墨烯复合膜的厚度为53μm，石墨烯片层褶皱密度为113mm/mm 2,且石墨烯片的缺陷极少，其ID/TG＝0.005，孔隙率为9.0％，密度为 1.99g/cm 3，孔隙率，面向导热率为1563.9W/mK。石墨烯厚膜无分层现象，任意两个相邻的石墨烯片的片层间距小于20nm。
实施例10-2：
(1)将平均尺寸大于50μm的氧化石墨烯配制成浓度为7mg/mL氧化石墨烯水溶液，用刮膜法，铺厚度为5mm的氧化石墨烯溶液成膜后自然晾干得到氧化石墨烯膜。
(2)将十张尺寸为8cm*8cm的氧化石墨烯膜分别用不同液体涂覆进行复合，具体为：在氧化石墨烯膜表面进行均匀喷涂去离子水，使之表面溶胀，然后将多张氧化石墨烯膜沿厚度方向粘接在一起，此方法制成的样品标记为样品A；在氧化石墨烯膜表面进行均匀涂覆一层浓度为4mg/mL的氧化石墨烯水溶液，然后将多张氧化石墨烯膜沿厚度方向粘接在一起，此方法制成的样品标记为样品B。
(3)将两种粘接后的氧化石墨烯复合膜放置在烘箱烘干，烘箱的温度低于40℃。
(4)将烘干后的氧化石墨烯复合膜置于热压机的热压腔中，以2℃/min的速率升温到200℃后进行热压，重复以下热压过程10次：维持压力20MPa，维持1h；逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-50KPa；然后再以2℃/min的速率升温300℃，保温0.5h，然后进行热压，重复以下热压过程5次：维持压力60MPa，维持1h，逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-50KPa；热压过程结束后自然降温。
(5)将步骤4热压后的氧化石墨烯复合膜在惰性气体氛围下以5℃/min的速率升温到2800℃进行进一步热压，保温保压2h；压力为60MPa。降温后，得到高导热的石墨烯厚膜。
经过以上步骤，氧化石墨烯膜通过粘处的作用力融合，形成整体结构。通过进一步低温热压，高温热压退火还原，最终得到高导热的石墨烯复合厚膜。而通过涂覆氧化石墨烯溶液粘接成的石墨烯复合厚膜，因其中的氧化石墨烯还可以填充缝隙处，故缺陷更少结构更加密实完整。经测试，样品A厚度为279μm，石墨烯片层褶皱密度为143mm/mm 2,且石墨烯片的缺陷极少，其ID/TG＝0.008，孔隙率为11.8％，密度为1.94g/cm 3，如图7所示，石墨烯厚膜无分层现象，任意两个相邻的石墨烯片的片层间距小于20nm。导热率为1448.9W/mK。样品B厚度为291μm，石墨烯片层褶皱密度为134mm/mm 2,且石墨烯片的缺陷极少，其ID/TG＝0.007，孔隙率为11.4％，密度为1.95g/cm 3，如图8所示，石墨烯厚膜无分层现象，任意两个相邻的石墨烯片的片层间距小于20nm，导热率为1495.8W/mK。
实施例10-3：
(1)平均尺寸大于50μm的高氧化程度的氧化石墨烯和低氧化程度的氧化石墨烯分别配制成7mg/mL的氧化石墨烯水溶液，用刮膜法，铺厚度为5mm的氧化石墨烯溶液成膜后自然晾干得到高氧化程度的氧化石墨烯膜和低氧化程度的氧化石墨烯膜。
(2)将十张高氧化程度的氧化石墨烯膜和低氧化程度的氧化石墨烯膜分别进行复合， 具体为：在氧化石墨烯膜表面进行均匀喷涂去离子水，使之表面溶胀，然后将多张氧化石墨烯膜沿厚度方向粘接在一起。氧化石墨烯薄膜可通过粘结界面处的作用力实现自粘结，得到高氧化程度的氧化石墨烯复合膜和低氧化程度的氧化石墨烯复合膜，分别标记为样品C和样品D。
(3)将粘接后的两个氧化石墨烯复合膜放置在烘箱烘干，烘箱的温度低于40℃，并在干燥过程中逐渐施加一些压力。
(4)将烘干后的氧化石墨烯复合膜置于热压机的热压腔中，以2℃/min的速率升温到200℃后进行热压，重复以下热压过程10次：维持压力20MPa，维持1h；逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-50KPa；然后再以2℃/min的速率升温300℃，保温0.5h，然后进行热压，重复以下热压过程5次：维持压力60MPa，维持1h，逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-50KPa；热压过程结束后自然降温。
(5)将步骤4热压后的氧化石墨烯复合膜在惰性气体氛围下以5℃/min的速率升温到2800℃进行进一步热压，保温保压2h；压力为60MPa。降温后，得到高导热的石墨烯厚膜。
经过以上步骤，氧化石墨烯膜通过粘处的作用力融合，形成整体结构。通过进一步低温热压，高温热压退火还原，最终得到高导热的石墨烯复合厚膜。而由于高氧化程度的氧化石墨烯由于具有较多的官能团，使得将高氧化程度的氧化石墨烯薄膜在均匀涂覆一层水粘接后，界面处的氢键和范德华力作用更大，使得粘结效果更好，结构更为密实。经测试，样品C厚度为261μm，石墨烯片层褶皱密度为151mm/mm 2,且石墨烯片的缺陷极少，其ID/TG＝0.008，孔隙率为12.3％，密度为1.93g/cm 3，面向导热率为1466.9W/mK，石墨烯厚膜无分层现象，任意两个相邻的石墨烯片的片层间距小于20nm。样品B厚度为255μm，石墨烯片层褶皱密度为139mm/mm 2,且石墨烯片的缺陷极少，其ID/TG＝0.09，孔隙率为13.2％，密度为1.91g/cm 3，导热率为1418.7W/mK，石墨烯厚膜无分层现象，任意两个相邻的石墨烯片的片层间距小于20nm。
实施例10-4：
(1)将平均尺寸大于50μm的氧化石墨烯分别配制成7mg/mL的氧化石墨烯水溶液，用刮膜法，分别铺厚度为5mm和2.5mm的氧化石墨烯膜，成膜后自然晾干得到两种厚度的氧化石墨烯膜。
(2)将五张较厚的氧化石墨烯膜和十张较薄的氧化石墨烯膜分别进行复合，具体为：在氧化石墨烯膜表面进行均匀涂覆一层浓度为4mg/mL的氧化石墨烯水溶液，然后将多张氧化石墨烯膜沿厚度方向粘接在一起，得到两个不同的氧化石墨烯复合膜，分别标记为样品E和样品F。
(3)将粘接后的两个氧化石墨烯复合膜放置在烘箱烘干，烘箱的温度低于40℃，并 在干燥过程中逐渐施加一些压力。
(4)将烘干后的氧化石墨烯复合膜置于热压机的热压腔中，以2℃/min的速率升温到200℃后进行热压，重复以下热压过程10次：维持压力20MPa，维持1h；逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-50KPa；然后再以2℃/min的速率升温300℃，保温0.5h，然后进行热压，重复以下热压过程5次：维持压力60MPa，维持1h，逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-50KPa；热压过程结束后自然降温。
(5)将步骤4热压后的氧化石墨烯复合膜在惰性气体氛围下以5℃/min的速率升温到2800℃进行进一步热压，保温保压2h；压力为60MPa。降温后，得到高导热的石墨烯厚膜。
经过以上步骤，氧化石墨烯膜通过粘处的作用力融合，形成整体结构。通过进一步低温热压，高温热处理修复缺陷，最终得到高导热的石墨烯厚膜。经测试，样品E厚度为135μm，石墨烯片层褶皱密度为121mm/mm 2,且石墨烯片的缺陷极少，其ID/TG＝0.009，孔隙率为12.7％，密度为1.92g/cm 3，导热率为1518.4W/mK，石墨烯厚膜无分层现象，任意两个相邻的石墨烯片的片层间距小于20nm；样品F厚度为138μm，石墨烯片层褶皱密度为118mm/mm 2,且石墨烯片的缺陷极少，其ID/TG＝0.009，孔隙率为13.2％，密度为1.91g/cm 3，导热率为1521.7W/mK，石墨烯厚膜无分层现象，任意两个相邻的石墨烯片的片层间距小于20nm。
实施例10-5：
(1)将平均尺寸大于50μm的氧化石墨烯配制成浓度为7mg/mL氧化石墨烯水溶液，用刮膜法，铺厚度为5mm的氧化石墨烯溶液成膜后自然晾干得到氧化石墨烯膜。
(2)将一百张尺寸为4cm*4cm的氧化石墨烯膜进行复合，具体为：在氧化石墨烯膜表面进行均匀涂覆一层浓度为4mg/mL的氧化石墨烯水溶液，然后将多张氧化石墨烯膜沿厚度方向粘接在一起。
(3)将粘接后的氧化石墨烯复合膜放置在烘箱烘干，烘箱的温度低于40℃。
(4)将烘干后的氧化石墨烯复合膜置于热压机的热压腔中，以2℃/min的速率升温到200℃后进行热压，重复以下热压过程10次：维持压力20MPa，维持1h；逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-100～10KPa；然后再以2℃/min的速率升温300℃，保温0.5h，然后进行热压，重复以下热压过程5次：维持压力60MPa，维持1h，逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-100～10KPa；热压过程结束后自然降温。
(5)将步骤4热压后的氧化石墨烯复合膜在惰性气体氛围下以5℃/min的速率升温到2500℃进行进一步热压，保温保压2h；压力为60MPa。降温后，得到高导热的石墨烯厚膜。
经过以上步骤，氧化石墨烯膜通过粘处的作用力融合以及涂覆液体中氧化石墨烯的填充缝隙，形成整体结构。通过进一步低温热压，高温热压退火还原，最终得到高导热的石墨烯复合厚膜。经测试，该石墨烯膜的厚度为2.93mm，石墨烯片层褶皱密度为310mm/mm 2,且石墨烯片的缺陷极少，其ID/TG＝0.018，孔隙率为20.1％，密度为1.74g/cm 3，导热率为1287.1W/mK，石墨烯厚膜无分层现象，任意两个相邻的石墨烯片的片层间距小于20nm。
实施例10-6：
(1)将平均尺寸大于100μm的氧化石墨烯配制成浓度为1mg/mL氧化石墨烯水溶液，溶液成膜后自然晾干，得到氧化石墨烯膜。氧化石墨烯膜的厚度为15μm，氧化石墨烯膜的碳氧比1.8。
(2)将多张氧化石墨烯膜进行复合，具体为：在氧化石墨烯膜表面进行均匀喷涂水，使之表面溶胀，然后将多张氧化石墨烯膜沿厚度方向粘接在一起。
(3)将粘接后的氧化石墨烯复合膜放置在烘箱烘干，烘箱的温度为40℃。
(4)将烘干后的氧化石墨烯复合膜置于热压机的热压腔中，以0.1℃/min的速率升温到200℃后进行热压，重复以下热压过程8次：维持压力20MPa，维持1h；逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-100KPa；然后再以0.1℃/min的速率升温300℃，保温0.5h，然后进行热压，重复以下热压过程4次：维持压力60MPa，维持1h，逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-100KPa；热压过程结束后自然降温。
(5)将步骤4热压后的氧化石墨烯膜在惰性气体氛围下以1℃/min的速率升温到1800℃进行进一步热压，保温保压8h；压力为60MPa。降温压制后，得到高导热的石墨烯厚膜。
经测试，所制备的石墨烯厚膜的厚度为54μm，密度为2.1g/cm 3，孔隙率为5％；导热率为1987.1W/mK，石墨烯片层褶皱密度位50mm/mm 2，且石墨烯片的缺陷少，其ID/TG＝0.005，石墨烯厚膜无分层现象，任意两个相邻的石墨烯片的片层间距小于20nm。
实施例10-7：
(1)将平均尺寸大于50μm的氧化石墨烯配制成浓度为20mg/mL氧化石墨烯水溶液，溶液成膜后自然晾干，得到氧化石墨烯膜，厚度为50μm，碳氧比2.1。
(2)将多张氧化石墨烯膜进行复合，具体为：在氧化石墨烯膜表面进行均匀喷涂浓度为1mg/mL的氧化石墨烯水溶液，使之表面溶胀，然后将多张氧化石墨烯膜沿厚度方向粘接在一起。
(3)将粘接后的氧化石墨烯复合膜放置在烘箱烘干，烘箱的温度为30℃。
(4)将烘干后的氧化石墨烯复合膜置于热压机的热压腔中，以5℃/min的速率升温到200℃后进行热压，重复以下热压过程10次：维持压力20MPa，维持1h；逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-10KPa；然后再以5℃/min的速率升温300℃，保温0.5h，然后进行热压，重复以下热压过程6次：维持压力60MPa，维持1h，逐渐释放压力至 0MPa，对热压腔抽真空5min至真空度为-10KPa；热压过程结束后自然降温。
(5)将步骤4热压后的氧化石墨烯膜在惰性气体氛围下以20℃/min的速率升温到3000℃进行进一步热压，保温保压0.5h；压力为10MPa。降温压制后，得到高导热的石墨烯厚膜。
经测试，所制备的石墨烯厚膜的厚度为4.56mm，孔隙率为40％；石墨烯片层褶皱密度为500mm/mm 2左右，且石墨烯片的缺陷少，其ID/TG＝0.02，石墨烯厚膜无分层现象，任意两个相邻的石墨烯片的片层间距小于20nm。

Claims (30)

  1. 一种石墨烯-氮化硼纤维复合材料的制备方法，其特征在于，包括以下步骤：
    (1)使用氧化石墨烯分散液对氮化硼纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的氮化硼纤维；
    (2)将涂覆氧化石墨烯的氮化硼纤维置于溶剂中进行表面溶胀，然后将纤维合并经干燥后形成无捻纱，或将纤维相互搭接经干燥后形成无纺布或短切毡，干燥温度低于100℃；
    (3)还原后得到石墨烯-氮化硼纤维复合材料。
  2. 一种石墨烯-石英纤维复合材料的制备方法，其特征在于，包括以下步骤：
    (1)将石英纤维置于甲苯中浸泡，加热至300℃保持10min，烘干；
    (2)使用氧化石墨烯分散液对石英纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的石英纤维；
    (3)将涂覆氧化石墨烯的石英纤维置于溶剂中进行表面溶胀，然后将纤维合并经干燥后形成无捻纱，或将纤维相互搭接经干燥后形成无纺布或短切毡，干燥温度低于100℃；
    (4)还原后得到石墨烯-石英纤维复合材料。
  3. 一种石墨烯-碳化硅纤维复合材料的制备方法，其特征在于，包括以下步骤：
    (1)使用氧化石墨烯分散液对碳化硅纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的碳化硅纤维；
    (2)将涂覆氧化石墨烯的碳化硅纤维置于溶剂中进行表面溶胀，然后将纤维合并经干燥后形成无捻纱，或将纤维相互搭接经干燥后形成无纺布或短切毡，干燥温度低于100℃；
    (3)还原后得到石墨烯-碳化硅纤维复合材料；
  4. 根据权利要求3所述的方法，其特征在于，所述步骤(1)中碳化硅纤维含有钛、铁、镍、硼、铝、锆元素中的一种或多种，纤维截面形状为圆形、三叶形、三折叶形、六叶形、条形、十字形、中空形中的一种。
  5. 一种石墨烯-玄武岩纤维复合材料的制备方法，其特征在于，包括以下步骤：
    (1)将玄武岩纤维置于甲苯中加热至250℃，超声清洗10～30min，除去表面浸润剂和油剂，烘干；
    (2)使用氧化石墨烯分散液对玄武岩纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的玄武岩纤维；
    (3)将涂覆氧化石墨烯的玄武岩纤维置于溶剂中进行表面溶胀，然后将纤维合并经干燥后形成无捻纱，或将纤维相互搭接经干燥后形成无纺布或短切毡，干燥温度低于100摄氏度；
    (4)还原后得到石墨烯-玄武岩纤维复合材料。
  6. 一种石墨烯-氧化铝纤维复合材料的制备方法，其特征在于，包括以下步骤：
    (1)使用氧化石墨烯分散液对氧化铝纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的氧化铝纤维；
    (2)将涂覆氧化石墨烯的氧化铝纤维置于溶剂中进行表面溶胀，然后将纤维合并经干燥后形成无捻纱，或将纤维相互搭接经干燥后形成无纺布或短切毡，干燥温度低于100℃；
    (3)还原后得到石墨烯-氧化铝纤维复合材料。
  7. 一种石墨烯-玻璃纤维复合材料的制备方法，其特征在于，包括以下步骤：
    (1)将玻璃纤维置于丙酮中超声清洗，除去表面油渍，烘干；
    (2)使用氧化石墨烯分散液对玻璃纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的玻璃纤维；
    (3)将涂覆氧化石墨烯的玻璃纤维置于溶剂中进行表面溶胀，然后将纤维合并，经干燥后形成无捻纱，或将纤维相互搭接，经干燥后形成无纺布或短切毡，干燥温度低于100摄氏度；
    (4)还原后得到石墨烯-玻璃纤维复合材料。
  8. 根据权利要求1～7任一项所述的方法，其特征在于，所述氧化石墨烯分散液的浓度为7mg/g，分散剂为水、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙醇、乙二醇、N-甲基吡咯烷酮、四氢呋喃、二甲亚砜、二甘醇、吡啶、二氧六环、丁酮、异丙醇。
  9. 根据权利要求1～7任一项所述的方法，其特征在于，使用氧化石墨烯分散液对纤维进行多次涂覆，每次涂覆后干燥，最终干燥后的氧化石墨烯层厚度为3μm。
  10. 根据权利要求1～7任一项所述的方法，其特征在于，表面溶胀所采用的溶剂为水、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。
  11. 根据权利要求1～7任一项所述的方法，其特征在于，还原方法为使用化学还原剂进行还原或100～600℃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。
  12. 一种石墨烯交联的碳纤维丝束的制备方法，其特征在于，包括以下步骤：
    (1)去除碳纤维表面的上浆剂，并对其表面进行氧化改性；
    (2)使用氧化石墨烯分散液对氧化改性后的碳纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的碳纤维；
    (3)将多根涂覆氧化石墨烯的碳纤维置于溶剂中进行表面溶胀，然后将溶胀后的纤维并成丝束，随后在低于100℃的温度下干燥，使得溶剂挥发；
    (4)还原后得到石墨烯交联的碳纤维丝束。
  13. 一种石墨烯交联的碳纤维织物的制备方法，其特征在于，包括以下步骤：
    (1)去除碳纤维表面的上浆剂，并对其表面进行氧化改性；
    (2)使用氧化石墨烯分散液对氧化改性后的碳纤维进行表面涂覆，干燥后得到表面涂覆有氧化石墨烯的碳纤维；
    (3)将多根涂覆氧化石墨烯的碳纤维编织成织物，置于溶剂中进行表面溶胀、融合，随后在低于100℃的温度下干燥，使得溶剂挥发；
    (4)还原后得到石墨烯交联的碳纤维织物。
  14. 根据权利要求12或13所述的方法，其特征在于，所述步骤(2)中氧化石墨烯分散液的分散剂为水、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、乙醇、乙二醇、N-甲基吡咯烷酮、四氢呋喃、二甲亚砜、二甘醇、吡啶、二氧六环、丁酮、异丙醇。
  15. 根据权利要求12或13所述的方法，其特征在于，所述步骤(2)中，使用氧化石墨烯分散液对氧化改性后的碳纤维进行多次涂覆，每次涂覆后干燥，干燥温度约为25～50℃。
  16. 根据权利要求12或13所述的方法，其特征在于，所述步骤(3)中溶剂为水、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。
  17. 根据权利要求12或13所述的方法，其特征在于，所述步骤(4)中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。
  18. 根据权利要求12或13所述的方法，其特征在于，所述步骤2中采用氧化石墨烯分散液的浓度为7mg/ml，干燥后碳纤维表面的氧化石墨烯厚度为3μm。
  19. 一种高导热的石墨烯厚膜，其特征在于，厚度大于50μm，孔隙率为5～40％，面向热导率为1000～2000W/mK，；石墨烯片层褶皱密度控制在50～500mm/mm 2，且石墨烯片的缺陷少，其ID/TG＜0.02，石墨烯厚膜无分层现象，任意两个相邻的石墨烯片的片层间距小于20nm，其制备方法包含如下步骤：
    (1)将平均尺寸大于50μm的氧化石墨烯配制成浓度为1～20mg/mL氧化石墨烯水溶液，溶液成膜后自然晾干，得到氧化石墨烯膜；
    (2)将多张氧化石墨烯膜进行复合，具体为：在氧化石墨烯膜表面进行均匀喷涂液体，使之表面溶胀，然后将多张氧化石墨烯膜沿厚度方向粘接在一起；
    (3)将粘接后的氧化石墨烯复合膜放置在烘箱烘干，烘箱的温度不高于40℃；
    (4)将烘干后的氧化石墨烯复合膜置于热压机的热压腔中，以0.1～5℃/min的速率升 温到200℃后进行热压，重复以下热压过程8-10次：维持压力20MPa，维持1h；逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-100～10KPa；然后再以0.1～5℃/min的速率升温300℃，保温0.5h，然后进行热压，重复以下热压过程4-6次：维持压力60MPa，维持1h，逐渐释放压力至0MPa，对热压腔抽真空5min至真空度为-100～10KPa；热压过程结束后自然降温；
    (5)将步骤4热压后的氧化石墨烯膜在惰性气体氛围下以1-20℃/min的速率升温到1800～3000℃进行进一步热压，保温保压0.5～8h；压力为10～60MPa；降温压制后，得到高导热的石墨烯厚膜。
  20. 根据权利要求19所述的一种高导热石墨烯厚膜的制备方法，其特征在于，所述步骤1制备的氧化石墨烯膜的厚度为1μm～30μm。
  21. 根据权利要求19所述的一种高导热石墨烯厚膜的制备方法，其特征在于，所述步骤1中的成膜方法选自抽滤法、刮膜法、旋涂法、喷涂法和浸涂法。
  22. 根据权利要求19所述的一种高导热的石墨烯厚膜的制备方法，其特征在于，所述的步骤1制备的氧化石墨烯膜的碳氧比1.8～2.1。
  23. 根据权利要求19所述的一种高导热的石墨烯厚膜的制备方法，其特征在于，所述所述的步骤2喷涂所使用的液体为：去离子水，浓度为1～10mg/mL的氧化石墨烯水溶液，或其它含有去离子水的溶液。
  24. 一种氧化石墨烯粘接剂，其特征在于：包括溶剂，以及分散于溶剂中的氧化石墨烯，所述氧化石墨烯的浓度大于等于4mg/ml，C/O比小于等于3:1，氧化石墨烯单层率大于80％；氧化石墨烯片层尺寸为1um～100um，尺寸小于5um的氧化石墨烯片的量少于等于10％，且尺寸大于30um的氧化石墨烯片的量不少于60％。
  25. 根据权利要求24所述的氧化石墨烯粘接剂，其特征在于，溶剂为水、DMF。
  26. 一种基于石墨烯材料的粘结方法，其特征在于，该方法为：首先对粘结材料表面进行亲水处理，之后将氧化石墨烯粘接剂均匀涂覆在多个待粘接材料之间，待其干燥后，待粘接材料之间通过氧化石墨烯实现粘接。
  27. 一种利用石墨烯实现材料粘接的方法，其特征在于，该方法为：首先将氧化石墨烯溶液均匀涂覆在多个待粘接材料之间，待其干燥后进行还原，即可在待粘接材料之间通过石墨烯实现粘接；所述氧化石墨烯溶液中，氧化石墨烯片层尺寸为1um～100um，尺寸小于5um的氧化石墨烯片少于等于10％，且尺寸大于30um的氧化石墨烯片不少于65％；氧化石墨烯单层率大于80％；氧化石墨烯的浓度大于等于4mg/mL。
  28. 根据权利要求4所述的方法，其特征在于，还原后的石墨烯的C/O大于4:1。
  29. 根据权利要求1所述的方法，其特征在于，所述溶剂为水、乙醇、N,N-二甲基甲酰胺(DMF)。
  30. 根据权利要求1所述的方法，其特征在于，还原方法为在80-100℃下利用氢碘酸或水合肼蒸汽进行化学还原，或在加压或真空状态下按1℃/min升温速率缓慢升温至100-500℃热还原。
PCT/CN2018/078765 2017-05-27 2018-03-13 基于石墨烯粘结的复合材料的制备方法 WO2018219008A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US16/617,531 US11542411B2 (en) 2017-05-27 2018-03-13 Method for preparing composites on basis of graphene bonding
JP2019565907A JP6952134B2 (ja) 2017-05-27 2018-03-13 グラフェン粘着に基づく複合材料の製造方法

Applications Claiming Priority (20)

Application Number Priority Date Filing Date Title
CN201710391093.9A CN107163861A (zh) 2017-05-27 2017-05-27 一种利用石墨烯实现材料粘接的方法
CN201710391092.4 2017-05-27
CN201710391843.2A CN107022312A (zh) 2017-05-27 2017-05-27 一种氧化石墨烯粘接剂及粘接方法
CN201710391093.9 2017-05-27
CN201710391092.4A CN107140619B (zh) 2017-05-27 2017-05-27 一种高导热的石墨烯厚膜及其制备方法
CN201710391843.2 2017-05-27
CN201710691600.0 2017-08-14
CN201710691600.0A CN107687090A (zh) 2017-08-14 2017-08-14 一种石墨烯交联的碳纤维丝束、织物及其制备方法
CN201711150773.8 2017-11-18
CN201711150786.5 2017-11-18
CN201711150763.4A CN107858777A (zh) 2017-11-18 2017-11-18 一种石墨烯‑氧化铝纤维复合材料及其制备方法
CN201711150791.6 2017-11-18
CN201711150773.8A CN107675488A (zh) 2017-11-18 2017-11-18 一种石墨烯‑碳化硅纤维复合材料及其制备方法
CN201711150778.0A CN107815789A (zh) 2017-11-18 2017-11-18 一种石墨烯‑石英纤维复合材料及其制备方法
CN201711150786.5A CN107761249A (zh) 2017-11-18 2017-11-18 一种石墨烯‑玻璃纤维复合材料及其制备方法
CN201711150778.0 2017-11-18
CN201711150776.1A CN107869047A (zh) 2017-11-18 2017-11-18 一种石墨烯‑氮化硼纤维复合材料及其制备方法
CN201711150776.1 2017-11-18
CN201711150791.6A CN107805886A (zh) 2017-11-18 2017-11-18 一种石墨烯‑玄武岩纤维复合材料及其制备方法
CN201711150763.4 2017-11-18

Publications (1)

Publication Number Publication Date
WO2018219008A1 true WO2018219008A1 (zh) 2018-12-06

Family

ID=64454415

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/078765 WO2018219008A1 (zh) 2017-05-27 2018-03-13 基于石墨烯粘结的复合材料的制备方法

Country Status (3)

Country Link
US (1) US11542411B2 (zh)
JP (1) JP6952134B2 (zh)
WO (1) WO2018219008A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020117573A (ja) * 2019-01-21 2020-08-06 三井化学株式会社 熱伝導性樹脂組成物、熱伝導シートおよび電子部品
CN115464941A (zh) * 2022-09-15 2022-12-13 上海伽材新材料科技有限公司 一种碳纤维/石墨烯复合电磁屏蔽预浸料的制备方法

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11551857B2 (en) * 2018-04-13 2023-01-10 Cyntec Co., Ltd. Shielded magnetic device and the method to make the same
CN110482539B (zh) * 2019-09-06 2021-09-21 常州富烯科技股份有限公司 强、弱氧化石墨烯的混合浆料及其制备方法、强、弱氧化石墨烯的复合膜及其制备方法
CN112900077B (zh) * 2021-03-29 2022-01-11 吉林大学 一种具有吸波特性的氧化石墨烯/碳纤维织物的制备方法
CN113321208B (zh) * 2021-07-06 2023-08-04 山东热坤新材料有限公司 一种高致密性石墨烯膜的制备方法
CN114525114A (zh) * 2022-02-28 2022-05-24 中国电子科技集团公司第三十三研究所 一种基于石墨烯纤维的导热吸波粉体材料的制备方法
CN114864946A (zh) * 2022-05-27 2022-08-05 哈尔滨工程大学 一种改性还原氧化石墨烯粘结剂及其制备方法和应用
CN115072709B (zh) * 2022-07-27 2023-07-21 广东墨睿科技有限公司 石墨烯导热膜及其制备方法
WO2024031194A1 (en) * 2022-08-12 2024-02-15 Bio Graphene Solutions Inc. Process for producing a material comprising graphene and/or graphite on a matrix, and materials prepared therefrom
CN115975423B (zh) * 2023-02-08 2024-02-27 大连交通大学 还原氧化石墨烯/铝防腐蚀材料及其制备方法和应用
CN116675221B (zh) * 2023-06-01 2024-04-09 南京工业大学 一种高电导率高热导率石墨烯膜及其制备方法与应用
CN116814181A (zh) * 2023-08-01 2023-09-29 凯仁精密材料(江苏)有限公司 一种超薄导热胶带及其制备方法
CN118175826A (zh) * 2024-05-16 2024-06-11 浙江大华技术股份有限公司 复合吸波材料、制备方法及器件

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104130719A (zh) * 2014-08-12 2014-11-05 哈尔滨工业大学 一种氧化石墨烯导电粘结剂及其制备和使用方法
WO2015163595A1 (ko) * 2014-04-24 2015-10-29 서울대학교산학협력단 층간 자기조립을 이용한 그래핀 기반 나노탄소 섬유 제조 방법
CN105692601A (zh) * 2016-01-27 2016-06-22 常州富烯科技股份有限公司 一种石墨烯块材的制备方法及得到的石墨烯块材
CN106245441A (zh) * 2016-07-29 2016-12-21 佛山市高明区诚睿基科技有限公司 一种石墨烯改性复合玻璃纤维在玻璃纤维过滤纸的应用
US20170073553A1 (en) * 2015-09-15 2017-03-16 Kuo-Hsin CHANG Graphene glue, its composition and using method
CN107022312A (zh) * 2017-05-27 2017-08-08 杭州高烯科技有限公司 一种氧化石墨烯粘接剂及粘接方法
CN107140619A (zh) * 2017-05-27 2017-09-08 杭州高烯科技有限公司 一种高导热的石墨烯厚膜及其制备方法
CN107163861A (zh) * 2017-05-27 2017-09-15 杭州高烯科技有限公司 一种利用石墨烯实现材料粘接的方法
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
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
CN107761249A (zh) * 2017-11-18 2018-03-06 杭州高烯科技有限公司 一种石墨烯‑玻璃纤维复合材料及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10343916B2 (en) * 2010-06-16 2019-07-09 The Research Foundation For The State University Of New York Graphene films and methods of making thereof
CN104591551A (zh) 2015-01-16 2015-05-06 东华大学 一种石墨烯包覆玻璃纤维复合材料的制备方法
CN105696312A (zh) 2016-01-28 2016-06-22 西北工业大学 酸化辅助电泳沉积引发氧化石墨烯沉积改性碳纤维的方法
CN106183142B (zh) 2016-07-18 2018-02-09 浙江大学 一种基于石墨烯纤维无纺布的自热膜
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
US11629420B2 (en) * 2018-03-26 2023-04-18 Global Graphene Group, Inc. Production process for metal matrix nanocomposite containing oriented graphene sheets

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015163595A1 (ko) * 2014-04-24 2015-10-29 서울대학교산학협력단 층간 자기조립을 이용한 그래핀 기반 나노탄소 섬유 제조 방법
CN104130719A (zh) * 2014-08-12 2014-11-05 哈尔滨工业大学 一种氧化石墨烯导电粘结剂及其制备和使用方法
US20170073553A1 (en) * 2015-09-15 2017-03-16 Kuo-Hsin CHANG Graphene glue, its composition and using method
CN105692601A (zh) * 2016-01-27 2016-06-22 常州富烯科技股份有限公司 一种石墨烯块材的制备方法及得到的石墨烯块材
CN106245441A (zh) * 2016-07-29 2016-12-21 佛山市高明区诚睿基科技有限公司 一种石墨烯改性复合玻璃纤维在玻璃纤维过滤纸的应用
CN107022312A (zh) * 2017-05-27 2017-08-08 杭州高烯科技有限公司 一种氧化石墨烯粘接剂及粘接方法
CN107140619A (zh) * 2017-05-27 2017-09-08 杭州高烯科技有限公司 一种高导热的石墨烯厚膜及其制备方法
CN107163861A (zh) * 2017-05-27 2017-09-15 杭州高烯科技有限公司 一种利用石墨烯实现材料粘接的方法
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
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
CN107761249A (zh) * 2017-11-18 2018-03-06 杭州高烯科技有限公司 一种石墨烯‑玻璃纤维复合材料及其制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020117573A (ja) * 2019-01-21 2020-08-06 三井化学株式会社 熱伝導性樹脂組成物、熱伝導シートおよび電子部品
JP7402610B2 (ja) 2019-01-21 2023-12-21 三井化学株式会社 熱伝導性樹脂組成物、熱伝導シートおよび電子部品
CN115464941A (zh) * 2022-09-15 2022-12-13 上海伽材新材料科技有限公司 一种碳纤维/石墨烯复合电磁屏蔽预浸料的制备方法

Also Published As

Publication number Publication date
US11542411B2 (en) 2023-01-03
JP6952134B2 (ja) 2021-10-20
JP2020521713A (ja) 2020-07-27
US20200131405A1 (en) 2020-04-30

Similar Documents

Publication Publication Date Title
WO2018219008A1 (zh) 基于石墨烯粘结的复合材料的制备方法
CN110982114B (zh) 芳纶/碳纳米管杂化气凝胶薄膜、其制备方法及应用
CN107140619B (zh) 一种高导热的石墨烯厚膜及其制备方法
WO2018196475A1 (zh) 一种自融合石墨烯纤维及其制备方法
TW200306376A (en) Carbon paper and carbon electrode base material for fuel cell made therefrom
WO2018014583A1 (zh) 一种石墨烯纤维无纺布及其制备方法
CN107805886A (zh) 一种石墨烯‑玄武岩纤维复合材料及其制备方法
Ding et al. Layered cotton/rGO/NiWP fabric prepared by electroless plating for excellent electromagnetic shielding performance
CN111073059B (zh) 一种纳米纤维素电热膜及其制备方法
CN113774720B (zh) 一种碳纤维纸及其制备方法
EP3558867A1 (en) Graphite material
Lee et al. Environment-friendly, durable, electro-conductive, and highly transparent heaters based on silver nanowire functionalized keratin nanofiber textiles
CN113527761A (zh) 一种气凝胶基主-客体复合薄膜、其制备方法及应用
CN107675488A (zh) 一种石墨烯‑碳化硅纤维复合材料及其制备方法
CN107687090A (zh) 一种石墨烯交联的碳纤维丝束、织物及其制备方法
KR20180106625A (ko) 면상 발열체 및 이의 제조방법
Tang et al. Flexible metalized polyimide nonwoven fabrics for efficient electromagnetic interference shielding
KR102153921B1 (ko) 탄소 섬유 복합재 및 그의 제조 방법
CN113981675B (zh) 光致发热纺织品的制备方法
JP5297701B2 (ja) 固体高分子型燃料電池用電極基材の製造方法
JP6035084B2 (ja) カーボン／カーボンコンポジット用の中間材料
KR102033583B1 (ko) 그래핀을 이용한 수퍼커패시터 전극 및 이의 제조방법
CN109267416A (zh) 一种自融合的还原石墨烯纤维纸及其制备方法
KR101873122B1 (ko) 높은 인장 강도 및 낮은 시트 저항을 갖는 그래핀 종이 및 그 제조방법
Khadka et al. Eco-friendly cellulose wearable heaters using Korean traditional Han paper coated with graphene nanosheets via binder-free supersonic spraying

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: 18808729

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019565907

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18808729

Country of ref document: EP

Kind code of ref document: A1