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WO2019029191A1 - Fibre de graphène drapée et non-tissé de fibre de graphène et leur procédé de préparation - Google Patents

Fibre de graphène drapée et non-tissé de fibre de graphène et leur procédé de préparation Download PDF

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Publication number
WO2019029191A1
WO2019029191A1 PCT/CN2018/084334 CN2018084334W WO2019029191A1 WO 2019029191 A1 WO2019029191 A1 WO 2019029191A1 CN 2018084334 W CN2018084334 W CN 2018084334W WO 2019029191 A1 WO2019029191 A1 WO 2019029191A1
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WIPO (PCT)
Prior art keywords
graphene
graphene fiber
fiber
pleated
nonwoven fabric
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Ceased
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PCT/CN2018/084334
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English (en)
Chinese (zh)
Inventor
高超
李拯
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Hangzhou Gaoxi Technology Co Ltd
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Hangzhou Gaoxi Technology Co Ltd
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Publication of WO2019029191A1 publication Critical patent/WO2019029191A1/fr
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/16—Chemical after-treatment of artificial filaments or the like during manufacture of carbon by physicochemical methods

Definitions

  • the present invention relates to graphene fibers and fabrics, and more particularly to a graphene fiber and a graphene fiber nonwoven fabric which are formed by stacking pleated graphene sheets and a preparation method thereof.
  • Graphene fiber nonwoven fabric is a new type of non-woven fabric composed of graphene fibers (Nature Communications, 2016, 13684). This kind of non-woven fabric is realized by the mutual fusion of graphene fibers at the joints.
  • the material has excellent electrical and thermal conductivity properties, which fully reflects the excellent properties of graphene on a macroscopic scale (Science, 2004, 306: 666-669). Thanks to the highly conductive network structure exhibited by the graphene fiber nonwoven fabric, it has great potential as a flexible fabric electrode in the field of energy storage devices such as capacitors and batteries.
  • the existing graphene fiber nonwoven fabric has better flexibility and high electrical conductivity.
  • the graphene fiber constituting the non-woven fabric has a small surface microstructure, and is extremely limited when used as an electrode material of a supercapacitor due to a small active surface area.
  • the specific capacitance value of the capacitor If a large number of microstructures can be constructed on the surface of the graphene fiber by special means to significantly increase the specific surface area of the fiber, the electric double layer capacitance of the graphene fiber non-woven electrode can be greatly improved, and a higher performance energy storage device can be obtained. .
  • graphene fiber nonwoven fabrics having a multistage structure have not been reported.
  • the object of the present invention is to provide a pleated graphene fiber and a graphene fiber nonwoven fabric and a preparation method thereof, in view of the deficiencies of the prior art.
  • a pleated graphene fiber which is formed by stacking pleated graphene sheets, and the pleated structure of the graphene sheet is formed by a capillary sheet having defects under capillary force.
  • a method for preparing graphene fibers comprising the steps of:
  • the spinning solution is an aqueous solution of graphene oxide or a solution of N,N-dimethylformamide.
  • the coagulation bath used in the spinning process is a calcium chloride/water/ethanol mixture or ethyl acetate.
  • a high-performance graphene fiber non-woven fabric in which a graphene fiber is overlapped to form a network, and graphene fibers at a mesh node are fused to each other.
  • a method for preparing a high-performance graphene fiber nonwoven fabric wherein the graphene fiber after hydrothermal treatment in the step 3 of claim 2 is pulverized in an aqueous solution into short fibers having a length of 1-7 mm, using a high-speed shear mixer, and then The screen is deposited and dried in air to obtain a graphene fiber nonwoven fabric.
  • the high speed shear agitation speed is 3000-8000 rpm.
  • the method further comprises further reducing the dried graphene fiber nonwoven fabric.
  • the reduction method is reduction using a chemical reducing agent such as hydriodic acid, hydrazine hydrate, vitamin C or sodium borohydride or thermal reduction at 100-3000 °C.
  • the invention has the following beneficial effects:
  • Graphene fibers are stacked from pleated graphene sheets, which significantly increase the specific surface area and have a larger active surface, which is advantageous for their application in fabric electrodes.
  • the preparation method is simple, and the microstructure of the fiber surface can be controlled and controlled by the change of the fiber pre-drying temperature and the hydrothermal treatment temperature.
  • Figure 1 is a scanning electron micrograph of pleated graphene fibers at different magnifications.
  • Figure 2 is a schematic view of the forming process of the pleated graphene fibers (a) and scanning electron micrographs (b ⁇ e) of each stage;
  • Figure 3 is a schematic view (a) of a pleated graphene fiber nonwoven fabric and a schematic view (b) of the fusion zone.
  • the invention fully utilizes the hydrophilicity of the graphene oxide, so that the graphene oxide is immersed in water, and the graphene sheet layer is given a certain degree of freedom by the water swelling action, which is favorable for the formation of the pleat structure and the lower temperature water is used.
  • the heat treatment of the microstructure of the graphene fiber is low, and the method is simple.
  • a defect is introduced into the graphene sheet layer by reduction of the graphene oxide sheet layer (removal of the oxidized functional group), thereby providing a stress concentration point formed by the wrinkle structure.
  • the graphene fiber After hydrothermal treatment, the graphene fiber is naturally dried in the air, and the solvent water contained in the fiber volatilizes to form a huge capillary force, causing the graphene sheet to spontaneously produce wrinkles, forming a microstructure on the surface and inside of the graphene fiber, and significantly increasing The specific surface area of the graphene fiber.
  • the specific process is shown in Figure 2.
  • the fibers are fused together into a network structure to form a pure graphene nonwoven fabric.
  • the specific surface area of the graphene fiber nonwoven fabric is remarkably improved while ensuring high electrical conductivity of the nonwoven fabric.
  • the multi-stage pleated structure graphene fiber and the graphene fiber nonwoven fabric of the present invention can provide an energy storage device with high flexibility while obtaining excellent electrochemical performance when used as a fabric electrode, and is promising in wearable electrons.
  • the device field has been applied.
  • the obtained graphene fiber has a distinct wrinkle structure, the fiber strength is about 90 MPa, and the electrical conductivity is 102 S/m.
  • a graphene oxide/N,N-dimethylformamide solution having a concentration of 5 mg/mL was used as a spinning solution, and ethyl acetate was used as a coagulation bath for continuous wet spinning.
  • the hydrothermally treated graphene fibers were pulverized into short fibers having a length of 4 mm at a rotation speed of 3000 rpm using a high-speed shear mixer, and deposited on a sieve, and dried in air to obtain a graphene fiber nonwoven fabric.
  • the obtained graphene fiber nonwoven fabric has a multi-stage structure, the surface of the graphene fiber is rough, and contains a large number of microstructures of wrinkles and protrusions, the specific surface area is 190 m 2 /g, the electrical conductivity is 80 S/m, and the absence
  • the woven material is flexible and resistant to multiple bends to maintain structural stability.
  • the aqueous solution of graphene oxide having a concentration of 15 mg/mL is used as a dispersion, and the calcium chloride/water/ethanol mixture is continuously wet-spun as a coagulation bath.
  • the hydrothermally treated graphene fibers were pulverized into short fibers at a speed of 5000 rpm using a high-speed shear mixer, and deposited on a sieve, and dried in air to obtain a multi-stage graphene fiber nonwoven fabric.
  • the obtained graphene fiber non-woven fabric has a multi-stage pleated structure, but due to the preheating drying temperature in step 2, the hydrophilicity of the graphene fiber is lowered, so that the surface of the graphene fiber is not high in wrinkles.
  • the surface microstructure of the fiber is mostly a loose strip-shaped ridge.
  • the nonwoven fabric had a specific surface area of 63 m 2 /g and a conductivity of 88 S/m.
  • Steps 1-4 were the same as in Example 1, and no further reduction of Step 5 was carried out.
  • the obtained graphene fiber nonwoven fabric had a multi-stage pleated structure and a conductivity of 1.2 S/m.
  • Step 1 is: continuous wet spinning of a graphene oxide/N,N-dimethylformamide solution having a concentration of 5 mg/mL as a spinning solution and ethyl acetate as a coagulation bath.
  • Step 2-5 is the same as in Example 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Nonwoven Fabrics (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Inorganic Fibers (AREA)

Abstract

La présente invention concerne une fibre de graphène et un non-tissé de fibre de graphène ayant une structure drapée, et leur procédé de préparation ; une surface de la fibre de graphène contient un grand nombre de micro-structures drapées et peut être utilisée pour former un non-tissé de fibre de graphène ayant une structure multi-drapée de telle sorte que l'aire spécifique du non-tissé est considérablement augmentée, et la fibre de graphène et une structure de réseau de communication composée des fibres ont simultanément une flexibilité et une conductivité électrique élevées, et peuvent ainsi être utilisées comme matériau d'électrode flexible et peuvent être appliquées dans des dispositifs de stockage d'énergie pouvant être portés.
PCT/CN2018/084334 2017-08-08 2018-04-25 Fibre de graphène drapée et non-tissé de fibre de graphène et leur procédé de préparation Ceased WO2019029191A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710670077.3 2017-08-08
CN201710670077.3A CN107502995B (zh) 2017-08-08 2017-08-08 一种褶皱的石墨烯纤维和石墨烯纤维无纺布及其制备方法

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WO2019029191A1 true WO2019029191A1 (fr) 2019-02-14

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WO (1) WO2019029191A1 (fr)

Families Citing this family (16)

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CN107502995B (zh) * 2017-08-08 2019-08-16 杭州高烯科技有限公司 一种褶皱的石墨烯纤维和石墨烯纤维无纺布及其制备方法
CN108708076A (zh) * 2018-04-09 2018-10-26 南京捷纳思新材料有限公司 湿纺制备核壳结构聚氨酯-碳纳米管导电无纺布的方法
CN108707998A (zh) * 2018-04-11 2018-10-26 杭州牛墨科技有限公司 一种褶皱的石墨烯纤维和石墨烯纤维无纺布及其制备方法
CN108914251B (zh) * 2018-07-09 2020-10-30 杭州高烯科技有限公司 一种氮杂石墨纤维及其制备方法
CN109267416A (zh) * 2018-09-21 2019-01-25 杭州高烯科技有限公司 一种自融合的还原石墨烯纤维纸及其制备方法
CN109281224A (zh) * 2018-09-21 2019-01-29 杭州高烯科技有限公司 一种多孔石墨烯纤维无纺布及其制备方法
CN109295796A (zh) * 2018-09-21 2019-02-01 杭州高烯科技有限公司 一种自融合的氧化石墨烯纤维纸及其制备方法
CN110512311B (zh) * 2019-09-09 2022-12-30 苏州大学 一种利用微流控技术可控制备石墨烯纤维的方法
CN112647159B (zh) * 2019-10-10 2022-04-19 中国科学技术大学 一种多囊孔结构石墨烯基微米棒及其制备方法
CN110699779B (zh) * 2019-11-01 2022-05-13 常州富烯科技股份有限公司 氧化石墨烯纤维布及其制备方法、石墨烯气体扩散膜及其制备方法
CN111214962B (zh) * 2019-12-10 2021-04-13 中国科学院过程工程研究所 一种褶皱氧化石墨烯/纳米纤维复合膜及其制备方法和应用
CN112760813B (zh) * 2021-01-28 2022-01-07 广东春夏新材料科技股份有限公司 一种尿不湿用热风布及其制备方法
CN112941894A (zh) * 2021-02-01 2021-06-11 河北工业大学 一种微波诱导石墨烯纤维无纺布负载铋纳米颗粒的制备方法
CN113388905B (zh) * 2021-06-15 2022-07-05 广西大学 一种中空石墨烯纤维的自卷曲制备方法及其应用
CN113896186A (zh) * 2021-09-10 2022-01-07 山东建筑大学 一种缺陷化石墨烯的制备方法
CN115000355B (zh) * 2022-06-06 2024-01-30 中汽创智科技有限公司 一种三维金属锂-氧化物复合负极、其制备方法和应用

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