WO2020032684A1 - Bain de coagulation de filage de graphène par voie humide et procédé de fabrication d'une fibre d'oxyde de graphène l'utilisant - Google Patents

Bain de coagulation de filage de graphène par voie humide et procédé de fabrication d'une fibre d'oxyde de graphène l'utilisant Download PDF

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WO2020032684A1
WO2020032684A1 PCT/KR2019/010075 KR2019010075W WO2020032684A1 WO 2020032684 A1 WO2020032684 A1 WO 2020032684A1 KR 2019010075 W KR2019010075 W KR 2019010075W WO 2020032684 A1 WO2020032684 A1 WO 2020032684A1
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graphene oxide
coagulation bath
crosslinking agent
solvent
fiber
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PCT/KR2019/010075
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English (en)
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Tae Hee Han
Tae Hyun Sung
Won Sik Eom
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Industry-University Cooperation Foundation Hanyang University
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Publication of WO2020032684A1 publication Critical patent/WO2020032684A1/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D—TEXTILES; PAPER
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • Exemplary embodiments of the present invention relate in general to the field of a coagulation bath and more specifically to a coagulation bath for graphene wet spinning.
  • Nanocarbon-based materials such as graphene and carbon nanotubes (CNTs) are high-end materials which are used as next generation electronic materials, heat sink materials or ultra-high strength structural materials because of very excellent electrical properties, thermal properties, flexibility and mechanical strength.
  • CNTs carbon nanotubes
  • graphene is a two-dimensional carbon isotope in which carbon atoms form a sp 2 -hybridized hexagonal honeycomb lattice structure, and the thickness of monolayer graphene is 0.2 to 0.3 nm, which is the thickness of a single carbon atom. Due to high electronic conductivity and a large specific surface area, graphene has been used in various fields of electrodes (electrode active materials) for a super capacitor, a sensor, a battery, a touch panel, and a flexible display; an actuator, a high efficiency solar cell, a heat sink film, a coating material, a sea water desalination filter, an ultra-fast charger, etc.
  • electrodes electrode active materials
  • the use of the excellent physical properties of the nanocarbon-based material is implemented using CNTs and graphene at the molecular level formed utilizing chemical vapor deposition. However, at the bulk unit, the excellent properties may not be effectively expressed due to the difficulty in implementing a large-size, massively synthesized and uniform nanocarbon crystal structure.
  • a nanocarbon fiber spinning technique is attracting attention as a technique that maximizes electrical and thermal properties as well as mechanical properties of nanocarbons by maximizing the orientation and interaction of the graphene layer.
  • the fiberization of nanocarbon may be generally realized by spinning nanocarbon dispersion into a coagulation bath which can reduce a repulsive force between graphene layers thereby linearly coagulating the nanocarbon.
  • a conventional coagulation bath only using a coagulating solvent such as ethyl acetate has a problem of very high shrinkage and drying speeds of a fiber.
  • a high shrinkage speed is the cause of a structural defect of the fiber, and the high drying speed is the cause of difficult handling of the fiber.
  • Example embodiments of the present invention provide an organic coagulation bath which can control the shrinkage and drying speeds of a graphene gel fiber during spinning in manufacture of a graphene oxide fiber using wet spinning.
  • a method of manufacturing a graphene oxide fiber may include preparing a graphene oxide dispersion containing graphene oxide sheets and a dispersion medium, preparing a graphene oxide gel fiber by spinning the dispersion into a coagulation bath containing a coagulating solvent which extracts the dispersion medium, a crosslinking agent which forms crosslinks between graphene oxide sheets and an emulsifier for mixing the coagulating solvent and the crosslinking agent, and drying the graphene oxide gel fiber.
  • the dispersion medium may be a polar organic solvent.
  • the coagulating solvent may be an amine-based solvent of a secondary amine or tertiary amine.
  • the coagulating solvent may be triethylamine, diethylamine, or dipropylamine.
  • the crosslinking agent may be a monovalent metal salt or an ammonium salt.
  • the monovalent metal salt or the ammonium salt may include a nitrate ion (NO 3 - ), a chloride ion (Cl - ), a sulfide ion (S 2 - ), a sulfate ion (SO 4 2- ), a carbonate ion (CO 3 2- ) or a thiocyanate ion (SCN - ) as an anion.
  • the crosslinking agent may be ammonium thiocyanate or sodium thiocyanate.
  • the emulsifier may be an amphipathic solvent exhibiting Lewis basicity.
  • the emulsifier may be acetonitrile.
  • the coagulating solvent and the emulsifier may be contained at a volume ratio of 1:0.7 to 1:2.5.
  • the crosslinking agent is contained at a ratio of 0.005 to 0.23 g per 1 ml of the coagulating solvent.
  • the coagulating solvent, the emulsifier and the crosslinking agent are contained at a ratio of 1:1:0.005 to 1:1:0.23 (ml:ml:g).
  • a coagulation bath for graphene wet spinning comprises a coagulating solvent which extracts a dispersion medium from a spun graphene oxide dispersion containing graphene oxide sheets and the dispersion medium, a crosslinking agent which forms crosslinks between the graphene oxide sheets, and an emulsifier which mixes the coagulating solvent and the crosslinking agent.
  • the coagulation bath has a pH ranging from 10.1 to 10.55.
  • an organic coagulation bath which can control the shrinkage and drying speeds of a graphene gel fiber during spinning may be provided. Therefore, the manufactured graphene oxide fiber may exhibit excellent structural stability and facilitate hybridization with various materials.
  • FIG. 1 is a schematic diagram illustrating a process of manufacturing a graphene oxide fiber using a coagulation bath according to example embodiments of the present invention
  • FIG. 2 is a set of images showing graphene oxide fibers manufactured according to Preparation Example 5 and 6;
  • FIG. 3A is a graph showing the pH of a coagulation bath according to the volume ratio of acetonitrile to triethylamine under the condition that the composition ratio of ammonium thiocyanate to triethylamine is fixed at 0.01 g/ml;
  • FIG. 3B is a graph showing the pH of the coagulation bath according to the composition ratio of ammonium thiocyanate to triethylamine (g/ml) under the condition that the volume ratio of acetonitrile and ethylamine is fixed at 1:1 (v:v).
  • FIG. 1 is a schematic diagram illustrating a process of manufacturing a graphene oxide fiber using a coagulation bath according to example embodiments of the present invention.
  • a graphene oxide dispersion 100 may be prepared.
  • the dispersion 100 may be a spinning solution for performing wet spinning.
  • the dispersion 100 may contain graphene oxide sheets which are dispersed in a dispersion medium.
  • the graphene oxide sheet may be generally obtained by chemically delaminating graphite and have several to tens or hundreds of stacked layers of graphene unit layers to have a thickness ranging from several to tens of nanometers.
  • the dispersion medium may be an organic solvent, specifically, a polar organic solvent, capable of uniformly dispersing the graphene oxide sheets. Therefore, the graphene oxide sheet, specifically, the graphene oxide sheet including the oxygen functional group having polarity may be more uniformly mixed in the dispersion medium.
  • the dispersion medium may be dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), ethyl acetate (EA), an alcohol such as methanol, ethanol, ethylene glycol or n-butanol or the combination thereof.
  • the dispersion medium may be DMF or DMSO.
  • a concentration of the graphene oxide dispersion 100 may be 1 mg/ml to 80 mg/ml, specifically, 1 mg/ml to 50 mg/ml, more specifically, 1 mg/ml to 10 mg/ml, and further more specifically, approximately 5 mg/ml.
  • a graphene oxide gel fiber 30a may be manufactured by spinning the dispersion 100, that is, the spinning solution, into a coagulation bath 200 through a nozzle 101.
  • the coagulation bath 200 may contain a crosslinking agent, an emulsifier and a coagulating solvent.
  • the dispersion medium conatained between the graphene oxide sheets in the spun or extruded solution may be exchanged with the coagulating solvent in the coagulation bath 200.
  • the coagulating solvent may rapidly extract the dispersion medium from the spun or extruded solution to promote coagulation of the spun or extruded solution to provide the graphene oxide gel fiber 30a.
  • the coagulating solvent may be an organic solvent, specifically, an amine-based solvent of a secondary amine or tertiary amine, a ketone-based solvent such as acetone, an acetate-based solvent such as ethyl acetate or an alcohol-based solvent such as ethanol or propanol.
  • the coagulating solvent may be an alkylamine having 1 to 3 carbon atoms, and specifically, a dialkylamine or a trialkylamine having 1 to 3 carbon atoms.
  • the coagulating solvent may be triethylamine, diethylamine or dipropylamine, and specifically, triethylamine.
  • the crosslinking agent may enter into the spun or extruded solution along with the coagulating solvent to form crosslinks between the graphene oxide sheets, thereby improving a strength of the graphene oxide gel fiber 30a. Therefore, a conventional problem of the low strength of the graphene oxide fiber, which was made by only using, for example, a coagulating solvent such as ethyl acetate in the coagulating bath, may be compensated.
  • the shrinkage and drying speeds of the graphene oxide gel fiber 30a may be controlled by controlling a content of the crosslinking agent with respect to the coagulating solvent.
  • the crosslinking agent forms crosslinks between the graphene oxide sheets; therefore, rapid shrinkage of the graphene oxide gel fiber 30a may be prevented and a time to dry the gel fiber 30a may be slowed down. Therefore, it is possible to reduce the probability that a structural detect of a graphene oxide fiber (not shown) will be formed later.
  • the coagulation bath according to example embodiments of the present invention includes a crosslinking agent that forms crosslinks between the graphene oxide sheets, conventional problems caused by the high shrinkage and drying speeds generated when only the coagulating solvent is used in the coagulating bath are prevented, and therefore an effect of increasing the structural stability of the finally-formed graphene oxide fiber may be exhibited.
  • the crosslinking agent may have a component ratio to be contained at a sufficient amount with respect to the coagulating solvent in order to slow down the shrinkage and drying speeds of the graphene oxide gel fiber, and to prevent undrying of the gel fiber, which may be caused by a too high content of the crosslinking agent.
  • the crosslinking agent may be contained in an amount of 0.005 to 0.23g, specifically 0.01 to 0.2g, more specifically 0.05 to 0.2g, more specifically 0.09 to 0.2g, more specifically 0.1 to 0.16g, per 1 ml of the coagulating solvent.
  • the crosslinking agent may be in the form of a salt, specifically, a metal salt or a non-metal salt, and in one example, may be one which can be dissolved in a solvent like water to yield a metal cation or non-metal cation, and an anion.
  • the metal cation may be a monovalent metal cation, for example, a sodium ion (Na + ) or a potassium ion (K + ), and the non-metal cation may be an ammonium ion (NH 4 + ).
  • the anion may be a nitrate ion (NO 3 - ), a chloride ion (Cl - ), a sulfide ion (S 2 - ), a sulfate ion (SO 4 2- ), a carbonate ion (CO 3 2- ) or a thiocyanate ion (SCN - ).
  • the crosslinking agent may be ammonium thiocyanate (NH 4 SCN) or sodium thiocyanate (NaSCN), and more specifically, ammonium thiocyanate (NH 4 SCN).
  • the emulsifier may be used to mix the coagulating solvent with the crosslinking agent in the coagulation bath 200, and may be an amphipathic solvent having both hydrophobicity and hydrophilicity. Accordingly, the emulsifier may be used to well dissolve the crosslinking agent in the coagulating solvent which is an organic solvent.
  • the emulsifier may have a Lewis base characteristic.
  • the emulsifier may be amphipathic and exhibit Lewis basicity. Therefore, the emulsifier may allow the coagulating bath to have basicity without a pH adjustor. As a result, an attractive force between the negatively-charged graphene oxide in the dispersion spun into the coagulation bath and the positively-charged crosslinking agent may be increased.
  • the pH and characteristics of the coagulation bath will be described in further detail with respect to experimental examples below.
  • the emulsifier may be acetonitrile.
  • the coagulating solvent and the emulsifier may be contained at a volume ratio of 1:0.7 to 1:2.5, specifically 1:0.7 to 1:2, more specifically 1:1 to 1:2, and most specifically 1:1.
  • the coagulation bath may exhibit basicity. This may be due to the emulsifier in the coagulation bath. Therefore, an attractive force between the negatively-charged graphene oxide spun into the coagulating bath and the positively-charged crosslinking agent may be increased.
  • the characteristics of the graphene oxide negatively charged due to an oxygen functional group are changed according to a pH environment. For example, in an acidic environment, a negative charge characteristic is weakened, and in a basic environment, the negative charge characteristic is strengthen. Therefore, when the spinning solution is spun into the coagulation bath exhibiting basicity, a difference in charge potential between the positive charge of the crosslinking agent and the negative charge of the graphene oxide is larger, and thus an attractive force between the graphene oxide and the crosslinking agent is further increased. Therefore, the structural stability of the formed graphene oxide gel fiber 30a may be more improved.
  • the coagulation bath 200 may have a pH of 10 or more, specifically a pH of 10.1 to 10.55, more specifically a pH of 10.36 to 10.46, further more specifically a pH of 10.37 to 10.45, and still further more specifically a pH of 10.38 to 10.44.
  • the coagulation bath 200 may increase the attractive force between the graphene oxide and the crosslinking agent, and therefore the structural stability of the formed gel fiber 30a may be improved.
  • the pH of the coagulation bath 200 may be controlled by a component ratio of the coagulating solvent, the emulsifier and the crosslinking agent.
  • the coagulating solvent and the emulsifier may be contained at a volume ratio of 1:0.7 to 1:2.5, specifically 1:0.7 to 1:2, more specifically 1:1 to 1:2, and further more specifically 1:1.
  • the coagulating solvent, the emulsifier and the crosslinking agent may be contained at a ratio of 1:1:0.005 to 1:1:0.23 (ml:ml:g), specifically 1:1:0.01 to 1:1:0.2 (ml:ml:g), specifically 1:1:0.05 to 1:1:0.2 (ml:ml:g), more specifically 1:1:0.09 to 1:1:0.20 (ml:ml:g), and further more specifically 1:1:0.1 to 1:1:0.16 (ml:ml:g).
  • the graphene oxide gel fiber 30a may be dried, for example, at room temperature, under an atmospheric environment. Accordingly, a graphene oxide fiber in which a plurality of graphene oxide sheets are stacked in a thickness direction, and the stacked graphene oxide sheets are arranged in a length-wise direction i.e., in a axial direction of the fiber can be manufactured to have a structure in which the inner surface of the graphene oxide sheet is shrunk.
  • the graphene oxide fiber may have a higher mechanical strength than the conventional graphene oxide fiber, and exhibit internal structural stability between the graphene oxide sheets.
  • the dried graphene oxide fiber may be thermally treated.
  • the thermal treatment may reduce graphene oxide in the graphene oxide fiber, and thus reduced graphene oxide fiber having excellent structural stability may be manufactured.
  • almost all of the materials introduced into the fiber from coagulation bath 200 may be removed, but in some cases, a small amount of material from the coagulation bath 200, that is, the crosslinking agent, the emulsifier and the coagulating solvent may be still contained in the reduced graphene oxide fiber. Due to high volatility, the coagulating solvent may remain at an ultimately smaller amount than the crosslinking agent and the emulsifier.
  • the thermal treatment may be performed in an inert gas atmosphere such as an argon gas at a temperature ranging from 800°C to 1300°C, and specifically, approximately 1200°C.
  • the strength and structural stability of the formed graphene oxide fiber may be improved by controlling a component and a component ratio in the coagulation bath.
  • the coagulation bath may include a crosslinking agent capable of forming crosslinks between the graphene oxide sheets, a coagulating solvent, which is an amine-based solvent for rapid extraction of a dispersion medium from a spun spinning solution extruded through a nozzle, and an emulsifier for mixing the crosslinking agent and the coagulating solvent. Therefore, the shrinkage and drying speeds of the graphene oxide gel fiber may be controlled.
  • a crosslinking agent capable of forming crosslinks between the graphene oxide sheets
  • a coagulating solvent which is an amine-based solvent for rapid extraction of a dispersion medium from a spun spinning solution extruded through a nozzle
  • an emulsifier for mixing the crosslinking agent and the coagulating solvent. Therefore, the shrinkage and drying speeds of the graphene oxide gel fiber may be controlled.
  • the crosslinking agent may be contained in an amount of 0.005 to 0.23g, specifically 0.01 to 0.2g, specifically 0.05 to 0.2g, more specifically 0.09 to 0.2g, more specifically 0.1 to 0.16g, per 1 ml of the coagulating solvent in the coagulation bath.
  • the coagulating solvent and the emulsifier may be contained at a volume ratio of 1:0.7 to 1:2.5, specifically 1:0.7 to 1:2, more specifically, 1:1 to 1:2, and further more specifically 1:1.
  • the coagulating solvent and the emulsifier may be mixed at a volume ratio of 1:0.7 to 1:2.5, and specifically 1:1 to 1:2.
  • the coagulating solvent, the emulsifier and the cross-linking agent may be mixed at a ratio of 1:1:0.005 to 1:1:0.23 (ml:ml:g), specifically 1:1:0.01 to 1:1:0.2 (ml:ml:g), specifically 1:1:0.05 to 1:1:0.2 (ml:ml:g), more specifically 1:1:0.09 to 1:1:0.20 (ml:ml:g), and further more specifically 1:1:0.1 to 1:1:0.16 (ml:ml:g).
  • a graphene oxide dispersion i.e., a graphene oxide DMF dispersion was prepared in which the graphene oxide powder was dispersed in DMF at a concentration of 5 mg/ml.
  • the graphene oxide dispersion was formed by dispersing the graphene oxide powder in water, putting a large amount of DMF therein, and then removing most of water using a centrifuge.
  • the graphene oxide dispersion was spun into a coagulation bath containing triethylamine (TEA) which is a coagulating solvent, acetonitrile (ACN) which is an emulsifier and ammonium thiocyanate(NH 4 SCN) which is a crosslinking agent to prepare graphene oxide gel fibers. Thereafter, the gel fibers were dried at room temperature (25 °C) to prepare the graphene oxide fiber.
  • TSA triethylamine
  • ACN acetonitrile
  • ammonium thiocyanate(NH 4 SCN) which is a crosslinking agent
  • the content of TEA, ACN, and NH 4 SCN in the preparation of graphene oxide fibers according to the preparation example was varied as shown in Table 1 below.
  • the gel fiber strength, the physical properties of the fibers, the pH of the coagulation bath were measured and are shown in Table 1 below.
  • Preparation Examples 3 to 7 when the volume ratio of TEA and ACN was 1:1, spinning was smoothly performed.
  • the higher the content of the crosslinking agent i.e. ammonium thiocyanate(NH 4 SCN), the higher the strength of the fiber.
  • Preparation Examples 4 to 6 showed decreases in drying speed and (thickness-direction) shrinkage rate during the formation of the fiber.
  • the content of the crosslinking agent was so high that the drying speed of the fiber was too low and thereby producing fiber not completely dried.
  • the crosslinking agent when the crosslinking agent is contained in the coagulation bath of the above-described embodiments while the coagulation solvent and emulsifier are mixed at a ratio of 1: 1 to 1: 2, phase separation does not occur and the spinning can proceed well. Furthermore, when the coagulating solvent and the emulsifier are contained in a ratio of 1: 1 and the crosslinking agent is contained, the gel fiber drying rate is slowed and the shrinkage in the thickness direction is reduced. Particularly, when the crosslinking agent is contained at a ratio of 0.05 to 0.16 g per 1 ml of the coagulation solvent while the coagulating solvent and emulsifier is contained in a ratio of 1:1, the shrinkage in the thickness direction can be further reduced. Accordingly, it is possible to reduce the possibility of occurrence of structural defects in the fiber and to exhibit excellent strength characteristics of the fiber.
  • FIG. 2 is a set of images showing graphene oxide fibers manufactured according to Preparation Example 5 and 6.
  • the gel fiber was more uniformly and stably spun into the coagulation bath, and the spun fiber exhibited a strength sufficiently high so as to facilitate continuous spinning.
  • FIG. 3A is a graph showing the pH of a coagulation bath according to the volume ratio of acetonitrile to triethylamine under the condition that the composition ratio of ammonium thiocyanate to triethylamine is fixed at 0.01 g/ml
  • FIG. 3B is a graph showing the pH of the coagulation bath according to the composition ratio of ammonium thiocyanate to triethylamine (g/ml) under the condition that the volume ratio of acetonitrile and ethylamine is fixed at 1:1 (v:v).
  • the coagulation bath is prepared by adding acetonitrile as an emulsifier as well as ammonia thiocyanate as a crosslinking agent to triethylamine as a coagulating solvent
  • spinning can proceed smoothly.
  • the coagulating solvent and the emulsifier were mixed in a ratio of 1: 1 to 1: 2 and the crosslinking agent is contained 0.01 to 0.24 g per 1 ml of the coagulating solvent, the spinning was smoothly proceeded.
  • the crosslinking agent when the crosslinking agent is contained at a ratio of 0.01 to 0.16 g relative to 1 ml of the coagulating solvent while the coagulating solvent and the emulsifying agent are mixed at a ratio of 1:1, the strength of the fiber is increased while the fiber is dried properly together with the smooth spinning.
  • the crosslinking agent is contained at a ratio of 0.1 to 0.16 g per 1 ml of the coagulating solvent, the shrinkage in the thickness direction can be further reduced and the strength of the fiber can be greatly increased.
  • the pH of the coagulation bath which enables smooth or optimal spinning is in the range of 10.36 to 10.5, and that the pH of the coagulation bath is preferably in the range of 10.38 to 10.44 in consideration of the strength of the fiber.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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Abstract

La présente invention concerne un bain de coagulation de filage de graphène par voie humide et un procédé de fabrication d'une fibre d'oxyde de graphène l'utilisant. Le procédé de fabrication d'une fibre d'oxyde de graphène de l'invention comprend la préparation d'une dispersion d'oxyde de graphène contenant des feuilles d'oxyde de graphène et un milieu de dispersion, la préparation d'une fibre de gel d'oxyde de graphène par filage de la dispersion dans un bain de coagulation contenant un solvant coagulant qui extrait le milieu de dispersion, un agent de réticulation qui forme des réticulations entre les feuilles d'oxyde de graphène et un émulsifiant pour mélanger le solvant coagulant et l'agent de réticulation, et le séchage de la fibre de gel d'oxyde de graphène.
PCT/KR2019/010075 2018-08-09 2019-08-09 Bain de coagulation de filage de graphène par voie humide et procédé de fabrication d'une fibre d'oxyde de graphène l'utilisant WO2020032684A1 (fr)

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CN113823456A (zh) * 2020-06-19 2021-12-21 北京石墨烯研究院 柔性石墨烯电极及其制备方法和应用
CN114990734A (zh) * 2022-06-07 2022-09-02 苏州大学 一种石墨烯组装体纤维及其制备方法与应用
WO2022265586A1 (fr) * 2021-06-19 2022-12-22 National Science And Technology Development Agency Procédé de préparation de fibres d'oxyde de graphène par filage humide

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CN113493935A (zh) * 2020-04-01 2021-10-12 苏州合祥纺织科技有限公司 一种琼胶纤维的制备方法

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