WO2019066492A2 - Fibre de graphène fabriquée par chauffe par effet joule et son procédé de fabrication - Google Patents

Fibre de graphène fabriquée par chauffe par effet joule et son procédé de fabrication Download PDF

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WO2019066492A2
WO2019066492A2 PCT/KR2018/011428 KR2018011428W WO2019066492A2 WO 2019066492 A2 WO2019066492 A2 WO 2019066492A2 KR 2018011428 W KR2018011428 W KR 2018011428W WO 2019066492 A2 WO2019066492 A2 WO 2019066492A2
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Prior art keywords
graphene fiber
graphene
fiber
primary
joule
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PCT/KR2018/011428
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English (en)
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WO2019066492A3 (fr
Inventor
Tae Hee Han
Sung Hyun Noh
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Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University)
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Priority claimed from KR1020180014797A external-priority patent/KR102650379B1/ko
Application filed by Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University) filed Critical Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University)
Priority to US16/651,806 priority Critical patent/US11661677B2/en
Publication of WO2019066492A2 publication Critical patent/WO2019066492A2/fr
Publication of WO2019066492A3 publication Critical patent/WO2019066492A3/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
    • 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
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • 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
    • 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
    • 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

Definitions

  • Embodiments of the inventive concepts relate to a graphene fiber manufactured by a Joule heating method and a method of manufacturing the same and, more particularly, to a graphene fiber manufactured by a Joule heating method using a method of reducing a graphene oxide fiber and a method of manufacturing the same.
  • Fiber-based wearable electronic devices attract attention as e-textiles.
  • the fiber-based wearable electronic devices may be free to change the design and may not be broken when dropped, and thus they may be foldable, bendable and rollable and may be lighter.
  • the possibility of 'wearable electronics' increases.
  • Embodiments of the inventive concepts may provide a graphene fiber with improved electrical conductivity and a method of manufacturing the same using Joule heating.
  • Embodiments of the inventive concepts may also provide a graphene fiber manufactured by simple processes and a method of manufacturing the same using Joule heating.
  • Embodiments of the inventive concepts may further provide a graphene fiber in which amorphous carbon is crystallized, and a method of manufacturing the same using Joule heating.
  • a method of manufacturing a graphene fiber may include preparing a source solution including graphene oxide, supplying the source solution into a coagulation solution to form a graphene oxide fiber, reducing the graphene oxide fiber to form a primary graphene fiber, and Joule-heating the primary graphene fiber to form a secondary graphene fiber.
  • the primary graphene fiber may be Joule-heated such that amorphous carbon in the primary graphene fiber is crystallized.
  • a value of a current applied to the primary graphene fiber for Joule-heating the primary graphene fiber may be controlled according to a reduction level of the primary graphene fiber, in the Joule-heating of the primary graphene fiber to form the secondary graphene fiber.
  • the value of the current applied to the primary graphene fiber for Joule-heating the primary graphene fiber may increase as the reduction level of the primary graphene fiber increases, in the Joule-heating of the primary graphene fiber to form the secondary graphene fiber.
  • an electrical conductivity of the secondary graphene fiber may increase as a concentration of the graphene oxide in the source solution increases.
  • a value of a current applied to the primary graphene fiber for Joule-heating the primary graphene fiber may increase in the Joule-heating of the primary graphene fiber to form the secondary graphene fiber.
  • an elongation percentage of the secondary graphene fiber may be controlled by controlling a concentration of the graphene oxide in the source solution or a supply rate of the source solution.
  • the reducing of the graphene oxide fiber to form the primary graphene fiber may include preparing a reduction solution including a reducing agent, and immersing the graphene oxide fiber in the reduction solution.
  • the Joule-heating of the primary graphene fiber to form the secondary graphene fiber may be performed using a roll-to-roll process.
  • a roller may be used as an electrode in the roll-to-roll process.
  • a graphene fiber may include a secondary graphene fiber formed by Joule-heating a primary graphene fiber formed by reducing a graphene oxide fiber.
  • the secondary graphene fiber may include a plurality of graphene sheets agglomerated and extending in one direction.
  • a crystallinity of the primary graphene fiber may be lower than a crystallinity of the secondary graphene fiber.
  • each of the primary graphene fiber and the secondary graphene fiber may include a stack structure in which the graphene sheets are stacked.
  • a thickness of the stack structure and a grain size of the graphene sheet in the secondary graphene fiber may be greater than a thickness of the stack structure and a grain size of the graphene sheet in the primary graphene fiber, respectively.
  • an electrical conductivity of the secondary graphene fiber may increase as a value of a current applied to the primary graphene fiber increases.
  • a value of a current applied to the primary graphene fiber for Joule-heating the primary graphene fiber may be controlled according to a reduction level of the primary graphene fiber.
  • a value of a current applied to the primary graphene fiber may be controlled according to a degree of orientation of a plurality of graphene sheets in the primary graphene fiber.
  • the method of manufacturing the graphene fiber may include preparing the source solution including the graphene oxide, supplying the source solution into the coagulation solution to form the graphene oxide fiber, reducing the graphene oxide fiber to form the primary graphene fiber, and Joule-heating the primary graphene fiber to form the secondary graphene fiber.
  • the amorphous carbon in the primary graphene fiber may be crystallized by Joule-heating the primary graphene fiber.
  • the high-efficiency graphene fiber with the improved electrical conductivity may be manufactured by simplified processes.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a graphene fiber according to some embodiments of the inventive concepts.
  • FIGS. 2 to 4 are schematic views illustrating processes of manufacturing a graphene fiber according to some embodiments of the inventive concepts.
  • FIG. 5 is a schematic view illustrating another embodiment of a process of forming a secondary graphene fiber in a method of manufacturing a graphene fiber according to some embodiments of the inventive concepts.
  • FIG. 6 shows images obtained from a graphene fiber according to an embodiment of the inventive concepts and an apparatus used to manufacture the graphene fiber.
  • FIG. 7 is a graph showing durability of a graphene fiber according to an embodiment of the inventive concepts.
  • FIGS. 8 and 9 are graphs showing a structural feature of an inside of a graphene fiber according to an embodiment of the inventive concepts.
  • FIGS. 10 and 11 are graphs showing electrical characteristics of a graphene fiber according to an embodiment of the inventive concepts.
  • FIG. 12 is a graph showing a temperature change of a graphene fiber according to an embodiment of the inventive concepts.
  • FIGS. 13 and 14 show a graph and images obtained from light generated from a graphene fiber according to an embodiment of the inventive concepts.
  • FIG. 15 shows comparison images before and after a current is applied to a graphene fiber according to an embodiment of the inventive concepts.
  • FIGS. 16 and 17 are images obtained from a cross section of a graphene fiber according to an embodiment of the inventive concepts.
  • FIG. 18 is a graph comparing characteristics of an inner structure according to a current applied to a graphene fiber according to an embodiment of the inventive concepts.
  • FIG. 19 is a graph showing characteristics of an inside of a graphene fiber according to an embodiment of the inventive concepts.
  • FIG. 20 is a graph comparing a structural feature of a graphene fiber according to an embodiment of the inventive concepts with graphite.
  • FIG. 21 is a graph showing a ratio of carbon to oxygen in a graphene fiber according to an embodiment of the inventive concepts.
  • FIG. 22 shows wide angle x-ray diffraction (WAXD) images of a graphene fiber according to an embodiment of the inventive concepts.
  • WAXD wide angle x-ray diffraction
  • FIGS. 23 and 24 are graphs obtained by analyzing characteristics of the WAXD images of FIG. 22.
  • FIG. 25a ⁇ 25c shows graphs comparing characteristics of an inner structure according to a value of a current applied to a graphene fiber according to an embodiment of the inventive concepts.
  • FIG. 26 is a diagram illustrating a change in an inner structure according to a current applied to a graphene fiber according to an embodiment of the inventive concepts.
  • FIG. 27 shows an image and a graph which show a temperature of a graphene fiber according to an embodiment of the inventive concepts.
  • FIG. 28 is a graph comparing characteristics of a graphene fiber according to an embodiment of the inventive concepts with those of a copper wire.
  • FIG. 29 is a graph showing reaction of a graphene fiber according to an embodiment of the inventive concepts and oxygen in air.
  • inventive concepts will now be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the inventive concepts are shown. It should be noted, however, that the inventive concepts are not limited to the following exemplary embodiments, and may be implemented in various forms. Accordingly, the exemplary embodiments are provided only to disclose the inventive concepts and let those skilled in the art know the category of the inventive concepts.
  • the term 'reduction level' means the degree of reduction. In other words, it will be understood that when the reduction level of an object is high, the object may be in a completely reduced state or may be close to the completely reduced state. On the contrary, it will be understood that when the reduction level of an object is low, the object may be in an original state or may be close to the original state.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a graphene fiber according to some embodiments of the inventive concepts
  • FIGS. 2 to 4 are schematic views illustrating processes of manufacturing a graphene fiber according to some embodiments of the inventive concepts.
  • a source solution 10 may be prepared (S100).
  • the source solution 10 may include graphene oxide.
  • the source solution 10 may be formed by adding the graphene oxide into a solvent.
  • the solvent may be water or an organic solvent.
  • the organic solvent may be dimethyl sulfoxide (DMSO), ethylene glycol, n-methyl-2-pyrrolidone (NMP), or dimethylformamide (DMF).
  • the source solution 10 may be formed by adding the graphene oxide into the organic solvent at a concentration of 5 mg/mL.
  • the source solution 10 may be supplied into a coagulation solution 20 to form a graphene oxide fiber 30 (S200).
  • the coagulation solution 20 may include a coagulant.
  • the graphene oxide fiber 30 formed by supplying the source solution 10 into the coagulation solution 20 may be coagulated by the coagulant included in the coagulation solution 20.
  • the coagulant may be calcium chloride (CaCl 2 ), potassium hydroxide (KOH), sodium hydroxide (NaOH), sodium chloride (NaCl), copper sulfate (CuSO 4 ), cetyltrimethylammonium bromide (CTAB), or chitosan.
  • the source solution 10 provided in a source container 100 may be supplied into a coagulation bath 200 having the coagulation solution 20 through a spinneret 120 connected to the source container 100.
  • the graphene oxide fiber 30 may be separated from the coagulation solution 20 and then may be cleaned and dried. By a guide roller 130, the graphene oxide fiber 30 may be separated from the coagulation bath 200 having the coagulation solution 20 and may exit to the outside. The graphene oxide fiber 30 separated from the coagulation solution 20 may include the coagulant.
  • a cleaning solution used in the cleaning process may be an alcoholic aqueous solution.
  • water included in the graphene oxide fiber 30 may be naturally dried in air through the separating and cleaning processes.
  • the graphene oxide fiber 30 naturally dried in the air may be additionally dried through a heating process. In other words, at least a portion of water remaining in the graphene oxide fiber 30 may be removed through the heating process.
  • the graphene oxide fiber 30 may be winded while being dried through the heating process. As illustrated in FIG. 2, after the cleaning process, the graphene oxide fiber 30 may be winded by a winding roller 140 while the drying process is performed.
  • the graphene oxide fiber 30 may be reduced to form a primary graphene fiber 50 (S300).
  • the formation of the primary graphene fiber 50 may include preparing a reduction solution 40 including a reducing agent, and immersing the graphene oxide fiber 30 in the reduction solution 40.
  • the reducing agent may be hydroiodic acid (HI).
  • the reduction solution 40 may be a solution in which HI having a concentration of 50 wt% is mixed with water having a concentration of 50 wt%.
  • a reduction level of the primary graphene fiber 50 may be controlled by controlling a concentration of the reducing agent included in the reduction solution 40 and a time for which the graphene oxide fiber 30 is immersed in the reduction solution 40.
  • the reduction level of the primary graphene fiber 50 may increase as the concentration of the reducing agent included in the reduction solution 40 increases.
  • the reduction level of the primary graphene fiber 50 may increase as the time for which the graphene oxide fiber 30 is immersed in the reduction solution 40 increases.
  • the reduction level of the primary graphene fiber 50 may decrease as the concentration of the reducing agent included in the reduction solution 40 decreases.
  • the reduction level of the primary graphene fiber 50 may decrease as the time for which the graphene oxide fiber 30 is immersed in the reduction solution 40 decreases.
  • the graphene oxide fiber 30 may be reduced in a reducing gas atmosphere to form the primary graphene fiber 50.
  • the reduction level of the primary graphene fiber 50 may increase as a concentration of the reducing gas increases or as a time for which the reducing gas is provided increases.
  • the reduction level of the primary graphene fiber 50 may decrease as the concentration of the reducing gas decreases or as the time for which the reducing gas is provided decreases.
  • the primary graphene fiber 50 may be Joule-heated to form a secondary graphene fiber 60 (S400).
  • an apparatus for Joule-heating the primary graphene fiber 50 may include a chamber 300 and a power source 330.
  • the chamber 300 may include electrodes 310 and a gas inlet 320.
  • the primary graphene fiber 50 may be disposed between the electrodes 310 in the chamber 300 and may be Joule-heated.
  • the electrodes 310 may include copper (Cu).
  • the inside of the chamber 300 may be filled with an inert gas injected through the gas inlet 320.
  • the inert gas may be an argon (Ar) gas.
  • the primary graphene fiber 50 is Joule-heated, amorphous carbon in the primary graphene fiber 50 may be crystallized.
  • the secondary graphene fiber 60 may be formed by crystallizing the amorphous carbon in the primary graphene fiber 50.
  • the secondary graphene fiber 60 may include a plurality of agglomerated graphene sheets extending in one direction.
  • each of the primary graphene fiber 50 and the secondary graphene fiber 60 may include a stack structure in which graphene sheets are stacked.
  • a thickness of the stack structure and a grain size of the graphene sheet may be changed.
  • the thickness of the stack structure and the grain size of the graphene sheet may be increased.
  • the thickness of the stack structure and the grain size of the graphene sheet in the secondary graphene fiber 60 may be greater than the thickness of the stack structure and the grain size of the graphene sheet in the primary graphene fiber 50, respectively.
  • a crystallinity of the primary graphene fiber 50 may be lower than a crystallinity of the secondary graphene fiber 60.
  • An elongation percentage of the secondary graphene fiber 60 may be controlled by a concentration of the graphene oxide in the source solution 10 or a supply rate of the source solution 10 through the spinneret 120.
  • a degree of orientation of the secondary graphene fiber 60 may decrease and a porosity of the secondary graphene fiber 60 may increase.
  • the elongation percentage of the secondary graphene fiber 60 may increase.
  • the degree of orientation of the secondary graphene fiber 60 may decrease and the porosity of the secondary graphene fiber 60 may increase.
  • the elongation percentage of the secondary graphene fiber 60 may increase.
  • An electrical conductivity of the secondary graphene fiber 60 may be controlled by a value of a current applied to the primary graphene fiber 50.
  • the electrical conductivity of the secondary graphene fiber 60 may increase as the value of the current applied to the primary graphene fiber 50 increases.
  • the value of the current applied to the primary graphene fiber 50 may be controlled according to the reduction level of the primary graphene fiber 50 or the supply rate of the source solution 10.
  • the value of the current applied to the primary graphene fiber 50 may be adjusted according to the reduction level of the primary graphene fiber 50 or the supply rate of the source solution 10, and thus the electrical conductivity of the secondary graphene fiber 60 may be controlled.
  • Mechanisms for controlling the value of the current applied to the primary graphene fiber 50 will be described hereinafter in more detail.
  • the value of the current applied to the primary graphene fiber 50 may be controlled according to the reduction level of the primary graphene fiber 50.
  • the value of the current applied to the primary graphene fiber 50 may increase as the reduction level of the primary graphene fiber 50 increases.
  • the reduction level of the primary graphene fiber 50 when the reduction level of the primary graphene fiber 50 is low, an oxygen concentration in the primary graphene fiber 50 may be high, and thus a resistance of the primary graphene fiber 50 may be high. In this case, if the value of the current applied to the primary graphene fiber 50 is increased, the primary graphene fiber 50 may be broken. Thus, when the reduction level of the primary graphene fiber 50 is low, the value of the current applied to the primary graphene fiber 50 may be controlled to be relatively low.
  • the value of the current applied to the primary graphene fiber 50 may be controlled to be relatively high.
  • the value of the current applied to the primary graphene fiber 50 may be controlled according to the supply rate of the source solution 10.
  • the value of the current applied to the primary graphene fiber 50 may increase as the supply rate of the source solution 10 increases.
  • the supply rate of the source solution 10 when the supply rate of the source solution 10 is low, degrees of orientation of the plurality of graphene sheets in the primary graphene fiber 50 may be low, and thus the resistance of the primary graphene fiber 50 may be high. In this case, if the value of the current applied to the primary graphene fiber 50 is increased, the primary graphene fiber 50 may be broken. Thus, when the supply rate of the source solution 10 is relatively low, the value of the current applied to the primary graphene fiber 50 may be controlled to be relatively low.
  • the degrees of orientation of the plurality of graphene sheets in the primary graphene fiber 50 may be high, and thus the resistance of the primary graphene fiber 50 may be low.
  • the value of the current applied to the primary graphene fiber 50 may be controlled to be relatively high.
  • the value of the current applied to the primary graphene fiber 50 for Joule-heating the primary graphene fiber 50 may be increased through the method of increasing the reduction level of the primary graphene fiber 50 or the method of increasing the supply rate of the source solution 10.
  • the electrical conductivity of the secondary graphene fiber 60 may be increased to manufacture a high-efficiency graphene fiber.
  • the concentration of the graphene oxide in the source solution 10 may be controlled to improve the electrical conductivity of the secondary graphene fiber 60.
  • the electrical conductivity of the secondary graphene fiber 60 may be improved as the concentration of the graphene oxide in the source solution 10 increases.
  • the graphene sheets in the secondary graphene fiber 60 may be increased, and thus the electrical conductivity of the secondary graphene fiber 60 may be improved.
  • FIG. 5 is a schematic view illustrating another embodiment of a process of forming a secondary graphene fiber in a method of manufacturing a graphene fiber according to some embodiments of the inventive concepts.
  • a roll-to-roll apparatus 400 for performing the roll-to-roll process may include a roller 410 and electrodes 420.
  • the roller 410 may be provided in plurality, and the rollers 410 may be spaced apart from each other.
  • the primary graphene fiber 50 may be provided on the rollers 410.
  • the primary graphene fiber 50 may be moved by rotation of the rollers 410.
  • the primary graphene fiber 50 may come in contact with the electrodes 420 while being moved by the rollers 410, and thus the primary graphene fiber 50 may be Joule-heated.
  • the electrodes 420 may be spaced apart from each other on the primary graphene fiber 50. In other embodiments, the rollers 410 may be used as the electrodes 420.
  • the method of manufacturing the graphene fiber may include preparing the source solution 10 including the graphene oxide, supplying the source solution 10 into the coagulation solution 20 to form the graphene oxide fiber 30, reducing the graphene oxide fiber 30 to form the primary graphene fiber 50, and Joule-heating the primary graphene fiber 50 to form the secondary graphene fiber 60.
  • the amorphous carbon in the primary graphene fiber 50 may be crystallized by Joule-heating the primary graphene fiber 50.
  • the high-efficiency graphene fiber with the improved electrical conductivity may be manufactured.
  • a graphene oxide solution having a concentration of 5 mg/mL was prepared.
  • the graphene oxide solution was supplied into a CaCl 2 solution having a concentration of 0.45 mol/L at a supply rate of 20 mL/hour through a needle having a diameter of 20 ⁇ m to form a graphene oxide fiber.
  • a hydroiodic acid (HI) solution of 50 wt% was mixed with water of 50 wt% to prepare a solution, and the solution was maintained at a temperature of 80 degrees Celsius.
  • the formed graphene oxide fiber was immersed in the solution of 80 degrees Celsius for 1 hour, and thus the graphene oxide fiber was reduced to form a primary graphene fiber.
  • the reduced graphene oxide fiber i.e., the primary graphene fiber
  • the reduced graphene oxide fiber was provided into a chamber filled with argon, and copper electrodes were connected to the reduced graphene oxide fiber through silver paste.
  • a current from 0 mA to 100 mA was applied to the reduced graphene oxide fiber at a rate of 250 ⁇ A/s, and thus a graphene fiber according to the embodiment was manufactured.
  • 'GOF' represents the graphene oxide fiber
  • 'GF' represents the primary graphene fiber
  • 'Current-treated GF' represents the graphene fiber according to the embodiment.
  • FIG. 6 shows images obtained from a graphene fiber according to an embodiment of the inventive concepts and an apparatus used to manufacture the graphene fiber.
  • an image of the graphene oxide fiber was obtained using a general camera in the process of manufacturing the graphene fiber.
  • the graphene oxide fiber is formed by supplying the graphene oxide solution into the CaCl 2 solution.
  • an image of the graphene fiber according to the embodiment was obtained using a scanning electron microscope (SEM). As shown in the image (b) of FIG. 6, graphene sheets are stacked in the graphene fiber according to the embodiment.
  • an image of an apparatus of manufacturing the graphene fiber according to the embodiment was obtained using a general camera. As shown in the image (c) of FIG. 6, heat is generated by applying the current to the primary graphene fiber in the process of manufacturing the graphene fiber according to the embodiment.
  • FIG. 7 is a graph showing durability of a graphene fiber according to an embodiment of the inventive concepts.
  • An image (b) of FIG. 7 shows the primary graphene fiber broken as described with reference to the graph (a) of FIG. 7.
  • the primary graphene fiber is broken.
  • FIGS. 8 and 9 are graphs showing a structural feature of an inside of a graphene fiber according to an embodiment of the inventive concepts.
  • FIG. 8 shows an intensity (a.u.) according to Raman shift (cm -1 ) of each of the graphene oxide fiber (GOF), the primary graphene fiber (GF) and the graphene fiber (Current-treated GF) according to the embodiment.
  • both a G-band representing a sp 2 structure and a D-band representing a defective site structure are shown in the graphene oxide fiber and the primary graphene fiber.
  • the G-band is shown but a substantial D-band is not shown. In other words, it is recognized that defect structures in the graphene fiber according to the embodiment are removed since the primary graphene fiber is Joule-heated.
  • FIG. 9 shows a relative resistivity according to a current density (A cm -2 ) of the graphene fiber according to the embodiment in each case.
  • the relative resistivity of the graphene fiber according to the embodiment decreases as the value of the current applied to the primary graphene fiber increases.
  • a resistance value when the current is interrupted is greater than a resistance value when the current is applied.
  • a difference between the resistance value when the current is interrupted and the resistance value when the current is applied decreases as the number of the cycles increases.
  • FIGS. 10 and 11 are graphs showing electrical characteristics of a graphene fiber according to an embodiment of the inventive concepts.
  • a current (mA) according to a voltage (V) was measured from each of the graphene oxide fiber (GOF), the primary graphene fiber (GF) and the graphene fiber (Current-treated GF) according to the embodiment.
  • a gradient of a graph of the current according to the voltage of the graphene oxide fiber is substantially equal to a gradient of a graph of the current according to the voltage of the primary graphene fiber, but a gradient of a graph of the current according to the voltage of the graphene fiber of the embodiment is steeper than the gradients of the graphene oxide fiber and the primary graphene fiber.
  • a resistance of the graphene fiber according to the embodiment is lower than those of the graphene oxide fiber and the primary graphene fiber.
  • a peck current density (A cm -2 ) according to a relative resistivity was measured from the primary graphene fiber (GF) before applying the current.
  • a peck current density (A cm -2 ) according to a relative resistivity was measured from the graphene fiber according to the embodiment after applying each of currents of 10 mA, 20 mA, 30 mA, 40 mA, 50 mA and 60 mA.
  • the relative resistivity of the primary graphene fiber is the highest, and the relative resistivity of the graphene fiber according to the embodiment decreases as the value of the current applied to the primary graphene fiber increases.
  • a voltage (V) and a resistance (k ⁇ ) of the graphene fiber according to a current (mA) applied to the graphene fiber of the were measured, and the measured values were shown in the graph (b) of FIG. 11.
  • the resistance of the graphene fiber according to the decreases as the value of the applied current increases.
  • the voltage of the graphene fiber according to the embodiment increases and then is maintained constant from 30 mA.
  • FIG. 12 is a graph showing a temperature change of a graphene fiber according to an embodiment of the inventive concepts.
  • a change in temperature according to a value of a current applied to the graphene fiber of the embodiment was measured, and the measured results were shown in FIG. 12. As shown in FIG. 12, the temperature of the graphene fiber according to the embodiment increases as the value of the applied current increases.
  • FIGS. 13 and 14 show a graph and images obtained from light generated from a graphene fiber according to an embodiment of the inventive concepts.
  • the spectral radiance according to the emission wavelength of the graphene fiber of the embodiment increases as the value of the applied current increases.
  • an intensity of light generated from the graphene fiber of the embodiment increases as the value of the current applied to the graphene fiber increases.
  • Images (a) to (d) of FIG. 14 show lights generated from the graphene fiber of the embodiment when applying the currents of 20 mA, 40 mA, 80 mA and 100 mA to the graphene fiber.
  • the light generated from the graphene fiber according to the embodiment becomes brighter as the value of the current applied to the graphene fiber increases. Accordingly, it is considered that the number of electrons colliding with nuclei of carbon atoms increases to emit stronger radiant energy as the value of the applied current increases. In other words, a Joule heating phenomenon occurs at the graphene fiber according to the embodiment as shown in FIGS. 13 and 14.
  • FIG. 15 shows comparison images before and after a current is applied to a graphene fiber according to an embodiment of the inventive concepts.
  • images (a) and (b) of the graphene fiber of the embodiment before and after applying a current to the graphene fiber were obtained by a scanning electron microscope (SEM) at a scale of 10 ⁇ m.
  • SEM scanning electron microscope
  • FIGS. 16 and 17 are images obtained from a cross section of a graphene fiber according to an embodiment of the inventive concepts.
  • images (a) to (d) of FIG. 16 an image of a cross section of the graphene fiber before applying a current was obtained by a SEM, and images of cross sections of the graphene fibers after applying currents of 40 mA, 60 mA and 80 mA were obtained by the SEM.
  • Images (a) to (d) of FIG. 17 are enlarged SEM images of the images (a) to (d) of FIG. 16, respectively.
  • graphene sheets are stacked in each of the graphene fibers according to the embodiment.
  • FIG. 18 is a graph comparing characteristics of an inner structure according to a current applied to a graphene fiber according to an embodiment of the inventive concepts.
  • an intensity (a.u.) according to Raman shift (cm -1 ) of the graphene fiber (GF) of the embodiment before applying a current was measured.
  • currents of 10 mA (GF10) to 100 mA (FG100) were applied to the graphene fiber of the embodiment, and an intensity (a.u.) according to Raman shift (cm -1 ) of the graphene fiber with respect to each current was measured.
  • a peak of a D-band becomes smaller as the value of the current applied to the graphene fiber of the embodiment increases.
  • inner defects of the graphene fiber of the embodiment decreases as the value of the current applied to the graphene fiber increases.
  • FIG. 19 is a graph showing characteristics of an inside of a graphene fiber according to an embodiment of the inventive concepts.
  • a graph (a) of FIG. 19 currents of 10 mA to 100 mA were applied to the graphene fiber according to the embodiment, a ID/IG value and a conductivity (S cm -1 ) of the graphene fiber at each current were measured. The measured results were shown in the graph (a) of FIG. 19.
  • ID and IG mean an intensity of a D peak and an intensity of a G peak shown in the graph of FIG. 18, respectively.
  • the ID/IG value of the graphene fiber of the embodiment decreases and the conductivity of the graphene fiber increases.
  • the decrease in the ID/IG value means that the sp 2 structure in the graphene fiber is gradually recovered, and thus the conductivity increases.
  • a graph (b) of FIG. 19 currents of 10 mA to 100 mA were applied to the graphene fiber according to the embodiment, a ID/IG value and a L a value (nm) of the graphene fiber at each current were measured. The measured results were shown in the graph (b) of FIG. 19.
  • the L a value means a grain size of the graphene sheet disposed in the graphene fiber.
  • the ID/IG value of the graphene fiber of the embodiment decreases and the L a value of the graphene fiber increases.
  • FIG. 20 is a graph comparing a structural feature of a graphene fiber according to an embodiment of the inventive concepts with graphite.
  • intensities (a.u.) according to Raman Shift (cm -1 ) were measured from the graphene oxide fiber (GOF), the primary graphene fiber GF, a graphene fiber GF40 to which a current of 40 mA was applied, a graphene fiber GF80 to which a current of 80 mA was applied, and graphite, and the measured results were shown in FIG. 20.
  • a shape of a T-band, shown in the vicinity of 1600cm -1 , of the graphene fiber according to the embodiment becomes similar to a shape of a T-band of the graphite as the value of the applied current increases.
  • FIG. 21 is a graph showing a ratio of carbon to oxygen in a graphene fiber according to an embodiment of the inventive concepts.
  • C/O carbon/oxygen
  • the C/O ratio of the graphene fiber according to the embodiment increases as the value of the current applied to the graphene fiber increases.
  • oxygen atoms in the graphene fiber decreases as the value of the current applied to the graphene fiber increases.
  • FIG. 22 shows wide angle x-ray diffraction (WAXD) images of a graphene fiber according to an embodiment of the inventive concepts
  • FIGS. 23 and 24 are graphs obtained by analyzing characteristics of the WAXD images of FIG. 22.
  • images (a) to (e) of FIG. 22 a WAXD image of the graphene fiber before applying a current was obtained, and WAXD images of the graphene fibers to which currents of 40 mA, 60 mA, 80 mA and 100 mA were applied were obtained.
  • the images (a) to (e) of FIG. 22 will be analyzed to explain characteristics of a grain size of the graphene sheet in the graphene fiber and a distance between the graphene sheets.
  • FIG. 23 the images (a), (b), (d) and (e) of FIG. 22 were analyzed to measure an intensity (a.u.) according to an azimuthal angle ( ⁇ ), and the measured results were shown in FIG. 23.
  • a peak at 90 degrees ( ⁇ ) of the graphene fiber of the embodiment is the greatest even though the value of the applied current increases.
  • a graph (b) of FIG. 23 the images (a) to (e) of FIG. 22 were analyzed to measure an intensity (a.u.) according to 2 ⁇ degree, and the measured results were shown in the graph (b). As shown in the graph (b) of FIG. 23, peaks of the graphene fibers according to the embodiment are shown after 24.5 degrees since the currents are applied.
  • the grain size L a of the graphene sheet in the graphene fiber of the embodiment significantly increases as the value of the applied current increases.
  • FIG. 25a ⁇ 25c shows graphs comparing characteristics of an inner structure according to a value of a current applied to a graphene fiber according to an embodiment of the inventive concepts.
  • an intensity (a.u.) according to Raman shift (cm -1 ) of the graphene fiber of the embodiment before applying a current was measured.
  • currents of 10 mA to 100 mA were applied to the graphene fiber of the embodiment, and an intensity (a.u.) according to Raman shift (cm -1 ) of the graphene fiber at each current was measured.
  • the measured results were shown in FIG. 25a ⁇ 25c.
  • inner defects of the graphene fiber according to the embodiment are gradually eliminated as the value of the current applied to the graphene fiber increases.
  • FIG. 26 is a diagram illustrating a change in an inner structure according to a current applied to a graphene fiber according to an embodiment of the inventive concepts.
  • FIG. 26 shows an inner structure of the graphene fiber (GF, i.e., the primary graphene fiber) before applying a current, an inner structure of the graphene fiber (GF40) to which a current of 40 mA was applied, an inner structure of the graphene fiber (GF80) to which a current of 80 mA was applied, and an inner structure of the graphene fiber (GF100) to which a current of 100 mA was applied.
  • GF graphene fiber
  • the graphene fiber (i.e., the primary graphene fiber) before applying the current has stacked graphene sheets, and each of the graphene fibers after applying the currents also have stacked graphene sheets.
  • a grain size L a of the graphene sheet is 3.79nm
  • a distance d 002 between the graphene sheets is 3.6 ⁇
  • a thickness L c of the stacked graphene sheets is 2.82 nm.
  • a grain size L a is 2.93nm, a distance d 002 is 3.4 ⁇ , and a thickness L c is 3.33nm.
  • a grain size L a is 12.4nm, a distance d 002 is 3.4 ⁇ , and a thickness L c is 5nm.
  • a grain size L a is 34nm, a distance d 002 is 3.4 ⁇ , and a thickness L c is 6.86nm.
  • FIG. 27 shows an image and a graph which show a temperature of a graphene fiber according to an embodiment of the inventive concepts.
  • thermal images of the primary graphene fiber (GF) and the graphene fiber (GF100) to which a current of 100 mA was applied were obtained by an infrared (IR) camera.
  • the images (a) of FIG. 27 are shown as a graph (b) of FIG. 27.
  • thermal stability of the graphene fiber is improved since the current is applied.
  • FIG. 28 is a graph comparing characteristics of a graphene fiber according to an embodiment of the inventive concepts with those of a copper wire.
  • a relative conductance according to a temperature was measured from each of the graphene fiber according to the embodiment and a copper wire, and the measured results were shown in FIG. 28.
  • the conductance of the graphene fiber according to the embodiment is higher than that of the copper wire when the temperature increases.
  • FIG. 29 is a graph showing reaction of a graphene fiber according to an embodiment of the inventive concepts and oxygen in air.
  • the graphene fiber according to the embodiment was exposed to the outside for 1 hour, and changes in voltage (V) and current (A) were measured. The measured results were shown in FIG. 29. As shown in FIG. 29, the voltage (V) and the current (A) are not changed even though the graphene fiber according to the embodiment is exposed to the outside for 1 hour. In other words, it is recognized that the graphene fiber according to the embodiment does not react with oxygen in external air.
  • the method of manufacturing the graphene fiber may include preparing the source solution including the graphene oxide, supplying the source solution into the coagulation solution to form the graphene oxide fiber, reducing the graphene oxide fiber to form the primary graphene fiber, and Joule-heating the primary graphene fiber to form the secondary graphene fiber.
  • the amorphous carbon in the primary graphene fiber may be crystallized by Joule-heating the primary graphene fiber.
  • the high-efficiency graphene fiber with the improved electrical conductivity may be manufactured by simplified processes.

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

L'invention concerne un procédé de fabrication de fibre de graphène. Le procédé consiste à préparer une solution source comprenant de l'oxyde de graphène, à mettre la solution source dans une solution de coagulation pour former une fibre d'oxyde de graphène, à réduire la fibre d'oxyde de graphène pour former une fibre de graphène primaire, et à chauffer par effet Joule la fibre de graphène primaire pour former une fibre de graphène secondaire.
PCT/KR2018/011428 2017-09-28 2018-09-28 Fibre de graphène fabriquée par chauffe par effet joule et son procédé de fabrication WO2019066492A2 (fr)

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US20220243365A1 (en) * 2019-09-27 2022-08-04 Korea Electrotechnology Research Institute High heat-resistant graphene oxide, method for manufacturing conductive graphene fiber by using same, and conductive graphene fiber manufactured therefrom

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WO2006098275A1 (fr) * 2005-03-15 2006-09-21 Matsushita Electric Industrial Co., Ltd. Dispositif de fixation, rouleau chauffant et dispositif de formation d'image
US9284193B2 (en) * 2013-10-21 2016-03-15 The Penn State Research Foundation Method for preparing graphene oxide films and fibers
US10273599B2 (en) * 2015-07-24 2019-04-30 Lg Chem, Ltd. Apparatus for manufacturing carbon nanotube fiber
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

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US20220243365A1 (en) * 2019-09-27 2022-08-04 Korea Electrotechnology Research Institute High heat-resistant graphene oxide, method for manufacturing conductive graphene fiber by using same, and conductive graphene fiber manufactured therefrom

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