WO2019117663A1 - Fibre conjuguée de graphène, son appareil de fabrication et son procédé de fabrication - Google Patents

Fibre conjuguée de graphène, son appareil de fabrication et son procédé de fabrication Download PDF

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Publication number
WO2019117663A1
WO2019117663A1 PCT/KR2018/015905 KR2018015905W WO2019117663A1 WO 2019117663 A1 WO2019117663 A1 WO 2019117663A1 KR 2018015905 W KR2018015905 W KR 2018015905W WO 2019117663 A1 WO2019117663 A1 WO 2019117663A1
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graphene
graphene oxide
fiber
composite fiber
doping element
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PCT/KR2018/015905
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English (en)
Korean (ko)
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한태희
박헌
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한양대학교 산학협력단
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Priority claimed from KR1020180160920A external-priority patent/KR102144197B1/ko
Application filed by 한양대학교 산학협력단 filed Critical 한양대학교 산학협력단
Publication of WO2019117663A1 publication Critical patent/WO2019117663A1/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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/10—Filtering or de-aerating the spinning solution or melt
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/04—Dry spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • 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
    • 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

  • the present invention relates to a graphene conjugate fiber having graphene doped with a doping element, an apparatus for producing the graphene conjugate fiber, and a manufacturing method thereof.
  • Korean Patent Registration No. 10-1373049 (Application No. 10-2012-0131288, Applicant: Korea Institute of Science and Technology) has proposed that hydrophobic fibers are coated with reduced graphene oxide (RGO)
  • the present invention relates to a fiber grains coated with reduced graphene oxide and a method for producing the same, which can suppress the adsorption of contaminants when applying the fiber yarn filter in the wastewater treatment process and thereby enable the fiber yarn filter to be used for a long time, Swelling the swollen fiber yarn with graphene oxide (GO) by immersing the swollen fiber yarn in a polar aprotic solvent in which graphen oxide (GO) is dispersed, and swelling the graphen oxide (GO) GO) on the surface of the reduced graphene oxide-coated fiber yarn, and a method for producing the same.
  • the present invention provides a graphene conjugated fiber capable of uniform doping, an apparatus for producing the same, and a manufacturing method thereof.
  • Another technical problem to be solved by the present invention is to provide a graphene conjugated fiber having improved electrical properties, an apparatus for producing the same, and a manufacturing method thereof.
  • the technical problem to be solved by the present invention is not limited to the above.
  • the present invention provides a method for producing a graphene conjugated fiber.
  • the method of making the graphene conjugated fiber comprises the steps of preparing a base solution comprising graphene oxide, a dispersion solvent having a first solubility in the graphene oxide, and a functional source having a doping element, Spinning the base solution into a coagulation bath containing a coagulation solvent having a second solubility lower than the first solubility with respect to the graphene oxide to obtain a graphene oxide composite fiber, And heat-treating the grafted fiber to prepare graphene conjugated fibers doped with the doping element of the functional source.
  • the coagulation solvent may comprise, relative to the dispersion solvent, having a third solubility that is higher than the second solubility.
  • the dispersion solvent includes water (H 2 O), and the coagulation solvent may include at least one of methanol and acetone.
  • the dispersion solvent comprises DMF (dimethylformaide)
  • the coagulation solvent may include at least one of acetone, acetone, and ethyl acetate.
  • the heat treatment temperature of the graphene oxide composite fiber may be higher than the thermal decomposition temperature of the functional source.
  • the doping element includes at least one of sulfur, iodine, and selenium
  • the graphene conjugated fiber may include an N-type .
  • the doping element includes at least one of nitrogen, boron, and phosphorous
  • the graphene conjugate fiber may include a P-type
  • the present invention provides an apparatus for producing a graphene conjugate fiber.
  • the apparatus for producing a graphene conjugated fiber comprises spinning a base solution comprising graphene oxide, a dispersion solvent having a first solubility in respect of the graphene oxide, and a functional source having a doping element, A coagulation bath having a second solubility lower than the first solubility with respect to the graphene oxide and having a coagulation solvent for coagulating the pregranite composite fiber, And a winding module for winding up the graphene oxide composite fiber in which the graphene oxide composite fiber coagulates.
  • the apparatus for producing a graphene conjugate fiber includes a heat treatment module for heat-treating the graphene oxide composite fiber to produce a graphene composite fiber in which the doping element of the functional source is doped, .
  • the apparatus for producing a graphene conjugate fiber has an increase in elongation percentage of the graphene conjugate fiber when the spinning speed of the base solution is faster than the winding speed of the graphene oxide conjugate fiber .
  • the present invention provides a graphene conjugate fiber.
  • the graphene conjugate fiber includes graphene fibers that aggregate a plurality of graphene sheets and extend in one direction, wherein the graphene sheet includes graphene sheets doped with a doping element ≪ / RTI >
  • the doping element includes any one of sulfur, iodine, and selenium
  • the graphene conjugate fiber may include an N-type dopant
  • the doping element includes any one of nitrogen, boron, and phosphorus
  • the graphene conjugated fiber may include a P-type
  • a method for producing a graphene conjugate fiber includes the steps of preparing a base solution containing a graphene oxide, a dispersion solvent having a first solubility in the graphene oxide, and a functional source having a doping element , Spinning the base solution into a coagulation bath containing a coagulation solvent having a second solubility lower than the first solubility with respect to the graphene oxide to obtain a graphene oxide composite fiber, To prepare graphene conjugated fibers doped with the doping element of the functional source to the graphene fibers.
  • a method of fabricating a graphene conjugate fiber whose electrical characteristics are controlled by a simple method of controlling the doping element can be provided. Further, since the graphene conjugate fiber can be produced without a washing process, not only the process cost is reduced but also the problem that the doping element is removed in the washing process is solved, so that the graphene conjugate fiber improved in doping rate can be provided .
  • FIG. 1 is a flow chart illustrating a method for producing a graphene conjugate fiber according to a first embodiment of the present invention.
  • FIG. 2 is a view showing a process for producing a graphene conjugate fiber according to a first embodiment of the present invention.
  • FIG. 3 is a flowchart illustrating a method of manufacturing a graphene conjugate fiber according to a second embodiment of the present invention.
  • FIG. 4 is a view showing a process for producing a graphene conjugate fiber according to a second embodiment of the present invention.
  • Figs. 5 to 7 are photographs comparing optical images of the graphene conjugate fibers according to Example 1 and Comparative Example 2 of the present invention. Fig.
  • FIGS. 8 and 9 are graphs comparing the characteristics of the graphene conjugate fibers according to Examples and Comparative Examples of the present invention.
  • FIGS. 10 and 11 are optical photographs of a graphene conjugate fiber according to a second embodiment of the present invention.
  • first, second, third, etc. in the various embodiments of the present disclosure are used to describe various components, these components should not be limited by these terms. These terms have only been used to distinguish one component from another. Thus, what is referred to as a first component in any one embodiment may be referred to as a second component in another embodiment.
  • Each embodiment described and exemplified herein also includes its complementary embodiment. Also, in this specification, 'and / or' are used to include at least one of the front and rear components.
  • connection &quot is used to include both indirectly connecting and directly connecting a plurality of components.
  • FIG. 1 is a flow chart for explaining a method for producing a graphene conjugate fiber according to a first embodiment of the present invention
  • FIG. 2 is a view showing a process for producing a graphene conjugate fiber according to a first embodiment of the present invention.
  • a base solution 10 may be prepared (S110).
  • the base solution 10 may include grephene oxide, a dispersion solvent, and a functional source.
  • the step of preparing the base solution (S110) may include the steps of preparing a mixed solution in which the graphene oxide is dispersed in the dispersion solution, and dispersing the functional source in the mixed solution Step < / RTI > That is, the base solution 10 may be prepared by mixing the graphene oxide and the dispersion solvent, and then dispersing the functional source in a mixed solution.
  • the graphene oxide may be in the form of a graphene oxide sheet.
  • the dispersion solvent may have a first solubility to the graphene oxide.
  • the dispersion solvent may be water (H 2 O), dimethyl sulfoxide (DMSO), ethylene glycol (EG), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF)
  • the functional source may comprise a doping element.
  • the doping element may include at least one of nitrogen, sulfur, phosphorous, selenium, fluorine, iodine, and boron.
  • the functional source may be any one selected from the group consisting of Ammonium thiocyanate, Ammonium chloride, Ammonia, Ammonium acetate, Ammonium cyanate, Ammonium benzoate, Ammonium formate, Ammonium bicarbonate, Ammonium dichromate, Ammonium carbamate and Hydrazine One can be included.
  • the functional source may be selected from the group consisting of dimethyl sulfate, aluminum sulfate, calcium sulfate, cobalt (II) sulfate, copper sulfate, cadmium sulfate, Magnesium sulfate, and Manganese (II) sulfate.
  • the doping element comprises phosphorous
  • the functional source may be selected from the group consisting of aluminum phosphate, calcium phosphate, Chromium (III) phosphate, Cobalt phosphate, Copper (II) phosphate, Dicalcium phosphate, Dimagnesium phosphate, , Iron (II) phosphate, and magnesium phosphate.
  • the functional source is selected from Gallium (II) selenide, Indium (III) selenide, Sodium selenide, Cadmium selenide, Zinc selenide, Lead selenide, Copper selenide, Iron , ≪ / RTI > and Sodium selenite.
  • the functional source may be selected from the group consisting of Aluminum fluoride, Cadmium fluoride, Calcium fluoride, Cobalt (III) fluoride, Copper (II) fluoride, Gallium (III) Iron (III) fluoride, manganese (III) fluoride, and nickel (II) fluoride.
  • the functional source may be selected from the group consisting of Aluminum iodide, Cadmium iodide, Calcium iodide, Chromium (III) iodide, Cobalt (II) iodide, Copper (I) iodide, Gallium , Iron (II) iodide, Lithium iodide, Manganese (II) iodide, Nickel (II) iodide, and Potassium iodide.
  • Aluminum iodide Cadmium iodide, Calcium iodide, Chromium (III) iodide, Cobalt (II) iodide, Copper (I) iodide, Gallium , Iron (II) iodide, Lithium iodide, Manganese (II) iodide, Nickel (II) iodide, and Potassium iodide.
  • the functional source may be selected from the group consisting of Aluminum diboride, Calcium hexaboride, Cobalt boride, Nickel boride, Magenesium diboride, Iron boride, Iron tetraboride, Titanium diboride, Silicon boride, and Chromium Or the like.
  • the base solution 10 is radiated into the coagulation bath 200 containing the coagulation solvent 20 to obtain the graphene oxide composite fiber 40 at step S120.
  • the base solution 10 may be radiated from the spinning module 100 to the coagulation bath 200.
  • the spinning speed of the spinning module 100 may be 0.1 to 20 m / min.
  • the pregravure composite fiber 30 may be formed. That is, the spinning module 100 can form the base solution 10 in a fiber form. Accordingly, the preliminary graphene oxide composite fiber 30 may be a fibrous material including the graphene oxide, the dispersion solvent, and the functional source.
  • the pregravure composite fiber 30 formed from the radiation module 100 may be provided in the coagulation bath 200.
  • the coagulation solvent (20) contained in the coagulation bath (200) can coagulate the graphene oxide contained in the pregranine oxide composite fiber (30).
  • the coagulation solvent 20 may remove the dispersion solvent from the pregravidin composite fiber 30. That is, when the pregravovite composite fiber 30 is provided in the coagulation solvent 20, the dispersion solvent is separated from the pregravovite composite fiber 30 and dispersed in the coagulation solvent 20 . Accordingly, the graphene oxide composite fiber 40 including the graphene oxide and the functional source can be produced.
  • the coagulation solvent 20 may have a second solubility to the graphene oxide.
  • the second solubility may be lower than the first solubility. That is, the solubility of the graphene oxide dissolved in the coagulation solvent 20 may be lower than the solubility of the graphene oxide dissolved in the dispersion solvent.
  • the graphene oxide is easily dispersed and dissolved in the dispersion solvent, but may not be easily dispersed and dissolved in the coagulation solvent 20.
  • the dispersion solvent excluding the graphene oxide is selectively dissolved and dispersed in the coagulation solvent (20) from the pregravidin composite fiber (30), so that the graphene oxide composite fiber (40) .
  • the coagulation solution 20 can not penetrate into the pregranum oxide composite fiber 30,
  • the pin oxide composite fiber 40 can be easily formed.
  • the coagulation solvent 20 may have a third solubility in the dispersion solvent.
  • the third solubility may be higher than the second solubility. That is, the solubility of the dispersion solvent in the coagulation solvent 20 may be higher than the solubility of the graphene oxide in the coagulation solvent 20.
  • the dispersion solvent is easily dispersed and dissolved in the coagulation solvent 20
  • the graphene oxide may not be easily dispersed and dissolved. Accordingly, when the preliminary graphene oxide composite fiber 30 is provided in the coagulation solution 20, the dispersion solvent can easily escape from the pregravure composite fiber 30. As a result, the graphene oxide composite fiber 40 can be easily formed. That is, by using the difference in solubility between the graphene oxide, the dispersion solvent, and the coagulation solvent 20, the graphene oxide composite fiber can be easily formed.
  • the coagulation solvent 20 may be at least one selected from the group consisting of methanol and acetone.
  • the coagulation solvent 20 may be a mixed solution of acetone and ethyl acetate.
  • the coagulation solvent 20 may not comprise the functional source. That is, the base solution 10 includes the functional source, and the coagulation solvent 20 may not include the functional source. As a result, the homogeneity of the doping element doping of the graphene conjugate fiber described later can be improved.
  • pregelatinized oxide fibers are prepared from a base solution in which graphene oxide and a dispersion solvent are mixed, followed by coagulation with a solution containing a coagulation solvent and a functional source To prepare doped graphene conjugated fibers.
  • the doping element is not uniformly distributed in the graphene fiber, and the uniformity of doping of the graphene conjugate fiber may be lowered.
  • the salt as well as the doping elements of the functional source into the pregraphene oxide fibers are also impregnated and after the solidification a cleaning process has to be additionally performed Problems may arise. Also, such a problem may occur that the doping factor is lowered as the doping element is removed together with the salt during the cleaning process.
  • the method of manufacturing the graphene conjugate fiber according to the present embodiment is characterized in that the pregelatinized oxide fiber 30 is prepared with the base solution 10 containing graphene oxide, a dispersion solvent, and a functional source, And then solidifying the solution through the coagulation solvent (20).
  • the pregelatinized oxide fiber 30 is prepared with the base solution 10 containing graphene oxide, a dispersion solvent, and a functional source, And then solidifying the solution through the coagulation solvent (20).
  • the uniformity of doping of the graphene conjugate fiber described later can be improved.
  • the graphene conjugated fiber can be produced with a smaller amount of functional source as compared with the case of producing a graphene conjugate fiber through a solution in which a coagulating solvent (20) and a functional source are mixed.
  • the graphene oxide composite fiber 40 can be wound by the winding modules 310 and 320.
  • the winding module 310, 320 may include a guide roller 310, and a winding roller 320.
  • the guide roller 310 separates the graphene oxide composite fiber 40 from the coagulation bath and discharges it to the outside.
  • the winding roller 320 may wind the graphene oxide composite fiber 40 discharged to the outside. That is, the graphene oxide composite fiber 40 may be separated from the coagulation bath 200 by a guide roller 310 and may be wound out by a winding roller 320.
  • the graphene oxide composite fiber 40 may be dried by the drying module 400 while being moved by the guide roller 310.
  • the drying module 400 may heat the graphene oxide composite fiber 40 to a temperature of 50 to 100 ° C. to dry the graphene oxide composite fiber 40.
  • the graphene oxide composite fiber 40 is heat-treated to produce a graphene conjugate fiber (S130).
  • the graphene oxide composite fibers 40 may be heat treated by a heat treatment module (not shown).
  • the graphene conjugate fiber (not shown) includes graphene fibers that are aggregated into a plurality of graphene sheets so as to extend in one direction, wherein the graphene sheets include graphene sheets, Lt; / RTI >
  • the graphene oxide composite fiber 40 when the graphene oxide composite fiber 40 is heat-treated, the graphene oxide composite fiber 40 is reduced to graphene, and the graphene oxide composite fiber 40 is , Can represent the shape of graphene fibers.
  • the doping element of the functional source when the graphene oxide composite fiber 40 is heat treated, the doping element of the functional source may penetrate into the lattice of the graphene to which the graphene oxide has been reduced. Accordingly, the graphene fiber can be produced by grafting the graphene fiber with the doping element (not shown).
  • the heat treatment temperature of the graphene oxide composite fiber 40 may be higher than the thermal decomposition temperature of the functional source.
  • the heat treatment temperature of the graphene oxide composite fiber 40 may be 50 to 100 ° C higher than the thermal decomposition temperature of the functional source.
  • the functional source is ammonium thiocyanate
  • the graphene oxide composite fiber 40 may be heat-treated at a temperature of 300 ° C.
  • the graphene oxide composite fiber 40 can be heat-treated in an inert gas atmosphere.
  • the inert gas may be Ar, N 2 , H 2 , and the like.
  • the electrical conductivity and the electrical properties of the graphene conjugate fiber can be controlled according to the type of the doping element.
  • the doping element includes nitrogen
  • the electrical conductivity of the graphene conjugate fiber can be improved.
  • the doping element includes any one of sulfur, iodine, and selenium
  • the graphene conjugated fiber may exhibit an N-type.
  • the doping element includes nitrogen, boron, or phosphorous
  • the graphene conjugated fiber may exhibit a P-type. Accordingly, the electrical characteristics of the graphene conjugate fiber according to the embodiment can be easily controlled by a simple method of controlling the doping element during the manufacturing process.
  • the elongation percentage of the graphene composite fiber can be controlled according to the winding speed of the graphene oxide composite fiber (not shown) and the spinning speed of the base solution 10. Specifically, when the spinning speed of the base solution 10 is faster than the winding speed of the graphene oxide composite fiber (not shown), the elongation of the graphene composite fiber can be increased.
  • the method for producing a graphene conjugate fiber according to the first embodiment of the present invention is characterized in that the graphene composite fiber includes the graphene oxide, the dispersion solvent having the first solubility to the graphene oxide, and the functional source having the doping element
  • FIG. 3 is a flow chart for explaining a method of manufacturing a graphene conjugate fiber according to a second embodiment of the present invention
  • FIG. 4 is a view showing a process for producing a graphene conjugate fiber according to a second embodiment of the present invention.
  • the base solution 10 may be prepared (S210).
  • the base solution 10 may be the same as the base solution 10 used in the method of manufacturing the graphene conjugate fiber according to the first embodiment described with reference to FIGS. Accordingly, a detailed description thereof will be omitted.
  • the base solution 10 is radiated into the coagulation bath 200 containing the coagulation solvent 20 to obtain the graphene oxide composite fiber 40 at step S220.
  • a specific method of obtaining the graphene oxide composite fiber 40 is the same as the method of producing the graphene oxide composite fiber according to the first embodiment described with reference to Figs. ≪ / RTI >
  • the coagulation bath 200 may be divided into a first region 210, a second region 220, a third region 230, and a fourth region 240.
  • the first to fourth regions 210, 220, 230, and 240 may be separated by the first to third separation membranes 200a, 200b, and 200c.
  • the first and second regions 210 and 220 may be separated by the first separation layer 200a.
  • the second and third regions 220 and 230 may be separated by the second separation layer 200b.
  • the third and fourth regions 230 and 240 may be separated by the third separation layer 200c.
  • the first to fourth coagulation solvents 20a, 20b, 20c, and 20d included in the coagulation solvent 20 may be added to the first to fourth regions 210, 220, 230, .
  • the first to fourth coagulation solvents may have different concentrations of (20a, 20b, 20c, 20d). Specifically, the first coagulation solvent 20a may have a lower concentration than the second coagulation solvent 20b.
  • the second coagulation solvent 20b may have a lower concentration than the third coagulation solvent 20c.
  • the fourth coagulation solvent 20d may have a lower concentration than the third coagulation solvent 20c.
  • the graphene oxide composite fiber 40 formed by spinning the base solution 10 from the spinning module 100 passes through the holes of the first to third separation membranes 200a to 200c, 4 coagulation solvents 20a, 20b, 20c, and 20d. That is, after the preliminary graphene oxide composite fiber 30 is provided to the first coagulation solvent 20a, the graphene oxide composite fiber 40 is formed by the first coagulation solvent 20a, The composite oxide fiber 40 is sequentially passed through the second to fourth coagulation solvents 20b, 20c and 20d and the fourth coagulation solvent 20d by the guide rollers 310, 200).
  • the dispersion solvent contained in the preliminary graphene oxide composite fiber 30 rapidly escapes to the coagulation solvent 20, thereby preventing the shape of the graphene oxide composite fiber 40 from being deformed . That is, the pregravidin composite fiber 30 sequentially passes through the second to fourth coagulation solvents 20b, 20c, and 20d gradually increasing in concentration from the first coagulation solvent 20a having a low concentration Accordingly, the dispersion solvent can be gradually dispersed in the coagulation solvent 20. Accordingly, the graphene oxide composite fiber 40 can be easily formed.
  • the graphene oxide composite fiber 40 is heat-treated to produce a graphene conjugate fiber (S230).
  • the method for producing the graphene conjugate fiber may be the same as the method for producing the graphene conjugate fiber according to the first embodiment described with reference to FIGS. 1 and 2 have. Accordingly, a detailed description thereof will be omitted.
  • the method for producing a graphene conjugate fiber according to the second embodiment of the present invention is characterized in that the graphene composite fiber comprises the graphene oxide, the dispersion solvent having a first solubility to the graphene oxide, and the functional source having the doping element Preparing a base solution (10), mixing the base solution (10) with a coagulation solution containing first to fourth coagulation solvents having a second solubility lower than the first solubility with respect to the graphene oxide Spinning the graphene oxide composite fiber (40) to obtain graphene oxide composite fibers (40); and heat treating the graphene oxide composite fibers (40) so that the graphene fibers are graphened with the doping element of the functional source And the step of fabricating the fiber. Accordingly, a method for producing a graphene conjugate fiber with improved durability and reliability can be provided.
  • a graphene oxide sheet was dispersed in dimethylformamide (DMF), and NH 4 Cl was added at a concentration of 0.05 M to 0.1 M to prepare a base solution.
  • DMF dimethylformamide
  • the base solution was put into a spinning module and spinning was carried out in a coagulation solvent in which acetone and ethyl acetate were mixed at a spinning speed of 0.1 to 20 m / min to prepare a graphene oxide composite fiber , And dried at a temperature of 50 to 100 ° C.
  • the dried graphene oxide composite fiber was heat-treated at a temperature of 300 ⁇ in an inert gas (N 2 ) environment to prepare the graphene composite fiber according to Example 1.
  • a graphene oxide sheet was dispersed in dimethylformamide (DMF), and NH 4 SCN (ammonium thiocynate) was added to prepare a base solution.
  • DMF dimethylformamide
  • NH 4 SCN ammonium thiocynate
  • the base solution was put into a spinning module and spinning was carried out in a coagulation solvent in which acetone and ethyl acetate were mixed at a spinning speed of 0.1 to 20 m / min to prepare a graphene oxide composite fiber , And dried at a temperature of 50 to 100 ° C.
  • the dried graphene oxide composite fiber was heat-treated at a temperature of 300 ⁇ in an inert gas (N 2 ) environment to prepare the graphene composite fiber according to Example 1.
  • Normal graphene fibers are prepared.
  • a base solution in which a graphene oxide sheet is dispersed in DI water is prepared. Thereafter, the base solution was put into a spinning module, and the resultant mixture was spun in a solution containing a coagulating solution and a 1 M concentration of NH 4 Cl to prepare a graphene oxide composite fiber, which was heat-treated to prepare the graphene composite fiber according to Comparative Example 2 Respectively.
  • FIGS. 5 to 7 are photographs comparing optical images of the graphene conjugate fibers according to Example 1 and Comparative Example 2 of the present invention.
  • FIG. 5 scanning electron microscope (SEM) photographs of the graphene conjugated fiber according to Comparative Example 2 and the graphene conjugated fiber according to Example 1 were respectively shown in FIGS. 5 (a) and 5 (b).
  • SEM scanning electron microscope
  • the distribution of carbon in the graphene conjugated fiber according to Comparative Example 2 and the graphene conjugated fiber according to Example 1 is shown by energy dispersive X-ray spectroscopy (EDS) (A) and (b) of Fig.
  • EDS energy dispersive X-ray spectroscopy
  • the graphene conjugate fiber according to Example 1 has a better distribution of carbon than the graphene conjugate fiber according to Comparative Example 2 there was.
  • the distribution of nitrogen is shown by energy dispersive X-ray spectroscopy (EDS) mapping on the graphene conjugate fiber according to Comparative Example 2 and the graphene conjugate fiber according to Example 1, (A) and (b) of Fig.
  • EDS energy dispersive X-ray spectroscopy
  • FIGS. 8 and 9 are graphs comparing the characteristics of the graphene conjugate fibers according to Examples and Comparative Examples of the present invention.
  • the electrical conductivity (Scm -1 ) was measured for each of the graphene conjugate fiber according to Example 1, the graphene fiber according to Comparative Example 1, and the graphene conjugate fiber according to Comparative Example 2 Respectively.
  • the graphene conjugate fibers according to Example 1 and Comparative Example 2 exhibited higher electric conductivity than the graphene fibers according to Example 1, and in particular, It was confirmed that the composite fibers exhibited remarkably higher electric conductivity than the graphene fibers according to Comparative Example 1 as well as the graphene conjugated fibers according to Comparative Example 2.
  • the nitrogen content (%) of the graphene conjugate fiber according to Example 1 and the graphene conjugate fiber according to Comparative Example 2 were shown. As shown in FIG. 9, the graphene conjugate fiber according to Example 1 exhibited a nitrogen gas flow rate of about 13 at%, and the graphene conjugate fiber according to Comparative Example 2 had a nitrogen gas flow rate of about 4 at , It was confirmed that the graphene conjugate fiber according to Example 1 exhibited a nitrogen content of about three times or more than that of the graphene conjugate fiber according to Comparative Example 2. [
  • the graphene composite fiber produced by the method in which the base solution contains graphene oxide, a dispersion solvent, and a functional material and is radiated into the coagulation solution is mixed with graphene oxide and a dispersion solvent Of the present invention exhibits a high nitrogen content and a high electrical conductivity as compared with the graphene conjugate fiber produced by the method in which the base solution containing the functional material and the coagulation solution is spun in a solution containing the functional material and the coagulation solution.
  • FIGS. 10 and 11 are optical photographs of a graphene conjugate fiber according to a second embodiment of the present invention.
  • the graphene conjugated fiber according to the second embodiment is photographed by SEM. As shown in FIG. 10, it was confirmed that the graphene composite fibers according to Example 2 were formed into a shape in which a plurality of graphene sheets were aggregated and extended in one direction.
  • the graphene conjugated fiber according to Example 2 is subjected to energy dispersive X-ray spectroscopy (EDS) mapping to obtain carbon, nitrogen, (sulfur), respectively.
  • EDS energy dispersive X-ray spectroscopy
  • the graphene conjugated fiber according to the embodiment of the present invention can be utilized in various industrial fields such as electric power supply lines, automobiles, electronic devices, and buildings.

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Abstract

L'invention concerne un procédé de fabrication d'une fibre conjuguée de graphène. Le procédé de production d'une fibre conjuguée de graphène comprend les étapes consistant à : préparer une solution de base contenant de l'oxyde de graphène, un solvant de dispersion ayant une première solubilité dans l'oxyde de graphène, et une source fonctionnelle comportant un élément dopant ; mettre en rotation la solution de base dans un bain de coagulation contenant un solvant de coagulation ayant une seconde solubilité inférieure à la première solubilité pour obtenir ainsi une fibre conjuguée d'oxyde de graphène ; et traiter thermiquement la fibre conjuguée d'oxyde de graphène pour fabriquer une fibre conjuguée de graphène dopée avec l'élément de dopage de la source fonctionnelle.
PCT/KR2018/015905 2017-12-14 2018-12-14 Fibre conjuguée de graphène, son appareil de fabrication et son procédé de fabrication WO2019117663A1 (fr)

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KR10-2017-0172546 2017-12-14
KR20170172546 2017-12-14
KR1020180160920A KR102144197B1 (ko) 2017-12-14 2018-12-13 그래핀 복합 섬유 및 그 제조장치, 및 그 제조방법
KR10-2018-0160920 2018-12-13

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