WO2018217042A1 - Procédé de production de flocons de graphène de haute qualité par exfoliation électrochimique et solution de dispersion de flocons de graphène - Google Patents

Procédé de production de flocons de graphène de haute qualité par exfoliation électrochimique et solution de dispersion de flocons de graphène Download PDF

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WO2018217042A1
WO2018217042A1 PCT/KR2018/005921 KR2018005921W WO2018217042A1 WO 2018217042 A1 WO2018217042 A1 WO 2018217042A1 KR 2018005921 W KR2018005921 W KR 2018005921W WO 2018217042 A1 WO2018217042 A1 WO 2018217042A1
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acid
naphthalene
carboxylic acid
anthracene
graphene
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PCT/KR2018/005921
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English (en)
Korean (ko)
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전석우
아잠아쉬라풀
김정모
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한국과학기술원
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds

Definitions

  • the present invention relates to a method for producing graphene flakes. More specifically, the present invention relates to a method for producing graphene flakes using electrochemical exfoliation and to a dispersion solution of graphene flakes.
  • Graphene is a two-dimensional planar carbon allotrope with sp2 hybrid structure in which carbon atoms are combined in a honeycomb or network.
  • Graphene has, for example, about twice the thermal conductivity of diamond and about 1,000 times the electrical conductivity of copper, and simultaneously has excellent mechanical properties such as tensile strength close to steel. Therefore, graphene has been applied / researched in various engineering fields such as nano scale electrical, electronic devices, nano sensors, optoelectronic devices, electrode additives, high functional composite materials, and the like.
  • Graphene is present in the graphite state by van der Waals forces between individual units, and may require a peeling process from the graphite to graphene for industrial applications.
  • Exemplary methods developed for graphene manufacturing are mainly a top-down method of peeling graphene flakes having a single layer or a water layer from a graphene precursor such as graphite, and using carbonaceous materials such as methane gas or organic monomolecules and polymers.
  • top-down methods include mechanical peeling methods such as scotch tape peeling or ball-milling, ultrasonic mixing or liquid phase peeling using a shear force of a solvent after mixing graphite in an organic solution, and oxidized graphite in a solution. Thereafter, there is an oxidation-reduction method in which graphene oxide prepared by exfoliation is used to produce graphene using a reduction reaction.
  • the bottom-up method may be chemical synthesis by chemical vapor deposition (CVD) or silicon carbide (SiC) heat treatment.
  • CVD chemical vapor deposition
  • SiC silicon carbide
  • the size of the graphene is limited to several hundred nanometers or less, or the defect rate and oxidation degree of the graphene are increased, thereby realizing excellent characteristics expected in the ideal graphene. Difficult to do
  • Non-Patent Document 1 reports a graphene peeling method through the previously reported electrochemical process.
  • Patent document 1 reports on the method of electrochemically peeling a graphene using a sulfuric acid electrolyte.
  • sulfuric acid electrolyte when used, there is a disadvantage in that a chemical reaction proceeds between the radicals generated from the decomposition of sulfuric acid molecules in the electrolyte and graphite, thereby increasing the defect rate of the finally produced graphene flake.
  • Patent document 2 reports on the graphene peeling method through an additional process following the intercalation of alkali metal into the graphite interlayer using an electrochemical method.
  • the peeling does not occur due to the relatively small size of the metal ion to be inserted or the efficiency thereof is not high, so an additional peeling process is required.
  • Patent document 3 reports on the method of peeling graphene and graphite flakes by electrochemically inserting an ammonium series monomolecule.
  • 90% or more may have a thickness of 10 layers or more, which is closer to the thin graphite flakes than the graphene in the conventional sense.
  • the graphene flake manufacturing method using the existing electrochemical method has a disadvantage that the defect rate of the manufactured graphene flake is high, requires an additional process, is limited in size, or is thick.
  • One object of the present invention is to provide a method for producing graphene flakes, which is economical, mass-producible, and capable of producing high quality graphene flakes.
  • Another object of the present invention is to provide a dispersion solution of graphene flakes with improved dispersibility.
  • a method for preparing graphene flakes includes a positive electrode and a negative electrode including a graphene precursor, including a metal salt of an anionic organic single molecule. Impregnating an electrolyte solution, applying a voltage to the positive electrode and the negative electrode to form an interlayer compound of the anionic organic monomolecule and the graphene precursor, thereby peeling graphene flakes from the graphene precursor, and Separating the graphene flakes from a precursor solution comprising graphene flakes.
  • the graphene precursor includes at least one selected from the group consisting of natural graphite, artificial graphite and carbon fiber.
  • the anionic organic monomolecule includes at least one anionic functional group and a chain structure or benzene derivative structure bonded thereto.
  • the anionic functional group is a sulfate group (SO 2 ⁇ ) sulfonate group (SO 3 ⁇ ), a nitrite group (NO 2 ⁇ ), a nitrate group (nitrate: NO 3 ⁇ ) ), phosphite group (phosphite: PO 3 3-), phosphate groups (phosphate: PO 4 3-), carboxylate group (carboxylate: -: consisting of CO 3 2-) COO) and carbonate group (carbonate It includes at least one selected from the group.
  • the anionic organic monomolecule includes at least one anionic functional group and a chain structure bonded thereto, and includes formic acid, acetic acid, 1,2-ethanediamine (1, 2-Ethanediamine, Ethanesulfonate, Ethyl Ethanesulfonate, 2- (Methylamino) Ethane sulfonate, 2-Bromoethanesulfonate Bromoethanesulfonate, Methyl Ethanesulfonate, Ethane Sulfonic Acid, Ethanenitrile, 2-Hydroxy-3- (Phosphonooxy) Propionic Acid (2-Hydroxy-3- (Phosphonooxy) Propanoic Acid, Glycerate 3-Phosphate, 2- (4-Isobutylphenyl) Propanoic Acid Phosphate, 3- (3,5-dihydroxy Phenyl) -1-propionic acid sulfate (3- (3,5-D)
  • the anionic organic monomolecule includes at least one anionic functional group and a chain structure bonded thereto, and includes a crude acid, 4-aminobenzoic acid, benzenesulfonic acid (Benzenesulfonic Acid, Benzene Sulfonamide, Alkylbenzene Sulfonate, Phenyl Phosphate, Dodecylbenzenesulphonic Acid, 2-formyl-benzene-1,4-disulfide 2-Formyl-Benzene-1,4-Disulfonic Acid, Naphthalene Sulfonic Acid, Naphthalene Carboxylic Acid, Naphthoquine Phosphate, Naphthalene Acetic Acid, Naphthalene Phosphoric Acid, 1-Naphthoic Acid, 4-Amino-1-Naphthalenesulfonic Acid, 6- (P-Toludino) -2 Naphthalenesulfonic acid (6- (P-Toluidino)
  • the electrolyte solution, water, propylene carbonate (propylene carbonate), ethylene carbonate (ethylene carbonate), dimethyl sulfoxide (dimethyl sulfoxide (DMSO) and methylpyrrolidone (N-Methyl-2-pyrrolidone: NMP) at least one selected from the group consisting of.
  • the ion concentration of the electrolyte solution is 0.0001 M to 3 M.
  • the surface of the graphene flake, the anionic organic monomolecule is bonded by non-covalent functionalization.
  • the step of separating the graphene flakes from the precursor solution the step of filtering the precursor solution; And washing the graphene flakes obtained by filtering the precursor solution.
  • the graphene flake dispersion solution according to an embodiment of the present invention the graphene flakes dispersed in the solvent and the solvent, the graphene flakes in which an anionic organic monomolecule is bonded to the surface by non-covalent functionalization.
  • the solvent is water, ethanol, methanol, isopropanol, tetrahydrofuran (THF), benzene, xylene, toluene, cyclohexane, methylpyrrolidone (N-methyl 2-pyrrolidinone: NMP ), Dimethylformamide, dimethyl sulfoxide, dimethoxyethane (1,2-dimethoxyethane: DME), dichloroethane (1,2-dichloroethane), methylene chloride, chlorobenzene, chloroform, ethyl acetate, ethylene glycol, heptane, butanol (1-butanol, 2-butanol), butanone (2-butanone), acetonitrile, acetone and at least one selected from the group consisting of acetic acid.
  • THF tetrahydrofuran
  • benzene benzene
  • xylene toluene
  • graphene flakes may be prepared by an electrochemical method without an additional peeling process, and the obtained graphene flakes may have a large size and a thin thickness. Therefore, the graphene flakes can be expected to have a high quality.
  • the graphene flakes, the anionic organic single molecule is bonded to the surface by non-covalent functionalization, it is excellent in dispersibility to the solvent and can prevent the aggregation phenomenon. Therefore, it can be easily applied to the process using the graphene flake dispersion.
  • FIG. 1 is a flowchart illustrating a method for manufacturing graphene flakes according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view illustrating an electronic device to which a graphene flake dispersion prepared according to an embodiment of the present invention is applied.
  • FIG. 3 is a photograph of graphene flakes prepared by Example 1.
  • Figure 4 is a graph showing the size and thickness distribution of the graphene flakes prepared by Example 1.
  • FIG. 5 is a transmission electron microscope (TEM) photograph of the graphene flakes prepared by Example 1.
  • TEM transmission electron microscope
  • Figure 6 is a graph showing the Raman spectroscopic analysis of the graphene flakes prepared in Example 1.
  • FIG. 7 is a graph showing the results of X-ray photoelectron spectroscopy (XPS) analysis of graphene flakes prepared according to Example 1.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 8 is a graph showing the results of Fourier transform infrared spectroscopy (FT-IR) analysis of the graphene flakes prepared in Example 1.
  • FT-IR Fourier transform infrared spectroscopy
  • FIG. 9 is a photograph of a graphene solution in which graphene flakes prepared in Example 1 are redispersed in acetone.
  • FIG. 1 is a flowchart illustrating a method for manufacturing graphene flakes according to an embodiment of the present invention.
  • an anode and a cathode including a graphene precursor are impregnated in an electrolyte solution including a metal salt of an anionic organic monomolecule (S10).
  • the electrolyte solution contains a metal salt of the anionic organic single molecule as an electrolyte. Therefore, the electrolyte solution may include an organic monomolecular anion and a metal cation.
  • the anionic organic monomolecule may have at least one anionic functional group and have a chain structure or a benzene derivative structure bonded to the anionic functional group.
  • the chain structure may include an alkyl group or alkylene group having 1 or more carbon atoms, preferably, an alkyl group or alkylene group having 2 to 10 carbon atoms.
  • the anionic functional group is a sulfate group (SO 2 ⁇ ) sulfonate group (sulfonate: SO 3 ⁇ ), a nitrite group (NO 2 ⁇ ), a nitrate group (nitrate: NO 3 ⁇ ), phosphite group (phosphite: PO 3 3-), phosphate groups (phosphate: PO 4 3-), carboxylate group (carboxylate: COO -) or a carbonate group: can include (carbonate CO 3 2-) have. These may each be used alone or in combination.
  • the anionic organic monomolecule having the chain structure includes formic acid, acetic acid, 1,2-ethanediamine, ethanesulfonate, ethylesulfonate, and ethyl.
  • the anionic organic monomolecule having the benzene derivative structure may include benzoic acid, 4-aminobenzoic acid, benzeneenesulfonic acid, benzenesulfonamide, Alkylbenzene Sulfonate, Phenyl Phosphate, Dodecylbenzenesulphonic Acid, 2-Formyl-benzene-1,4-disulfonic acid (2-Formyl-Benzene-1,4- Disulfonic Acid, Naphthalene Sulfonic Acid, Naphthalene Carboxylic Acid, Naphthoquine Phosphate, Naphthalene Acetic Acid, Naphthalene Phosphoric Acid, 1-naphthaic acid (1-Naphthoic Acid), 4-Amino-1-Naphthalenesulfonic Acid, 6- (P-Toludino) -2-naphthalenesulfonic acid (6- (P-Toluidino) 2-Naphthalenes, 6-
  • the metal salt of the anionic organic monomolecule may include an alkali metal, for example, lithium, sodium, potassium, calcium, and the like.
  • the metal salt of the anionic organic single molecule having the chain structure may include sodium ethanesulfonate, disodium succinate, sodium succinate dibasic hexahydrate, Sodium Pentanoate, Sodium Pentyl Sulfate, Sodium 1-Pentyl Sulfate, 1-Hexanesulfonic Acid Sodium, 1-Heptanesulfonic Acid Sodium (1-Heptanesulfonic Acid Sodium), lithium dodecyl sulfonate (Lithium Dodecyl Sulfate), and the like. These may each be used alone or in combination.
  • the metal salt of the anionic organic monomolecular having the benzene derivative structure may include sodium dodecylbenzenesulfonate, potassium phenyl sulfate, disodium phenyl phosphate, and benzene.
  • the metal salt of the anionic organic monomolecule is not limited to the above specific examples, and may include all of various combinations of the anionic organic monomolecule and the alkali metal.
  • the anionic organic single molecule may be an anionic organic single molecule having a benzene derivative structure.
  • the anionic organic monomolecule having a benzene derivative structure can enhance the separation efficiency of the graphene flakes by strongly binding to the graphene precursor by pi interaction.
  • the electrolyte solution may include a solvent for dissolving the electrolyte.
  • the solvent may include water, propylene carbonate, ethylene carbonate, dimethyl sulfoxide (DMSO) and methylpyrrolidone (NMP). Which may be used alone or in combination.
  • the ion concentration of the electrolyte may be from 0.0001 M to 3 M, it is possible to adjust the defect rate of the prepared graphene according to the ion concentration.
  • the graphene precursor may include natural graphite, artificial graphite, carbon fiber, and the like.
  • the graphite may include chysi graphite.
  • Kish graphite is a kind of natural graphite and has a high crystallinity and a relatively large crystal size, thereby improving the size of the finally produced graphene flakes.
  • the cathode may be a counter electrode of the electrode including the graphene precursor, and may include a general electrode material such as metal or carbon.
  • an anode voltage and a cathode voltage are applied to the anode and the cathode, respectively, to form an intercalation compound by combining the graphene precursor of the cathode and the anionic organic monomolecule (S20).
  • the anionic organic monomolecule is inserted into the graphene precursor (graphite) and forms an intercalation compound by non-covalent functionalization, van der Waals bonds between the graphite layers are weakened, and the electrostatic charge due to the newly generated surface charge
  • the graphene flakes may be peeled from the graphene precursor by the miracle repulsive force.
  • an electrolyte solution containing graphene flakes can be obtained.
  • the voltage may be a DC voltage
  • the voltage used may range from 100 mV to 20 V
  • the current value may range from 1 mA to 5 A.
  • the time for applying the voltage may vary depending on the set voltage and current values, for example, 30 seconds to 7 days.
  • residual electrolyte may be removed through a filtration and washing process using a filtration device such as a vacuum filter.
  • the washing process may be repeatedly washed using a washing solution containing distilled water and / or alcohol.
  • the filtered and washed graphene flakes may be redispersed in a solvent to obtain a dispersion solution including the exfoliated graphene flakes.
  • the solvent may be water, ethanol, methanol, isopropanol, tetrahydrofuran (THF), benzene, xylene, toluene, cyclohexane, methylpyrrolidone (N-methyl 2-pyrrolidinone: NMP ), Dimethylformamide, dimethyl sulfoxide, dimethoxyethane (1,2-dimethoxyethane: DME), dichloroethane (1,2-dichloroethane), methylene chloride, chlorobenzene, chloroform, ethyl acetate, ethylene glycol, heptane, butanol (1-butanol, 2-butanol), butanone (2-butanone), acetonitrile, acetone, acetic acid, and the like, which may each be used alone or in combination.
  • THF tetrahydrofuran
  • benzene benzene
  • xylene toluene
  • Graphene flakes obtained according to an embodiment of the present invention can be obtained by an electrochemical method without an additional peeling process.
  • the graphene flakes may have a large size, for example, 50 ⁇ m or more, preferably 100 ⁇ m or more.
  • the flakes may have a thin thickness so that the flakes may have substantially the properties of graphene. Therefore, the graphene flakes can be expected to have a high quality.
  • the graphene flakes, the anionic organic single molecule is bonded to the surface by non-covalent functionalization, it is excellent in dispersibility to the solvent and can prevent the aggregation phenomenon. Therefore, it can be easily applied to the process using the graphene flake dispersion.
  • FIG. 2 is a schematic cross-sectional view illustrating an electronic device to which a graphene flake dispersion prepared according to an embodiment of the present invention is applied.
  • FIG. 2 illustrates an electronic device including a barrier film formed by using the dispersion solution manufactured by the process described with reference to FIG. 1, and the electronic device may be, for example, a display device.
  • the electronic device may include a PET substrate 100, a barrier film 110, a display panel 120, and a sealing member 130.
  • the barrier film 110 may be formed using the dispersion solution including the graphene flakes peeled off by the process described with reference to FIG. 1.
  • the dispersion solution may be applied onto the PET substrate 100 or the display panel 120, and the barrier film 110 may be formed through a drying process.
  • a predetermined patterning process for the barrier film 110 may be further performed.
  • the barrier film 110 may include graphene. Gas barrier properties of the display panel may be improved by the barrier film 110.
  • graphene may be combined into a uniform film to block oxygen or moisture.
  • an electronic device can be obtained in which defects such as performance degradation through reaction of oxygen and moisture are reduced.
  • the display panel 120 may include, for example, a display circuit board including a thin film transistor (TFT).
  • TFT thin film transistor
  • the display panel 120 may include, for example, a liquid crystal display (LCD) panel and an organic light emitting display (OLED) panel.
  • LCD liquid crystal display
  • OLED organic light emitting display
  • the sealing member 130 may include various covers, bezels, sealants, and the like that protect the display device.
  • An electrolyte having a molar concentration of 0.1 was prepared by dissolving 2.3 g of sodium 2-naphthalene sulfonate in 100 ml of distilled water.
  • the electrolyte solution containing the graphene flakes was filtered using a filtration filter and then repeatedly washed with distilled water, acetone, and an alcohol solvent to a content of 5 times the volume of the graphene flake electrolyte solution, and the obtained graphene flakes were washed. It was dispersed in acetone through an ultrasonic process.
  • FIG. 3 is a photograph of graphene flakes prepared by Example 1.
  • SEM scanning electron microscope
  • AFM atomic force microscope
  • the graphene flakes prepared by Example 1 may have a size of 100 micrometers or more.
  • the thickness of the graphene flake was about 0.7nm, it can be seen that the monolayer graphene was obtained through this.
  • Figure 4 is a graph showing the size and thickness distribution of the graphene flakes prepared by Example 1.
  • FIG. 5 is a transmission electron microscope (TEM) photograph of the graphene flakes prepared by Example 1.
  • TEM transmission electron microscope
  • the graphene flakes prepared in Example 1 have a size of 10 ⁇ m or more, where the number of layers is 1 to 4 layers.
  • Example 6 is a Raman spectroscopic analysis result of the graphene flakes prepared in Example 1.
  • the ratio of the D-pick ( ⁇ 1350 cm ⁇ 1 ) and the G-pick ( ⁇ 1600 cm ⁇ 1 ), which is an indicator of defects, is about 0.13. This is lower than the graphene flakes prepared by the conventional oxidation-reduction method or the electrochemical method using a conventional sulfuric acid electrolyte, it can be confirmed that the high-quality graphene flakes prepared by Example 1.
  • FIG. 7 is a graph showing the results of X-ray photoelectron spectroscopy (XPS) analysis of graphene flakes prepared according to Example 1.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 8 is a graph showing the results of Fourier transform infrared spectroscopy (FT-IR) analysis of the graphene flakes prepared in Example 1.
  • FT-IR Fourier transform infrared spectroscopy
  • naphthalene sulfonate (naphthalene-2-sulfonate) was non-covalent functionalized on the surface of the graphene flakes prepared in Example 1, it can be seen that the rate of defects on the surface of the graphene is very low.
  • FIG. 9 is a photograph of a graphene solution in which graphene flakes prepared in Example 1 are redispersed in acetone.
  • the prepared graphene can be dispersed without aggregation in an organic solvent such as acetone.
  • Graphene flakes prepared according to the exemplary embodiments described above, or dispersion solution containing the same, various light weight / high strength composite materials, heat dissipating materials, nano-ink materials, secondary batteries, fuel cells, etc. having improved electrical / mechanical properties It can be applied as an electrode material and a barrier / coating material.
  • cover glass 110 barrier film

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Abstract

La présente invention concerne un procédé de production de flocons de graphène qui comprend les étapes consistant à : imprégner une électrode positive et une électrode négative, qui contiennent toutes deux un précurseur de graphène, avec une solution d'électrolyte contenant un sel métallique d'une unique molécule organique anionique ; appliquer une tension au niveau de l'électrode positive et de l'électrode négative pour former un composé d'intercalation entre l'unique molécule organique anionique et le précurseur de graphène, ce qui permet d'exfolier un flocon de graphène du précurseur de graphène ; et séparer les flocons de graphène d'une solution de précurseur contenant les flocons de graphène.
PCT/KR2018/005921 2017-05-25 2018-05-24 Procédé de production de flocons de graphène de haute qualité par exfoliation électrochimique et solution de dispersion de flocons de graphène WO2018217042A1 (fr)

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WO2020239143A1 (fr) * 2019-05-27 2020-12-03 华侨大学 Encre conductrice au graphène et son procédé de préparation
CN115182021A (zh) * 2021-04-01 2022-10-14 浙江正泰电器股份有限公司 复配型分散剂及混合电镀液
CN113929087A (zh) * 2021-10-19 2022-01-14 深圳市汉嵙新材料技术有限公司 石墨烯片及其制备方法和应用

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