WO2023095724A1 - Procédé de production d'une structure en forme de plaque mince de graphite, procédé de production de graphite exfolié, et graphite exfolié - Google Patents

Procédé de production d'une structure en forme de plaque mince de graphite, procédé de production de graphite exfolié, et graphite exfolié Download PDF

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WO2023095724A1
WO2023095724A1 PCT/JP2022/042850 JP2022042850W WO2023095724A1 WO 2023095724 A1 WO2023095724 A1 WO 2023095724A1 JP 2022042850 W JP2022042850 W JP 2022042850W WO 2023095724 A1 WO2023095724 A1 WO 2023095724A1
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graphite
less
exfoliated graphite
mass
electrolyte
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泰司 西川
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株式会社カネカ
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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
    • C01B32/194—After-treatment
    • 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
    • C01B32/198—Graphene oxide
    • 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
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/22—Intercalation
    • C01B32/225—Expansion; Exfoliation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/023—Measuring, analysing or testing during electrolytic production
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/023—Measuring, analysing or testing during electrolytic production
    • C25B15/025—Measuring, analysing or testing during electrolytic production of electrolyte parameters
    • C25B15/029—Concentration

Definitions

  • the present invention relates to a method for producing a graphite sheet-like structure, a method for producing exfoliated graphite, and exfoliated graphite.
  • Graphene has high carrier mobility, thermal conductivity, and transparency.
  • graphene is a sheet of sp2 - bonded carbon atoms with a thickness of one atom, it is easy to increase the area of devices and has high thermal and chemical stability. Due to such excellent properties, graphene is expected to be applied to advanced industrial materials including the electronics field.
  • graphite is a laminate composed of many graphenes stacked on top of each other, and is easy to obtain. For this reason, a method has been proposed for producing exfoliated graphite in which the number of laminated layers of graphene is much smaller than that of graphite by exfoliating the layers of graphite.
  • exfoliated graphite for example, in an electrochemical reaction system containing a graphite-containing anode, a cathode, and an electrolyte solution, a voltage is applied between the anode and the cathode to obtain a film between the graphite layers.
  • a method is known in which, after intercalating ions derived from an electrolyte to obtain a graphite sheet-like structure, the layers of the sheet-like structure are separated.
  • the exfoliated graphite thus obtained is composed of oxygen-containing graphene (graphene oxide), into which functional groups such as hydroxy groups and carboxy groups are introduced.
  • Such exfoliated graphite can be modified with functional groups to make it highly functional, so it is expected to be applied to polymer composite materials, paints, inks, drug conjugates, lubricants, catalysts, etc. there is
  • Patent Document 1 describes a method of electrolysis using tetrafluoroboric acid or hexafluorophosphoric acid as an electrolyte. Further, Patent Document 1 describes a method of electrolysis using an anode containing specific graphite as a working electrode and sulfuric acid or nitric acid as an electrolyte.
  • Patent Document 1 when tetrafluoroboric acid or hexafluorophosphoric acid is used as the electrolyte, the exfoliated graphite obtained has a high content of fluorine element and boron element, and is not applicable to advanced industrial materials. There was a risk of being restricted. Further, in Patent Document 1, when an anode containing specific graphite is used as the working electrode and sulfuric acid or nitric acid is used as the electrolyte, the resulting exfoliated graphite has a mass ratio of carbon element to oxygen element (C/O ratio) was large, and the introduction rate of functional groups was not sufficient. Furthermore, in Patent Document 1, since the concentration of the electrolyte is high when sulfuric acid or nitric acid is used as the electrolyte, it is also desired to lower the concentration of the electrolyte from the viewpoint of safety.
  • C/O ratio carbon element to oxygen element
  • an electrolyte solution having a low electrolyte concentration is used to obtain exfoliated graphite having a low content of fluorine element and boron element and a low mass ratio of carbon element to oxygen element (C/O ratio).
  • the aim is to provide a possible manufacturing method.
  • One aspect of the present invention is a method for producing a graphite thin plate structure, in which an electrochemical reaction system including an anode containing graphite, a cathode, and an electrolytic solution containing sulfuric acid and/or sulfate as an electrolyte, and applying a voltage between the anode and the cathode, wherein the graphite has a thermal diffusivity of 3.5 cm 2 /s or more, and the electrolyte solution has a concentration of the electrolyte of 0.005 M or more and 5 M or less. and the voltage is between 3V and 20V.
  • the graphite may be a heat-treated polycondensation polymer compound.
  • the polycondensation polymer compound may be an aromatic polyimide.
  • the anode may be a heat-treated expanded graphite sheet.
  • the expanded graphite sheet may be a pressed product of expanded graphite obtained by soaking natural graphite in a strong acid and then heat-treating it.
  • the electrolyte solution may have an electrolyte concentration of 0.005M or more and 0.05M or less, and the voltage may be 3V or more and 19V or less.
  • the electrolyte solution may have an electrolyte concentration of 0.05M or more and 0.5M or less, and the voltage may be 3V or more and 18V or less.
  • the electrolyte solution may have a concentration of 0.5M or more and 5M or less, and the voltage may be 3V or more and 17V or less.
  • Another aspect of the present invention is a method for producing exfoliated graphite, comprising: obtaining a graphite thin plate-like structure by the method for producing a graphite thin plate-like structure; and exfoliating to obtain exfoliated graphite.
  • the exfoliated graphite has a sulfur element content of 0.01% by mass or more and 2.5% by mass or less and a fluorine element content of less than 0.1% by mass,
  • the content of boron element is less than 0.1% by mass, and the mass ratio of carbon element to oxygen element is 0.7 or more and 3.0 or less.
  • the exfoliated graphite may have a mass ratio of carbon element to oxygen element of 1.5 or more and 2.6 or less.
  • the maximum intensity of the peak contained in the region where 2 ⁇ is 7° or more and 12° or less in the XRD spectrum is X
  • the maximum intensity of the peak contained in the region where 2 ⁇ is 23° or more and 30° or less is X
  • X and Y may satisfy the following formula: 0.8 ⁇ X/Y.
  • X and Y may satisfy the following formula: 2 ⁇ X/Y.
  • an electrolyte solution having a low electrolyte concentration is used to obtain exfoliated graphite having a low content of fluorine element and boron element and a low mass ratio of carbon element to oxygen element (C/O ratio). It is possible to provide a manufacturing method capable of
  • FIG. 1 is a diagram showing an XRD spectrum of exfoliated graphite of Example 1.
  • FIG. FIG. 10 shows an XRD spectrum of exfoliated graphite of Example 3;
  • FIG. 10 shows an XRD spectrum of exfoliated graphite of Example 4;
  • FIG. 11 shows an XRD spectrum of exfoliated graphite of Example 7;
  • FIG. 11 shows an XRD spectrum of exfoliated graphite of Example 8;
  • FIG. 11 shows an XRD spectrum of exfoliated graphite of Example 9;
  • FIG. 11 shows the XRD spectrum of exfoliated graphite of Example 14;
  • FIG. 11 shows an XRD spectrum of exfoliated graphite of Example 15;
  • FIG. 11 shows an XRD spectrum of exfoliated graphite of Example 18;
  • FIG. 11 shows an XRD spectrum of exfoliated graphite of Example 19; 1 is a diagram showing an XRD spectrum of exfoliated graphite of Comparative Example 1.
  • FIG. 3 is a diagram showing an XRD spectrum of exfoliated graphite of Comparative Example 2.
  • FIG. 3 is a diagram showing an XRD spectrum of exfoliated graphite of Comparative Example 3.
  • FIG. 4 is a diagram showing an XRD spectrum of exfoliated graphite of Comparative Example 4.
  • FIG. 10 is a diagram showing an XRD spectrum of exfoliated graphite of Comparative Example 5;
  • FIG. 10 is a diagram showing an XRD spectrum of exfoliated graphite of Comparative Example 6;
  • FIG. 10 is a diagram showing an XRD spectrum of exfoliated graphite of Comparative Example 7;
  • FIG. 10 is a diagram showing an XRD spectrum of exfoliated graphite of Comparative Example 8;
  • FIG. 11 shows an XRD spectrum of exfoliated graphite of Comparative Example 10;
  • FIG. 10 is a diagram showing an XRD spectrum of exfoliated graphite of Comparative Example 11;
  • FIG. 2 shows the electrical conductivity of 0.1 M and 1 M aqueous solutions of electrolytes.
  • FIG. 4 is a diagram showing the relationship between the type of electrolyte and the appearance of a graphite thin plate-like structure when the concentration of the electrolyte is 1M.
  • FIG. 4 is a diagram showing the relationship between the type of electrolyte and the appearance of a graphite thin plate-like structure when the concentration of the electrolyte is 1M.
  • FIG. 4 is a diagram showing the relationship between the type of electrolyte and the reactivity of electrochemical oxidation;
  • FIG. 4 is a diagram showing the relationship between the type of electrolyte and the reactivity of electrochemical oxidation;
  • FIG. 4 is a diagram showing the relationship between electrolyte concentration and electrochemical oxidation reactivity.
  • FIG. 4 is a diagram showing the relationship between electrolyte concentration and electrochemical oxidation reactivity.
  • FIG. 4 is a diagram showing the relationship between the type of electrolyte and the reaction time when the immersion size of the graphite sheet is 5 cm ⁇ 5 cm.
  • the method for producing a graphite thin plate structure comprises an electrochemical reaction system including an anode containing graphite, a cathode, and an electrolytic solution containing sulfuric acid and/or sulfate as an electrolyte, wherein the anode and the cathode and applying a voltage between.
  • Exfoliated graphite can be obtained by exfoliating the layers of the graphite sheet-like structure obtained by this production method.
  • graphite thin plate structure means that an interlayer material is inserted between layers of graphite (graphene laminate) to increase the distance between layers (distance between adjacent graphenes). It refers to a thin plate-like structure that is
  • exfoliated graphite refers to a graphene laminate in which the number of graphene laminates is smaller than that of graphite.
  • the thermal diffusivity of graphite contained in the anode is 3.5 cm 2 /s or more, preferably 5.0 cm 2 /s or more, more preferably 7.0 cm 2 /s or more. More preferably, it is 5 cm 2 /s or more.
  • the upper limit of the thermal diffusivity is not particularly limited, it is preferably 12 cm 2 /s or less, for example.
  • the thermal diffusivity of graphite is 3.5 cm 2 /s or more, the mass ratio (C/O ratio) of carbon element to oxygen element in exfoliated graphite tends to be small.
  • graphite-containing anode having a thermal diffusivity of 3.5 cm 2 /s or more is a graphite-containing anode obtained by heat-treating a polycondensation polymer compound.
  • polycondensation polymer compounds include aromatic polyimides, aromatic polyamides, polyoxadiazoles, and polyparaphenylene vinylenes. Among these, aromatic polyimides are preferred.
  • the heat treatment temperature of the polycondensation polymer compound is preferably, for example, 2400°C or higher and 3200°C or lower.
  • the heat treatment time of the polycondensation polymer compound is preferably, for example, 3 hours or more and 72 hours or less.
  • Graphite obtained by heat-treating a polycondensation polymer compound has a structure in which planar graphite crystals are laminated in layers, and intercalation of sulfate ions between graphite layers is particularly easy to proceed.
  • intercalated flakes and the like are particularly unlikely to occur from the graphite, and the overall form of the anode can be easily maintained. Therefore, it is possible to more efficiently produce a graphite sheet-like structure or exfoliated graphite of higher quality.
  • anode containing graphite having a thermal diffusivity of 3.5 cm 2 /s or more is an anode obtained by heat-treating an expanded graphite sheet.
  • the expanded graphite sheet can be obtained, for example, by soaking natural graphite in a strong acid, heat-treating it in an expansion furnace to obtain expanded graphite, and then pressing this expanded graphite at high pressure.
  • strong acids include concentrated sulfuric acid and nitric acid.
  • the heat treatment temperature of the expanded graphite sheet is preferably, for example, 900°C or higher and 3200°C or lower.
  • the heat treatment time of the expanded graphite sheet is preferably, for example, 1 hour or more and 72 hours or less.
  • the shape of the anode is not particularly limited, and examples thereof include rod-like, plate-like, block-like, sheet-like, foil-like, and roll-like shapes.
  • the material that constitutes the cathode is not particularly limited as long as it has the function of donating electrons to the cations generated in the anode reaction and is capable of constructing an electrochemically stable system.
  • Materials constituting the cathode include, for example, metals such as platinum, stainless steel, copper, zinc and lead; carbonaceous materials such as vitreous carbon and graphite; and the like.
  • the shape of the cathode is not particularly limited, and examples thereof include wire-like, plate-like, and mesh-like shapes.
  • the area of the cathode may be increased as much as possible in order not to impair the efficiency of the cathode reaction or to prevent the electrical resistance of the electrochemical reaction system from increasing unnecessarily. good.
  • an ion-exchange membrane, a spacer, or the like may be placed between both electrodes in order to prevent undesirable reactions from occurring at the anode and/or cathode, or to prevent short-circuiting between the anode and cathode.
  • the electrochemical reaction system may further include a reference electrode when performing precise potential control.
  • a reference electrode when performing precise potential control.
  • the reference electrode include, but are not limited to, Ag/AgCl electrodes.
  • the electrolyte solution is a solution in which sulfuric acid and/or sulfate are dissolved in a solvent.
  • sulfates include ammonium sulfate, sodium sulfate, magnesium sulfate, potassium sulfate, calcium sulfate, and the like.
  • Sulfuric acid, sodium sulfate, and ammonium sulfate are preferred as electrolytes.
  • the solvent is not particularly limited as long as it can be mixed with the electrolyte or electrolyte aqueous solution and is electrochemically stable when manufacturing the graphite thin plate structure.
  • solvents include protic polar solvents such as water and lower alcohols (methanol, ethanol, propanol, etc.); aprotic polar solvents such as acetonitrile, dimethylformamide, dimethoxyethane, dimethyl carbonate, propylene carbonate, and dimethylsulfoxide; and may be used in combination of two or more.
  • the solvent preferably contains water.
  • water may be used alone, water and a protic polar solvent other than water may be used in combination, or water and an aprotic polar solvent may be used in combination.
  • Exfoliated graphite obtained using a solvent containing water tends to have good affinity for water and excellent dispersibility in water.
  • the resulting graphite sheet-like structures and exfoliated graphite have alkoxy groups and/or alkyl groups derived from the alcohol solvent.
  • Exfoliated graphite obtained using an alcohol solvent tends to have good affinity for the alcohol solvent and excellent dispersibility in the alcohol solvent.
  • the concentration of the electrolyte in the electrolyte solution is 0.005M or more and 5M or less, preferably 0.01M or more and 3M or less, and more preferably 0.05M or more and 2M or less.
  • concentration of the electrolyte in the electrolyte solution is 0.005M or more, sulfate ions are likely to intercalate between the layers of graphite, so that the layers of the thin plate-like structure of graphite tend to be easily separated.
  • the concentration of the electrolyte in the electrolyte solution is 5M or less, the mass ratio (C/O ratio) of the carbon element to the oxygen element of the exfoliated graphite tends to be small.
  • the conductivity of the electrolyte solution is, for example, preferably 1 mS/cm or more and 2000 mS/cm or less, more preferably 5 mS/cm or more and 1000 mS/cm or less.
  • the electric conductivity of the electrolyte solution is 1 mS/cm or more, sulfate ions are likely to intercalate between the graphite layers, so that the layers of the graphite sheet-like structure tend to be easily separated.
  • the electric conductivity of the electrolyte solution is 2000 mS/cm or less, the mass ratio (C/O ratio) of the carbon element to the oxygen element of the exfoliated graphite tends to be small.
  • the temperature of the electrolyte solution can vary depending on the type of solvent that dissolves the electrolyte and the concentration of the electrolyte in the electrolyte solution, but effectively, the lower limit is the temperature at which the electrolyte solution does not freeze, and the upper limit is the boiling point of the electrolyte solution.
  • the temperature of the electrolyte solution is, for example, preferably 0° C. or higher and 100° C. or lower, and more preferably 0° C. or higher and 80° C. or lower.
  • the voltage applied between the anode and the cathode is 3 V or more and 20 V or less.
  • the voltage applied between the anode and the cathode is 3 V or more, sulfate ions are likely to intercalate between the graphite layers, so that the layers of the graphite sheet-like structure tend to be easily separated.
  • the voltage applied between the anode and the cathode is 20 V or less, the mass ratio (C/O ratio) of carbon element to oxygen element in exfoliated graphite tends to decrease.
  • the voltage applied between the anode and the cathode is preferably 3V or more and 20V or less, more preferably 3V or more and 19V or less. It is more preferable to have Further, when the concentration of the electrolyte in the electrolyte solution is 0.05 M or more and 0.5 M or less, the voltage applied between the anode and the cathode is preferably 3 V or more and 20 V or less, and is 3 V or more and 18 V or less. is more preferable.
  • the voltage applied between the anode and the cathode is preferably 3V or more and 20V or less, and more preferably 3V or more and 17V or less. more preferred.
  • the voltage applied between the anode and the cathode may fluctuate in the range of 3 V or more and 20 V or less, or may be constant, but it is preferable to apply a constant voltage in the range of 3 V or more and 20 V or less. .
  • the electrolyte, sulfuric acid and/or sulfate is theoretically not consumed before and after the electrolytic reaction. Therefore, the electrolyte solution can be reused after it has been used in the manufacture of graphite lamellar structures. However, the electrolyte that has been removed from the electrolyte solution and adhered to the thin plate-like structure of graphite may be replenished to the electrochemical reaction system, if necessary.
  • the method for recovering the electrolyte solution from the graphite thin plate-like structure is not particularly limited. Examples thereof include a method of continuously separating an electrolyte solution from a thin plate-like structure of graphite on a press.
  • the electrolyte solution can be removed from the graphite sheet-like structure by washing it with excess deionized water until the washing liquid becomes nearly neutral.
  • the thin plate-like structure of graphite can be dried as necessary and then applied to the method for producing exfoliated graphite described later.
  • drying the graphite sheet-like structure for example, it can be dried at a temperature of 80° C. or less using a constant temperature dryer or a vacuum dryer.
  • the method for producing exfoliated graphite according to the present embodiment comprises a step of obtaining a graphite thin plate-like structure and exfoliating the layers of the graphite thin plate-like structure by the method for producing a graphite thin plate-like structure according to the present embodiment. and obtaining exfoliated graphite.
  • the method for separating the layers of the graphite thin plate-like structure is not particularly limited. method, a method of heating a thin plate-like structure of graphite, and the like. Specifically, after dispersing a thin plate-like structure of graphite in an appropriate amount of deionized water, it can be irradiated with ultrasonic waves or treated with a mixer or an apparatus capable of applying a shearing force.
  • the exfoliated graphite may be freeze-dried, or may be filtered or centrifuged and then dried.
  • the method for drying the exfoliated graphite is the same as the method for drying the thin plate-like structure of graphite.
  • exfoliated graphite The exfoliated graphite according to this embodiment can be obtained by the method for producing exfoliated graphite according to this embodiment.
  • the exfoliated graphite according to the present embodiment has a sulfur element content of 0.01% by mass or more and 2.5% by mass or less, a fluorine element content of less than 0.1% by mass, and a boron element content % is less than 0.1% by mass.
  • the exfoliated graphite according to the present embodiment can have a low content of heavy metal elements as impurities.
  • the exfoliated graphite according to the present embodiment can have a manganese element content of less than 0.1% by mass.
  • the mass ratio of carbon element to oxygen element is 0.7 or more and 3.0 or less, preferably 1.5 or more and 3.0 or less, It is more preferably 1.5 or more and 2.6 or less.
  • X is the maximum intensity of the peak included in the region where 2 ⁇ is 7° or more and 12° or less in the XRD spectrum, and the maximum intensity of the peak included in the region where 2 ⁇ is 23° or more and 30° or less.
  • X and Y preferably satisfy the following expression: 0.8 ⁇ X/Y, and more preferably satisfy the following expression: 2 ⁇ X/Y.
  • the thickness of the exfoliated graphite according to the present embodiment is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 10 nm or less, and particularly preferably 1 nm or less.
  • the average particle size of the exfoliated graphite according to the present embodiment is preferably 30 nm or more and 1 mm or less, more preferably 100 nm or more and 200 ⁇ m or less, and even more preferably 200 nm or more and 100 ⁇ m or less.
  • ⁇ Thermal diffusivity of graphite> A sample of graphite cut into a shape of 40 mm ⁇ 40 mm was prepared, and a thermal diffusivity measuring device (Thermo Wave Analyzer TA3, Bethel Co., Ltd.) was used to measure the thermal diffusivity [ cm /s] was measured.
  • Elemental analysis of exfoliated graphite was performed using a scanning fluorescent X-ray spectrometer (ZSX PrimusIII+, manufactured by Rigaku Co., Ltd.), and the content of elemental sulfur (S) [% by mass] and the content of elemental fluorine (F) were determined.
  • the content [% by mass], the content [% by mass] of the boron element (B), and the mass ratio of the carbon element to the oxygen element (C/O ratio) were measured.
  • X-ray diffractometer X'Pert Pro, manufactured by Malvern Panalytical
  • graphite sheet A As the graphite sheet A, a graphite sheet (manufactured by Kaneka Corporation) having a thickness of 32 ⁇ m and a thermal diffusivity of 9 cm 2 /s obtained by heat-treating an aromatic polyimide film having a thickness of 62 ⁇ m at a temperature of 2900° C. or higher was used.
  • Graphite sheet B As the graphite sheet B, a graphite sheet having a thickness of 200 ⁇ m and a thermal diffusivity of 4 cm 2 /s obtained by heat-treating an expanded graphite sheet PF-HP (manufactured by Toyo Tanso Co., Ltd.) at 2400° C. was used.
  • Example 1 After adding 3 L of a 1 M sulfuric acid aqueous solution as an electrolyte solution to a PVC reactor, a graphite sheet A as an anode was fixed so that 6 cm ⁇ 25 cm of the surface area was immersed in the electrolyte solution, and a carbon plate was used as a cathode. was set. Next, the anode and the cathode were connected to a DC power supply, a voltage of 7 V was applied, and electrolysis was performed at room temperature until the current decreased and became constant, thereby obtaining a thin plate-like structure of graphite.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 0.9. Also, the exfoliated graphite had an X/Y ratio of 3.3 (see FIG. 1A).
  • Example 2 Exfoliated graphite was obtained in the same manner as in Example 1, except that the anode and cathode were connected to a DC power source and a voltage of 6 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 0.9.
  • the exfoliated graphite had an X/Y ratio of 3.3.
  • Example 3 Exfoliated graphite was obtained in the same manner as in Example 1, except that the anode and cathode were connected to a DC power source and a voltage of 5 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 1.0. Also, the exfoliated graphite had an X/Y ratio of 3.4 (see FIG. 1B).
  • Example 4 Exfoliated graphite was obtained in the same manner as in Example 1, except that the anode and cathode were connected to a DC power source and a voltage of 4 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 1.3. Also, the exfoliated graphite had an X/Y ratio of 3.6 (see FIG. 1C).
  • Example 5 Exfoliated graphite was obtained in the same manner as in Example 1, except that the anode and cathode were connected to a DC power source and a voltage of 3 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 2.3.
  • the exfoliated graphite had an X/Y ratio of 2.5.
  • Example 6 Exfoliated graphite was obtained in the same manner as in Example 1, except that a 0.1 M sulfuric acid aqueous solution was used as the electrolyte solution.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 1.1.
  • the exfoliated graphite had an X/Y ratio of 2.1.
  • Example 7 Exfoliated graphite was obtained in the same manner as in Example 6, except that the anode and cathode were connected to a DC power source and a voltage of 5 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 1.3. Also, the exfoliated graphite had an X/Y ratio of 2.1 (see FIG. 2A).
  • Example 8 Exfoliated graphite was obtained in the same manner as in Example 6, except that the anode and cathode were connected to a DC power source and a voltage of 4 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 2.1. Also, the exfoliated graphite had an X/Y ratio of 2.1 (see FIG. 2B).
  • Example 9 Exfoliated graphite was obtained in the same manner as in Example 6, except that the anode and cathode were connected to a DC power source and a voltage of 3.5 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 2.1. Also, the exfoliated graphite had an X/Y ratio of 3.5 (see FIG. 2C).
  • Example 10 Exfoliated graphite was obtained in the same manner as in Example 1, except that a 0.01 M sulfuric acid aqueous solution was used as the electrolyte solution.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 2.5.
  • the exfoliated graphite had an X/Y ratio of 1.5.
  • Example 11 Exfoliated graphite was obtained in the same manner as in Example 10, except that the anode and cathode were connected to a DC power source and a voltage of 6 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 2.5.
  • the exfoliated graphite had an X/Y ratio of 2.5.
  • Example 12 Exfoliated graphite was obtained in the same manner as in Example 7, except that graphite sheet B was used as the anode.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 3.0.
  • the exfoliated graphite had an X/Y ratio of 1.2.
  • Example 13 Exfoliated graphite was obtained in the same manner as in Example 8, except that graphite sheet B was used as the anode.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 2.7.
  • the exfoliated graphite had an X/Y ratio of 0.8.
  • Example 14 Exfoliated graphite was obtained in the same manner as in Example 1, except that ammonium sulfate was used as the electrolyte.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 1.3. Also, the exfoliated graphite had an X/Y ratio of 2.6 (see FIG. 3A).
  • Example 15 Exfoliated graphite was obtained in the same manner as in Example 14, except that the anode and cathode were connected to a DC power source and a voltage of 5 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 1.5. Also, the exfoliated graphite had an X/Y ratio of 3.0 (see FIG. 3B).
  • Example 16 Exfoliated graphite was obtained in the same manner as in Example 6, except that ammonium sulfate was used as the electrolyte.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 2.0.
  • the exfoliated graphite had an X/Y ratio of 2.5.
  • Example 17 Exfoliated graphite was obtained in the same manner as in Example 16, except that the anode and cathode were connected to a DC power source and a voltage of 5 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 2.2.
  • the exfoliated graphite had an X/Y ratio of 2.1.
  • Example 18 Exfoliated graphite was obtained in the same manner as in Example 1, except that sodium sulfate was used as the electrolyte.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 1.4. Also, the exfoliated graphite had an X/Y ratio of 2.8 (see FIG. 4A).
  • Example 19 Exfoliated graphite was obtained in the same manner as in Example 18, except that the anode and cathode were connected to a DC power source and a voltage of 5 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 1.6. Also, the exfoliated graphite had an X/Y ratio of 2.3 (see FIG. 4B).
  • Example 20 Exfoliated graphite was obtained in the same manner as in Example 6, except that sodium sulfate was used as the electrolyte.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 2.2.
  • the exfoliated graphite had an X/Y ratio of 2.5.
  • Example 21 Exfoliated graphite was obtained in the same manner as in Example 20, except that the anode and cathode were connected to a DC power supply and a voltage of 5 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of 1 to 2.5% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was 2.4.
  • the exfoliated graphite had an X/Y ratio of 2.1.
  • Exfoliated graphite was obtained in the same manner as in Example 1, except that hydroboric acid was used as the electrolyte.
  • the exfoliated graphite has a sulfur element (S) content of less than 0.1% by mass, a fluorine element (F) content of 1 to 3% by mass, and a boron element (B) content of 0.1 to 1%. % by mass, and the C/O ratio was 1.0.
  • the exfoliated graphite had an X/Y ratio greater than 10 (see FIG. 5A).
  • Exfoliated graphite was obtained in the same manner as in Comparative Example 1, except that the anode and cathode were connected to a DC power source and a voltage of 6 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of less than 0.1% by mass, a fluorine element (F) content of 1 to 3% by mass, and a boron element (B) content of 0.1 to 1%. % by mass, and the C/O ratio was 1.0.
  • the exfoliated graphite had an X/Y ratio greater than 10 (see FIG. 5B).
  • Exfoliated graphite was obtained in the same manner as in Comparative Example 1, except that the anode and cathode were connected to a DC power supply and a voltage of 5 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of less than 0.1% by mass, a fluorine element (F) content of 1 to 3% by mass, and a boron element (B) content of 0.1 to 1%. % by mass, and the C/O ratio was 1.1.
  • the exfoliated graphite had an X/Y ratio of 9.0 (see FIG. 5C).
  • Exfoliated graphite was obtained in the same manner as in Comparative Example 1, except that the anode and cathode were connected to a DC power supply and a voltage of 4 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of less than 0.1% by mass, a fluorine element (F) content of 1 to 3% by mass, and a boron element (B) content of 0.1 to 1%. % by mass, and the C/O ratio was 1.4.
  • the exfoliated graphite had an X/Y ratio of 3.0 (see FIG. 5D).
  • Exfoliated graphite was obtained in the same manner as in Example 6, except that hydroboric acid was used as the electrolyte.
  • the exfoliated graphite has a sulfur element (S) content of less than 0.1% by mass, a fluorine element (F) content of 1 to 3% by mass, and a boron element (B) content of 0.1 to 1%. % by mass, and the C/O ratio was 1.1.
  • the exfoliated graphite had an X/Y ratio of 7.8 (see FIG. 6A).
  • Exfoliated graphite was obtained in the same manner as in Comparative Example 5, except that the anode and cathode were connected to a DC power source and a voltage of 5 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of less than 0.1% by mass, a fluorine element (F) content of 1 to 3% by mass, and a boron element (B) content of 0.1 to 1%. % by mass, and the C/O ratio was 1.3.
  • the exfoliated graphite had an X/Y ratio of 4.2 (see FIG. 6B).
  • Exfoliated graphite was obtained in the same manner as in Example 1, except that ammonium hydroborofluorate was used as the electrolyte.
  • the exfoliated graphite has a sulfur element (S) content of less than 0.1% by mass, a fluorine element (F) content of 1 to 3% by mass, and a boron element (B) content of 0.1 to 1%. % by mass, and the C/O ratio was 1.0.
  • the exfoliated graphite had an X/Y ratio of 8.5 (see FIG. 7A).
  • Exfoliated graphite was obtained in the same manner as in Comparative Example 7, except that the anode and cathode were connected to a DC power source and a voltage of 5 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of less than 0.1% by mass, a fluorine element (F) content of 1 to 3% by mass, and a boron element (B) content of 0.1 to 1%. % by mass, and the C/O ratio was 1.3.
  • the exfoliated graphite had an X/Y ratio of 5.0 (see FIG. 7B).
  • Exfoliated graphite was obtained in the same manner as in Example 7, except that ammonium hydroborofluorate was used as the electrolyte.
  • the exfoliated graphite has a sulfur element (S) content of less than 0.1% by mass, a fluorine element (F) content of 1 to 3% by mass, and a boron element (B) content of 0.1 to 1%. % by mass, and the C/O ratio was 1.5.
  • the exfoliated graphite had an X/Y ratio of 2.8.
  • Exfoliated graphite was obtained in the same manner as in Example 1, except that sodium hydroborofluorate was used as the electrolyte.
  • the exfoliated graphite has a sulfur element (S) content of less than 0.1% by mass, a fluorine element (F) content of 1 to 3% by mass, and a boron element (B) content of 0.1 to 1%. % by mass, and the C/O ratio was 1.1.
  • the exfoliated graphite had an X/Y ratio of 9.9 (see FIG. 8A).
  • Exfoliated graphite was obtained in the same manner as in Comparative Example 10, except that the anode and cathode were connected to a DC power source and a voltage of 5 V was applied.
  • the exfoliated graphite has a sulfur element (S) content of less than 0.1% by mass, a fluorine element (F) content of 1 to 3% by mass, and a boron element (B) content of 0.1 to 1%. % by mass, and the C/O ratio was 1.4.
  • the exfoliated graphite had an X/Y ratio of 4.7 (see FIG. 8B).
  • Exfoliated graphite was obtained in the same manner as in Example 7, except that sodium hydroborofluorate was used as the electrolyte.
  • the exfoliated graphite has a sulfur element (S) content of less than 0.1% by mass, a fluorine element (F) content of 1 to 3% by mass, and a boron element (B) content of 0.1 to 1%. % by mass, and the C/O ratio was 1.6. Also, the exfoliated graphite had an X/Y ratio of 2.6.
  • Exfoliated graphite was obtained in the same manner as in Example 3, except that a 9.2 M sulfuric acid aqueous solution was used as the electrolyte solution.
  • the exfoliated graphite has a sulfur element (S) content of 0.1 to 2% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and C/ The O ratio was greater than 10. Also, the exfoliated graphite had an X/Y ratio of less than 0.7.
  • Exfoliated graphite has a sulfur element (S) content of less than 2% by mass, a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, and a C/O The ratio was greater than 4.1. Also, the exfoliated graphite had an X/Y ratio of less than 0.7.
  • Deionized water was added to the graphite thin plate structure to adjust the solid content concentration to about 1% by mass. After pulverizing the obtained solution for 5 minutes with a high-speed stirrer, the solution was placed in a petri dish so that the thickness after drying was about 25 ⁇ m, and dried at room temperature to obtain a film of exfoliated graphite.
  • the exfoliated graphite has a sulfur element (S) content of 2.6 to 4% by mass, and a fluorine element (F) and a boron element (B) content of both less than 0.1% by mass, The C/O ratio was less than 1.5. Also, the exfoliated graphite had an X/Y ratio greater than 2.
  • Tables 1 to 9 show the production conditions and characteristics of exfoliated graphite.
  • the exfoliated graphite of Examples 1 to 21 has a low content of fluorine element (F) and boron element (B) and a small C/O ratio.
  • fluorine element (F) and boron element (B) have a low content of fluorine element (F) and boron element (B) and a small C/O ratio.
  • elemental fluorine (F) and elemental boron (B) High content.
  • the exfoliated graphite of Comparative Example 13 has a large C/O ratio because a 9.2 M sulfuric acid aqueous solution is used as an electrolyte solution during production.
  • the exfoliated graphite of Comparative Example 14 has a low content of fluorine element (F) and boron element (B), but has a large C/O ratio.
  • the exfoliated graphite of Comparative Example 15 has a low content of fluorine element (F) and boron element (B) and a small C/O ratio, 18.3 M sulfuric acid aqueous solution (concentrated sulfuric acid) was used as an electrolyte solution during production. is used, and safety during manufacturing is lacking.
  • FIG. 9 shows the conductivity of 0.1M and 1M aqueous solutions of the electrolyte.
  • the electrolytes are HBF 4 , NH 4 BF 4 , NaBF 4 , H 2 SO 4 , (NH 4 ) 2 SO 4 and Na 2 SO 4 used in Examples and Comparative Examples.
  • FIG. 10 shows the relationship between the type of electrolyte and the appearance of the graphite thin plate-like structure when the concentration of the electrolyte is 1M.
  • the graphite sheet A was used as the anode, and the carbon plate was used as the cathode.
  • FIG. 13 shows the relationship between the type of electrolyte and the reaction time when the graphite sheet is immersed in a size of 5 cm ⁇ 5 cm.
  • the graphite sheet A was used as the anode, and the carbon plate was used as the cathode.

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Abstract

L'invention concerne un procédé de production d'une structure en forme de plaque mince de graphite qui comprend une étape d'application d'une tension entre une anode et une cathode dans un système de réaction électrochimique comprenant l'anode doté de graphite, la cathode, et une solution électrolytique qui comprend de l'acide sulfurique et/ou un sulfate comme électrolyte. Le graphite présente une diffusivité thermique de 3,5 cm2/s ou plus, la solution d'électrolyte présente une concentration de l'électrolyte de 0,005 à 5 M inclus, et la tension est de 3 à 20 V inclus.
PCT/JP2022/042850 2021-11-24 2022-11-18 Procédé de production d'une structure en forme de plaque mince de graphite, procédé de production de graphite exfolié, et graphite exfolié WO2023095724A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017502168A (ja) * 2013-11-20 2017-01-19 ザ・ユニバーシティ・オブ・マンチェスターＴｈｅ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｍａｎｃｈｅｓｔｅｒ 酸化グラフェンの製造
JP2019510721A (ja) * 2016-03-22 2019-04-18 中国科学院金属研究所 酸化グラフェンナノプレートレット連続調製法
WO2020129427A1 (fr) * 2018-12-19 2020-06-25 株式会社カネカ Procédé de production d'une structure en forme de feuille mince de graphite, graphite exfolié et son procédé de production
JP2021513750A (ja) * 2017-12-29 2021-05-27 シクソニア・テック・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 官能化された半導体−または導体材料の製造方法およびその使用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017502168A (ja) * 2013-11-20 2017-01-19 ザ・ユニバーシティ・オブ・マンチェスターＴｈｅ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｍａｎｃｈｅｓｔｅｒ 酸化グラフェンの製造
JP2019510721A (ja) * 2016-03-22 2019-04-18 中国科学院金属研究所 酸化グラフェンナノプレートレット連続調製法
JP2021513750A (ja) * 2017-12-29 2021-05-27 シクソニア・テック・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 官能化された半導体−または導体材料の製造方法およびその使用
WO2020129427A1 (fr) * 2018-12-19 2020-06-25 株式会社カネカ Procédé de production d'une structure en forme de feuille mince de graphite, graphite exfolié et son procédé de production

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