US20170174521A1 - Graphite-based carbon material useful as graphene precursor, as well as method of producing the same - Google Patents

Graphite-based carbon material useful as graphene precursor, as well as method of producing the same Download PDF

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US20170174521A1
US20170174521A1 US14/651,630 US201514651630A US2017174521A1 US 20170174521 A1 US20170174521 A1 US 20170174521A1 US 201514651630 A US201514651630 A US 201514651630A US 2017174521 A1 US2017174521 A1 US 2017174521A1
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Prior art keywords
graphene
graphite
carbon material
based carbon
rate
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Shoji Hasegawa
Nagisa Kamiya
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Graphene Platform Corp
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Graphene Platform Corp
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=52823288&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20170174521(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Graphene Platform Corp filed Critical Graphene Platform Corp
Assigned to GRAPHENE PLATFORM CORPORATION reassignment GRAPHENE PLATFORM CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HASEGAWA, SHOJI, KAMIYA, NAGISA
Priority to US14/863,233 priority Critical patent/US9598593B2/en
Priority to US14/973,071 priority patent/US9428393B2/en
Priority to US14/973,100 priority patent/US9587134B2/en
Publication of US20170174521A1 publication Critical patent/US20170174521A1/en
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    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/022—Well-defined aliphatic compounds saturated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a graphite-based carbon material useful as a graphene precursor which makes it possible to obtain graphene by a simple method, as well as a method of producing the same.
  • graphene is superior to other carbon materials in aspect of mass productivity, handleability, etc., as well as performance, and expectations have been placed on graphene in various fields.
  • NPL 1 Structural Change of Graphite with Griding; authors: Michio INAGAKI, Hisae MUGISHIMA, and Kenji HOSOKAWA; Feb. 1, 1973 (Received)
  • NPL 2 Changes of Probabilities P1, PABA, PABC with Heat Treatment of Carbons; authors: Tokiti NODA, Masaaki IWATSUKI, and Michio INAGAKI; Sep. 16, 1966 (Received)
  • NPL 4 Classification of solid carbon materials and their structural characteristics; Nagoya Institute of Technology; Shinji KAWASAKI
  • Patent Literature 2 even by subjecting natural graphite to an ultrasonic treatment for a long time, only weak parts of the surface are exfoliated, other large parts do not contribute to the exfoliation, and it is considered as a problem that the amount of exfoliated graphene is small.
  • an object of the invention is to provide a graphite-based carbon material useful as such a araphene precursor, as well as a method of producing the same.
  • the graphite-based carbon material useful as a graphene precursor of the invention is characterized by having a rhombohedral graphite layer (3R) and a hexagonal graphite layer (2H), wherein a Rate (3R) of the rhombohedral graphite layer (3R) and the hexagonal graphite layer (2H), based on an X-ray diffraction method, which is defined by following Equation 1 is 31% or more:
  • P3 is a peak intensity of a (101) plane of the rhombohedral graphite layer (3R) based on the X-ray diffraction method
  • P4 is a peak intensity of a (101) plane of the hexagonal graphite layer (2H) based on the X-ray diffraction method.
  • a graphite-based carbon material useful as a graphene precursor from which graphene is easily exfoliated when the graphite-based carbon material is useful as a precursor, and which makes it possible to disperse graphene at a high concentration or to a high degree can be obtained.
  • the graphite-based carbon material useful as a graphene precursor of the invention is characterized in that the Rate (3R) is 40% or more.
  • the Rate (3R) is 40% or more
  • a graphite-based carbon material useful as a graphene precursor from which graphene is more easily exfoliated compared with cases where the Rate (3R) is 31% or more and less than 40%, can easily be obtained.
  • the graphite-based carbon material useful as a graphene precursor of the invention is characterized in that the Rate (3R) is 50% or more.
  • a graphite-based carbon material useful as a graphene precursor from which graphene is more easily exfoliated compared with cases where the Rate (3R) is 40% or more and less than 50%, can easily be obtained.
  • the graphite-based carbon material useful as a graphene precursor of the invention is characterized in that an intensity ratio P1/P2 of the hexagonal graphite layer (2H) based on the X-ray diffraction method is 0.01 or more, wherein
  • P1 is a peak intensity of a (100) plane of the hexagonal graphite layer (2H) based on the X-ray diffraction method
  • P2 is a peak intensity of a (002) plane of the hexagonal graphite layer (2H) based on the X-ray diffraction method.
  • the intensity ratio P1/P2 of the hexagonal graphite layer (2H) is made 0.01 or more, the orientation disorder of crystal structure of carbon material will be higher, graphene is easily exfoliated, and the graphite-based carbon material can be made to more effectively function as the precursor.
  • the above-described graphite-based carbon material useful as a graphene precursor is characterized in that the graphite-based carbon material is produced by carrying out a radiowave-force-based treatment and a physical-force-based treatment in a vacuum or in the air.
  • a treatment based on a radiowave force by microwaves, millimeter waves, plasma, electromagnetic induction heating (IH), magnetic fields or the like, and a treatment based on a physical force by a ball mill, jet mill, centrifugal force, supercriticality or the like, to a natural graphite material in a vacuum or in the air a graphite-based carbon material including more rhombohedral graphite layers (3R) is obtained.
  • the treatments are carried out in a vacuum or in the air, aftertreatments are simple.
  • a method of producing a graphite-based carbon material useful as a graphene precursor of the invention is characterized by including: carrying out a radiowave-force-based treatment and a physical-force-based treatment to a natural graphite material in a vacuum or in the air.
  • a graphite-based carbon material useful as a graphene precursor which more easily separates into graphene, compared with use of either one of the treatments, can be obtained in a short time.
  • a method of producing a graphite-based carbon material useful as a graphene precursor of the invention is characterized in that the above-described natural graphite material has at least a hexagonal graphite layer (2H), and an intensity ratio P1/P2 of the hexagonal graphite layer (2H) based on the X-ray diffraction method is less than 0.01, wherein
  • P1 is a peak intensity of a (100) plane of the hexagonal graphite layer (2H) based on the X-ray diffraction method
  • P2 is a peak intensity of a (002) plane of the hexagonal graphite layer (2H) based on the X-ray diffraction method.
  • the carbon material can be produced from easily-available natural graphite of which the orientation disorder of crystal structure of carbon material is lower and general.
  • the graphite-based carbon material of the invention is characterized by having a rhombohedral graphite layer (3R) and a hexagonal graphite layer (2H), wherein a Rate (3R) of the rhombohedral graphite layer (3R) and the hexagonal graphite layer (2H), based on an X-ray diffraction method, which is defined by following Equation 1 is 31% or more:
  • P3 is a peak intensity of a (101) plane of the rhombohedral graphite layer (3R) based on the X-ray diffraction method
  • P4 is a peak intensity of a (101) plane of the hexagonal graphite layer (2H) based on the X-ray diffraction method.
  • a graphene dispersion is characterized in that the graphene dispersion is obtained by carrying out a radiowave-force-based treatment and a physical-force-based treatment to the above-described graphite-based carbon material useful as a graphene precursor in a liquid.
  • heat acts on the graphite-based carbon material due to the radiowave force by microwaves, millimeter waves, plasma, electromagnetic induction heating (IH), magnetic fields or the like, and a physical force further acts thereon by a ball mill, a jet mill, a centrifugal force, supercriticality or the like. Therefore, by combining the radiowave-force-based treatment and the physical-force-based treatment, a large amount of graphene is easily exfoliated in a short time, a graphite-based carbon material from which graphene is not exfoliated and which remains in the liquid as a solvent is less, and graphene is highly dispersed therein. Consequently, a large amount of graphene can be dispersed in the liquid such as a solvent, and a concentrated graphene dispersion is obtained.
  • the graphene dispersion is characterized by containing at least 0.01 or more parts by weight of graphene.
  • the graphene when at least 0.01 or more parts by weight of graphene is present, the graphene has high dispersibility, and therefore, functions caused by dispersions of the graphene can sufficiently be exerted.
  • a graphene composite is characterized in that the graphene composite is obtained by mixing the above-described graphite-based carbon material useful as a graphene precursor or the above-described graphene dispersion with a composite base material, followed by kneading them while applying a shearing force to them.
  • the above-described graphite-based carbon material or the above-described graphene dispersion and the composite base material are kneaded while applying a sharing force to them, and therefore, graphene is easily exfoliated therefrom, and exfoliated graphene is highly dispersed therein. Consequently, a graphene composite, which can disperse a large amount of graphene in a composite base material such as monomers, polymers, other carbon materials, ceramics, wood, cements, or metals, is obtained.
  • the graphene composite is characterized in that a compatibilizer is used in kneading the graphene precursor or the graphene dispersion with the composite base material.
  • the graphene dispersion is characterized in that, when 0.1 part by weight of the above-described graphite-based carbon material useful as a graphene precursor is mixed with N-methylpyrrolidone (NMP), and an ultrasonic wave with an output of 100 W and with a frequency of 20 kHz is applied to the resulting mixture for 3 hours to thereby disperse graphene, 50% or more of an amount of graphene each having 10 layers or less are exposed relative to a total amount of all graphene and graphene precursors.
  • NMP N-methylpyrrolidone
  • a graphene dispersion in which graphene is dispersed at a high concentration or to a high degree, such that the amount of graphene each having 10 layers or less is 50% or more relative to a total amount of all graphene and graphene precursors, can be obtained.
  • a graphite-based carbon material useful as a graphene precursor is characterized in that the graphite-based carbon material used with kneading a composite base material.
  • a sharing force is applied to the graphite-based carbon material with kneading them, and therefore, graphene is easily exfoliated therefrom, and exfoliated graphene is highly dispersed therein. Consequently, a graphene composite, which can disperse a large amount of graphene in a composite base material such as monomers, polymers, other carbon materials, ceramics, wood, cements, or metals, is obtained.
  • the graphene in a composite base material is characterized in that the composite base material is a resin.
  • a resin molded article having a high degree dispersed graphene can be obtained.
  • a resin molded article having an excellent elastic modulus can be obtained.
  • FIG. 1 is a figure which shows a crystal structure of graphite, where (a) refers to a crystal structure of hexagonal crystals, and (b) refers to a crystal structure of rhombohedral crystals.
  • FIG. 2 is a diagram which shows an X-ray diffraction profile of general natural graphite.
  • FIG. 3 is a diagram which illustrates a production apparatus A using a jet mill and plasma of Example 1.
  • FIG. 4 is a figure which illustrates a production apparatus B using a ball mill and magnetron of Example 1, where (a) is a diagram which illustrates a pulverizing state, and (b) is a diagram which illustrates a state where graphite-based carbon materials (precursors) are collected.
  • FIG. 5 is a diagram which shows an X-ray diffraction profile of a graphite-based carbon material of Sample 5 produced by the production apparatus B according to Example 1.
  • FIG. 6 is a diagram which shows an X-ray diffraction profile of a graphite-based carbon material of Sample 6 produced by the production apparatus A according to Example 1.
  • FIG. 7 is a diagram which shows an X-ray diffraction profile of a graphite-based carbon material of Sample 1 indicating a comparative example.
  • FIG. 8 is a diagram which shows a dispersion-producing apparatus which produces a dispersion using a graphite-based carbon material as a precursor.
  • FIG. 9 is a diagram which shows dispersing states of dispersions produced by using graphite-based carbon materials of Sample 1 indicating a comparative example, and Sample 5 produced by the production apparatus B of Example 1.
  • FIG. 10 is a TEM image of a graphite-based carbon material (graphene) dispersed in a dispersion.
  • FIG. 11 is a figure which shows distribution states of a graphite-based carbon material dispersed in a dispersion which was produced using a graphite-based carbon material (precursor) of Sample 5, where (a) is a diagram which shows an average size distribution, while (b) is a diagram which shows a distribution of the number of layers.
  • FIG. 12 is a figure which shows a distribution state of a graphite-based carbon material dispersed in a dispersion which was produced using a graphite-based carbon material of Sample 1 indicating the comparative example, where (a) is a diagram showing an average size distribution, and (b) is a diagram showing a distribution of the number of layers.
  • FIG. 13 is a diagram which shows distributions of the number of layers of graphite-based carbon materials each dispersed in dispersions that were produced using Samples 1 to 7 as precursors.
  • FIG. 14 is a diagram which shows proportions of graphene having 10 layers or less to a content of rhombohedral crystals dispersed in a dispersion.
  • FIG. 15 is a figure which shows a distribution state of graphite when varying conditions for producing a dispersion using a graphite-based carbon material (precursor) of Sample 5 according to Example 2, where (a) is a diagram showing a distribution in a case where an ultrasonic treatment and a microwave treatment were combined, while (b) is a diagram showing a distribution of the number of layers in a case where an ultrasonic treatment was conducted.
  • FIG. 16 is a diagram which shows a resistance value when a graphite-based carbon material of Example 3 was dispersed in a conductive ink.
  • FIG. 17 is a diagram which shows a tensile strength when a graphite-based carbon material of Example 4 was kneaded with a resin.
  • FIG. 18 is a diagram which shows a tensile strength when a graphite-based carbon material of Example 5 was kneaded with a resin.
  • FIG. 19 is a diagram which shows dispersing states of graphite-based carbon materials of dispersions for describing dispersing states of Example 5 supplementary, where (a) is a dispersing state of sample 12, and (b) is a dispersing state of sample 2.
  • the invention focuses on a crystal structure of graphite, and, at first, matters relating to the crystal structure will be explained. It has been known that natural graphite is classified into three types of crystal structures, namely hexagonal crystals, rhombohedral crystals and disordered crystals, depending on an overlapping manner of layers. As shown in FIG. 1 , hexagonal crystals have a crystal structure in which layers are arranged in the order of ABABAB . . . , while rhombohedral crystals have a crystal structure in which layers are arranged in the order of ABCABCABC . . .
  • Non-Patent Literatures 1 and 2 In natural graphite, there are almost no rhombohedral crystals in a stage where natural graphite is excavated. However, about 14% of rhombohedral crystals exist in general natural graphite-based carbon materials because pulverization or the like is carried out in a purification stage. In addition, it has been known that a proportion of rhombohedral crystals converges on about 30% even when pulverization is carried out during purification for a long time (Non-Patent Literatures 1 and 2).
  • Non-Patent Literature 3 a proportion of rhombohedral crystals is about 25% (Non-Patent Literature 3). Furthermore, the proportion is up to about 30% even when heat of an extremely high temperature of 3000° C. is applied thereto (Non-Patent Literature 2).
  • the upper limit is about 30%.
  • An energy required for the exfoliation is inversely proportional to the cube of the thickness. Therefore, in a thick state where numerous layers are overlapped, graphene is exfoliated by a weak physical force such as by very feeble ultrasonic waves.
  • a very large energy is required. In other words, even if graphite is treated for a long time, only weak parts of the surface are exfoliated, and large parts remain not exfoliated.
  • the present inventors succeeded in increasing a proportion of rhombohedral crystals (3R), which had been increased to only about 30% by treatments of pulverization or heating to an extremely high temperature, to 30% or more by carrying out predetermined treatments, as shown below, to natural graphite.
  • the following findings were obtained as results of experiments and studies. That is, when a content of rhombohedral crystals (3R) in a graphite-based carbon material is higher, particularly when the content is 31% or more, there is a tendency that graphene is easily exfoliated by use of such a graphite-based carbon material as a precursor, thereby easily obtaining a highly concentrated and dispersed graphene dispersion or the like.
  • a graphite-based carbon material from which graphene is easily exfoliated by carrying out predetermined treatments to natural graphite, and which makes it possible to disperse graphene at a high concentration or to a high degree, is called a graphene precursor.
  • a method of producing a graphene precursor showing predetermined treatments, a crystal structure of the graphene precursor, and a graphene dispersion using the graphene precursor will be described in that order in examples below.
  • a graphene refers to a flake-like or sheet-like graphene which is a crystal of a mean size of 100 nm or more but which is not a fine crystal of a mean size of several nanometers to tens of nanometers, and which has 10 layers or less.
  • a graphene composite means a composite which is produced by using the graphite-based carbon material useful as a graphene precursor according to the invention, i.e. a graphite-based carbon material having a Rate (3R) of 31% or more (e.g. Samples 2-7 of Example 1, samples 21, . . . of Example 5 described below).
  • the production apparatus A refers to a case in which plasma is applied for the radiowave-force-based treatment and in which the jet mill is used for the physical-force-based treatment.
  • the symbol 1 refers to a particle of 5 mm or less of a natural graphite material (flaky graphite ACB-50 manufactured by Nippon Graphite Industries, ltd.);
  • the symbol 2 refers to a hopper which stores the natural graphite material 1 ;
  • the symbol 3 refers to a Venturi nozzle which discharges the natural graphite material 1 from the hopper 2 ;
  • the symbol 4 refers to a jet mill which jets the air which has been pumped from a compressor 5 , while being divided into eight places, to thereby allow the natural graphite material to collide against the inside of a chamber by a jet blast;
  • the symbol 7 refers to a plasma generator which sprays a gas 9 , such as oxygen, argon, nitrogen or hydrogen, through a nozzle 8 from a tank 6 and which applies a voltage to a coil 11 , wound around the outer periphery of the nozzle 8 , from a high-voltage power supply 10 , thereby generating
  • the symbol 13 refers to a pipe which connects the jet mill 4 and a dust collector 14 to one another; the symbol 14 refers to a dust collector; the symbol 15 refers to a collection container; the symbol 16 refers to a graphite-based carbon material (graphene precursor); and the symbol 17 refers to a blower.
  • the conditions for the jet mill are as follows.
  • Nozzle inner Diameter 12 mm
  • the conditions for plasma are as follows.
  • the natural graphite materials 1 which have been charged into the chamber of the jet mill 4 from the Venturi nozzle 3 , are accelerated to the sonic velocity or higher inside the chamber, and are pulverized by impact between the natural graphite materials 1 or by impact of them against the wall, and that, simultaneously, the plasma 12 discharges an electric current or excites the natural graphite materials 1 , acts directly on atoms (electrons), and increases deformations of crystals, thereby promoting the pulverization.
  • the production apparatus A in this example about 800 g of a graphene precursor from 1 kg of the raw materials, i.e. natural graphite materials 1 , is used.
  • the graphite-based carbon material (graphene precursors) 16 was obtained (recovery efficiency: about 80%).
  • the apparatus B refers to, as an example, a case where microwaves are applied as the radiowave-force-based treatment and where a ball mill is used for the physical-force-based treatment.
  • a natural graphite material flaky graphite ACB-50 manufactured by Nippon Graphite Industries, ltd.
  • the symbol 26 refers to a collection container
  • the symbol 27 refers to a filter
  • the symbol 28 refers to graphite-based carbon material (graphene precursors).
  • the conditions for the ball mill are as follows.
  • microwave generator microwave generator
  • the measurement conditions for the X-ray diffraction apparatus are as follows.
  • each sample shows peak intensities P1, P2, P3 and P4 in the planes (100), (002) and (101) of hexagonal crystals 2H and in the plane (101) of rhombohedral crystals 3R. Therefore, these peak intensities will be explained.
  • Sample 5 produced by the production apparatus B which applies a treatment with a ball mill and a microwave treatment, had high rates of peak intensities P3 and P1, and a Rate (3R) defined by Equation 1 showing a rate of P3 to a sum of P3 and P4 was 46%. Additionally, the intensity ratio P1/P2 was 0.012.
  • P1 is a peak intensity of a (100) plane of the hexagonal graphite layer (2H) based on the X-ray diffraction method
  • P2 is a peak intensity of a (002) plane of the hexagonal graphite layer (2H) based on the X-ray diffraction method
  • P3 is a peak intensity of a (101) plane of the rhombohedral graphite layer (3R) based on the X-ray diffraction method
  • P4 is a peak intensity of a (101) plane of the hexagonal graphite layer (2H) based on the X-ray diffraction method.
  • Sample 6 produced by the production apparatus A which applies a treatment based on the jet mill and a treatment based on plasma, had high rates of peak intensities P3 and P1, and the Rate (3R) was 51%.
  • the intensity ratio P1/P2 was 0.014.
  • Sample 1 indicating a comparative example produced with only the ball mill had a small rate of a peak intensity P3, compared with Samples 5 and 6, and the Rate (3R) was 23%.
  • the intensity ratio P1/P2 was 0.008.
  • Sample 5 produced by the production apparatus B of Example 1 and Sample 6 produced by the production apparatus A of Example 1 had Rates (3R) of 46% and 51%, respectively, and it was shown that their Rates (3R) were 40% or more, or 50% or more, compared with the natural graphite shown in FIG. 2 and Sample 1 indicating a comparative example.
  • graphene dispersions were produced using the above-produced graphene precursors, and their easiness in exfoliation of graphene was evaluated.
  • FIG. 8 shows, as an example, a case where an ultrasonic treatment and a microwave treatment are combined in a liquid when a graphene dispersion is produced.
  • FIG. 9 refers to appearances of graphene dispersions produced in the above-described way when 24 hours had passed.
  • the graphene dispersion produced in the above-described way was diluted to an observable concentration, was coated onto a sample stage (TEM grid), and the grid was dried.
  • TEM transmission electron microscope
  • the grid coated with the diluted supernatant was used for Sample 1.
  • the size corresponds to a maximum length L of a flake 33 , which was 600 nm, based on FIG. 10( a ) .
  • the number of layers the end face of the flake 33 was observed in FIG.
  • a particle size distribution (distribution of sizes) of thin flakes included in the graphene dispersion of Sample 5 (Rate (R3) of 46%) produced by the production apparatus B of Example 1 was a distribution having a peak of 0.5 ⁇ m.
  • a distribution which had a peak in 3 layers and in which graphene having 10 layers or less were 68% was observed.
  • a particle size distribution (distribution of sizes) of thin flakes included in the dispersion of Sample 1 (Rate (R3) of 23%) of the comparative example was a distribution having a peak of 0.9 ⁇ m.
  • a distribution in which those having 30 layers or more occupied the greater portion and in which graphene having 10 layers or less were 10% was observed.
  • Samples 1, 5 and 6 in FIG. 13 are those described above.
  • Samples 2, 3 and 4 were produced by the production apparatus B which carried out a treatment based on a ball mill and a microwave treatment, and were graphene dispersions produced using graphene precursors which had been produced by making the irradiating time of microwaves shorter than that for Sample 5.
  • Sample 7 was produced by the production apparatus A which carried out a treatment based on a jet mill and a plasma treatment, and was a graphene dispersion produced by using a graphene precursor which had been produced by applying plasma of a higher output than that for Sample 6.
  • the Rate (3R) is preferably 40% or more from a view point that the proportion of dispersed graphene of 10 layers or less sharply increases to 50% or more.
  • an upper limit for the Rate (3R) is considered that the upper limit is not particularly defined. However, it is preferable that the upper limit is defined such that the intensity ratio P1/P2 simultaneously satisfies 0.01 or more, because graphene precursors are easily exfoliated when a dispersion or the like is produced. In addition, in cases of production methods using production apparatuses A and B, the upper limit is about 70%, from a viewpoint that graphene is easily produced. Also, a method combining a treatment based on the jet mill of the production apparatus A and a plasma treatment is more preferable, because a graphene precursor having a higher Rate (3R) can easily be obtained. Additionally, the Rate (3R) as long as it reaches 31% or more by combining the physical-force-based treatment and the radiowave-force-based treatment.
  • Example 1 a case where the ultrasonic treatment and the microwave treatment were combined for obtaining a graphene dispersion is explained.
  • Example 2 only an ultrasonic treatment was carried out while a microwave treatment was not carried out, and other conditions were the same as those for Example 1.
  • FIG. 15( a ) is the same as the distribution shown in FIG. 11( b ) of Sample 5 produced by the production apparatus B of Example 1.
  • Example 3 an example used for a conductive ink will be described.
  • Example 4 an example in which a graphene precursor was kneaded with a resin will be explained.
  • LLDPE polyethylene
  • Zinc stearate is explained above as an example of the dispersing agent. However, those suited for compounds may be selected. As examples of the dispersing agent, anionic (anion) surfactants, cationic (cation) surfactants, zwitterionic surfactants, and nonionic surfactants can be mentioned. In particular, anion surfactants and nonionic surfactants are preferable for graphene. Nonionic surfactants are more preferable.
  • nonionic surfactants are surfactants which do not dissociate into ions and which show hydrophilic properties by hydrogen bonds with water, as observed in oxyethylene groups, hydroxyl groups, carbohydrate chains such as glucoside, and the like, there is a merit that they can be used in nonpolar solvents, although they do not have a strength of hydrophilicity as high as ionic surfactants. Further, this is because, by varying chain lengths of their hydrophilic groups, their properties can freely be changed from lipophilic properties to hydrophilic properties.
  • anionic surfactants X acid salts (as for the X acid, for example, cholic acid, and deoxycholic acid), for example, SDC: sodium deoxycholate, and phosphate esters, are preferable.
  • nonionic surfactants glycerol fatty acid esters, sorbitan fatty acid esters, fatty alcohol ethoxylates, polyoxyethylene alkyl phenyl ether, alkyl glycosides, and the like are preferable.
  • the production apparatus A using a jet mill and plasma, and the production apparatus B using a ball mill and microwaves are described as production apparatuses which produce a graphene precursor.
  • a treatment based on a radiowave force such as by microwaves, millimeter waves, plasma, electromagnetic induction heating (IH), and magnetic fields
  • a treatment based on a physical force such as by a ball mill, a jet mill, centrifugal force, and supercriticality
  • a precursor having a high Rate (R3) can be obtained. Therefore, such combination of the treatments is preferable.
  • any specific treatments for the physical-force-based treatment and the radiowave-force-based treatment can be adopted.
  • effects based on a radiowave force and a physical force are simultaneously directed thereto.
  • a radiowave force and a physical force may alternately be directed thereto at predetermined intervals.
  • different radiowave forces such as treatments based on microwaves and plasma, may alternately be applied thereto, and, parallel with the treatments, treatments based on one or more physical forces may be carried out.
  • different physical forces such as treatments based on a jet mill and supercriticality, may alternately be applied thereto, and, parallel with the treatments, treatments based on one or more radiowave forces may be carried out.
  • the pellets produced in (2) were formed into a test piece according to JIS K7161 1A (length: 165 mm, width: 20 mm, thickness: 4 mm) by an injection molding machine.
  • the elastic modulus (Mpa) of the test piece produced in (3) was measured under a condition of a test speed of 500 mm/min according to JIS K7161 by a table-top type precision universal tester produced by Shimadzu Corporation (AUTOGRAPH AGS-J).
  • the kneading conditions were as follows.
  • Pressurization in furnace applying 0.3 MPa for 10 minutes after start, and depressurizing to atmospheric pressure after the 10 minutes elapsed
  • the dispersion of the above-described graphene dispersion into a resin is considered as follows.
  • the melting point of a resin is generally 100° C. or higher, water evaporates in atmosphere, but in a pressing-type kneader, the inside of a furnace can be pressurized. In the inside of the furnace, the boiling point of water is raised so that the dispersion is kept in a liquid form, whereby an emulsion of the dispersion and the resin can be obtained.
  • the inside After applying pressure for a predetermined time, the inside is gradually depressurized, which causes the boiling point of water to decrease, thereby allowing water to evaporate.
  • graphene confined in water are left in the resin. This causes graphene and graphite-based carbon materials to be dispersed at a high concentration in the resin.
  • the graphene dispersion is kneaded into the resin preferably immediately after the graphene dispersion is obtained.
  • the following may be used as the means for obtaining the emulsion of the dispersion and the resin, other than the pressing kneader: a chemical thruster; a vortex mixer; a homomixer; a high-pressure homogenizer; a hydroshear; a flow jet mixer; a wet jet mill; and an ultrasonic generator.
  • IPA 2-propanol
  • NMP N-methylpyrrolidone
  • DMF N,N-dimethyl formamide
  • Table 4 illustrates the relationship between the Rates (3R) of around 30% and the elastic moduli of resin molded articles. It should be noted that Sample 00 in Table 4 is a blank Sample in which no precursor was kneaded, Samples 11 and 12 have Rates (3R) between that of Sample 1 and that of Sample 2, and Sample 21 has a Rate (3R) between that of Sample 2 and that of Sample 3.
  • Example 5 clearly indicates that when the Rate (3R) is 31% or more, a graphite-based carbon material used as a graphene precursor tends to be separated into graphene having 10 or less layers and a thin graphite-based carbon material.
  • the production apparatus using microwaves and ultrasonic waves is described as a production apparatus for obtaining a graphene dispersion using a precursor.
  • a treatment based on a radiowave force such as by microwaves, millimeter waves, plasma, electromagnetic induction heating (IH) and magnetic fields
  • a treatment based on a physical force such as by ultrasonic waves, a ball mill, a jet mill, centrifugal force, and supercriticality
  • a graphene dispersion having a high graphene concentration can be obtained. Therefore, such combination of the treatments is preferable.
  • effects based on a radiowave force and a physical force are simultaneously directed thereto.
  • a radiowave force and a physical force may alternately be directed thereto at predetermined intervals.
  • the production apparatus using microwaves and ultrasonic waves is described as a production apparatus for obtaining a graphene dispersion using a precursor.
  • a treatment based on a radiowave force such as by microwaves, millimeter waves, plasma, electromagnetic induction heating (IH) and magnetic fields
  • a treatment based on a physical force such as by ultrasonic waves, a ball mill, a jet mill, centrifugal force, and supercriticality
  • a graphene dispersion having a high graphene concentration can be obtained. Therefore, such combination of the treatments is preferable.
  • effects based on a radiowave force and a physical force are simultaneously directed thereto.
  • a radiowave force and a physical force may alternately be directed thereto at predetermined intervals.
  • graphene dispersions, conductive inks and resin molded articles are described as applications using precursors.
  • precursors by mixing, as base materials, precursors into composite base materials such as monomers, polymers, other carbon materials, ceramics, woods, cements or metals, graphene composite may be obtained. That is, in the present specification, a graphene composite means products encompassing the above-described graphene dispersions, conductive inks and resin molded articles. Additionally, a graphene dispersion encompasses paste products with high viscosities.
  • Resins includes polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), ABS resins (ABS), acrylic resins (PMMA), polyamide/nylon (PA), polyacetal (POM), polycarbonate (PC), polyethylene terephthalate (PET), cyclic polyolefins (COP), polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), polysulfones (PSF), polyamide-imide (PAI), thermoplastic polyimide (PI), polyether ether ketone (PEEK), and liquid-crystal polymers (LCP).
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • PVC polyvinyl chloride
  • ABS resins ABS resins
  • acrylic resins PMMA
  • PA polyamide/nylon
  • PA polyacetal
  • PC polycarbonate
  • PET polyethylene terephthalate
  • COP cyclic poly
  • thermosetting resins thermoplastic resins such as epoxy resins (EP), phenolic resins (PF), melamine resins (MF), polyurethanes (PUR) and unsaturated polyester resins (UP) can be mentioned; fibrous nylon, and fibers of polyester, acryl, vinylon, polyolefin, polyurethane, rayon or the like can be mentioned; as elastomers, isoprene rubbers (IR), butadiene rubbers (BR), styrene/butadiene rubbers (SBR), chloroprene rubbers (CR), nitrile rubbers (NBR), polyisobutylene rubbers/butyl rubbers (IIR), ethylene propylene rubbers (EPM/EPDM), chlorosulfonated polyethylene (CSM), acrylic rubbers (ACM), epichlorohydrin rubbers (CO/ECO), and the like can be mentioned; as thermosetting resin-based elastomers, some urethane rubbers (IR), butadiene rubbers (
  • mineral oils lubricating oils, and greases
  • compounded oils for rubbers paraffin-based mineral oils, naphthenic mineral oil, aromatic mineral oils, and the like can be mentioned.
  • nonpolar products hexane, benzene, toluene, chloroform, ethyl acetate, and the like can be mentioned;
  • polar aprotic products acetone, N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), acetonitrile, and the like can be mentioned;
  • polar protic products acetic acid, ethanol, methanol, water, 1-butanol, 2-propanol, formic acid, and the like can be mentioned.
  • natural graphite for producing a graphite-based carbon material useful as a graphene precursor particles of 5 mm or less of a natural graphite material (flaky graphite ACE-50 manufactured by Nippon Graphite Industries, ltd.) is described above.
  • a natural graphite material flaky graphite ACE-50 manufactured by Nippon Graphite Industries, ltd.
  • products which are flaky graphite, being pulverized into 5 mm or less, and which have a Rate (3R) of less than 25% and an intensity ratio Pl/P2 of less than 0.01 are preferable, from a viewpoint that they are easily-available.
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US9428393B2 (en) 2016-08-30
KR101600837B1 (ko) 2016-03-10
EP3002322B1 (en) 2019-08-07
CL2017000568A1 (es) 2017-11-03
EP2993219A4 (en) 2016-04-06

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