WO2017110295A1 - Procédé de fabrication d'un matériau composite à base d'une substance bidimensionnelle et d'une substance fibreuse - Google Patents

Procédé de fabrication d'un matériau composite à base d'une substance bidimensionnelle et d'une substance fibreuse Download PDF

Info

Publication number
WO2017110295A1
WO2017110295A1 PCT/JP2016/083540 JP2016083540W WO2017110295A1 WO 2017110295 A1 WO2017110295 A1 WO 2017110295A1 JP 2016083540 W JP2016083540 W JP 2016083540W WO 2017110295 A1 WO2017110295 A1 WO 2017110295A1
Authority
WO
WIPO (PCT)
Prior art keywords
substance
dimensional
fibrous
composite material
composite
Prior art date
Application number
PCT/JP2016/083540
Other languages
English (en)
Japanese (ja)
Inventor
捷 唐
坤 張
ジン リー
松葉　頼重
畑　憲明
Original Assignee
国立研究開発法人物質・材料研究機構
ハリマ化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立研究開発法人物質・材料研究機構, ハリマ化成株式会社 filed Critical 国立研究開発法人物質・材料研究機構
Priority to JP2017557786A priority Critical patent/JP6573262B2/ja
Publication of WO2017110295A1 publication Critical patent/WO2017110295A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes

Definitions

  • the present invention relates to a method for producing a composite material of a two-dimensional substance and a fibrous substance.
  • the two-dimensional material is generally a single-layer or thin-layer solid in which atoms have a predetermined crystal structure, and graphene is known as a representative two-dimensional material.
  • Graphene is a single layer (monoatomic layer) structure in which carbon atoms form a hexagonal structure, and forms the basic structure of a layered structure of graphite (graphite).
  • Patent Document 1 a graphene derivative-carbon nanotube composite material containing graphene oxide and carbon nanotubes in a predetermined ratio has been proposed (Patent Document 1).
  • Patent Document 1 a graphene oxide prepared by ultrasonically treating graphite oxide obtained by oxidizing graphite is added to an alcohol dispersant together with carbon nanotubes, and a suspension obtained by performing ultrasonic dispersion for 120 to 150 minutes is used.
  • the target composite material is produced by filtering and drying.
  • the apparatus is originally assumed to homogenize the raw material while crushing it to a smaller particle size by combining the impact force and the grinding force into the raw material solution.
  • the configuration is designed.
  • the conventional high-pressure emulsification apparatus including the high-pressure homogenizer described in Patent Document 2 and the high-pressure emulsifier described in Patent Document 3 has a pressure generator (pump unit) and a portion in which the flow path is significantly narrowed. Parts (for example, nozzles and orifices, hereinafter also referred to as “nozzle portions”) are included, and these are essential components for performing the high-pressure emulsification method.
  • the pressure from the pump unit is converted into a jet flow at the nozzle unit, and the liquid ejected from the nozzle unit becomes a turbulent flow while passing through a member called an absorption cell, and an impact force or shear force is applied. Therefore, when the high-pressure emulsification method is applied to a two-dimensional substance such as graphene using such a conventional high-pressure emulsification apparatus, the two-dimensional structure is destroyed by applying an impact force in the plane direction.
  • the particle size in the plane direction becomes small flakes or fragments having a size of about several ⁇ m, and as a result, there may be a case where excellent properties that a two-dimensional substance can originally exhibit cannot be obtained.
  • the present invention has been made in view of the circumstances as described above, and combines a two-dimensional substance and a fibrous substance while suppressing the destruction and cutting of the characteristic structures of the two-dimensional substance and the fibrous substance. It is an object of the present invention to provide a method for producing a composite material of a two-dimensional material and a fibrous material, which can be used for industrial mass production.
  • the present inventors have found that a process in which a jet flow is generated by the operation of feeding the raw material solution to the nozzle part, which is an essential component in the conventional high-pressure emulsification apparatus.
  • a process in which a jet flow is generated by the operation of feeding the raw material solution to the nozzle part which is an essential component in the conventional high-pressure emulsification apparatus.
  • the conditions for generating the jet flow are not necessarily appropriate from the viewpoint of combining the two-dimensional substance and the fibrous substance.
  • the jet flow generated by the liquid passing operation to the nozzle part may cause destruction or cutting of the characteristic structure of the two-dimensional substance and the fibrous substance.
  • the present inventors have improved the method to be more suitable for the combination of the two-dimensional material and the fibrous material while taking advantage of the characteristics of the conventional high-pressure emulsification method, thereby achieving higher accuracy than the conventional method. It has been found that a composite material in which a fibrous substance is inserted between two-dimensional substance layers can be obtained with high yield.
  • this invention includes the following aspects.
  • (1) A step in which a suspension obtained by suspending a two-dimensional substance and a fibrous substance in a dispersion medium is subjected to high pressure treatment and supplied from a raw material introduction unit, and the suspension supplied from the raw material introduction unit is combined. Passing through the module to obtain a dispersion of the composite material in which the fibrous material is inserted between the layers of the two-dimensional material in the dispersion medium, and dispersing the composite material after passing through the composite module
  • a method for producing a composite material of a two-dimensional substance and a fibrous substance including a step of recovering a liquid in a recovery part, wherein the raw material introduction part and the composite module have an inner diameter of a liquid passage through which the suspension flows.
  • a method for producing a composite material of a two-dimensional substance and a fibrous substance characterized by not having a liquid passage having an inner diameter of 0.15 mm or more and an inner diameter of less than 0.15 mm.
  • (3) The composite module has a structure in which two or more liquid passing members are connected in series, and is downstream of the inner diameter of the liquid passing path of the upstream liquid passing member with respect to the flow of the suspension.
  • the method further comprises a step of supplying again the dispersion liquid of the composite material recovered by the recovery unit to the raw material introduction unit and allowing the composite module to pass through.
  • the two-dimensional material and the fibrous material can be combined while suppressing the destruction and cutting of the characteristic structure of the two-dimensional material and the fibrous material, which is suitable for industrial mass production.
  • a method for producing a composite material of a two-dimensional material and a fibrous material is provided.
  • the schematic diagram which shows the manufacturing apparatus of the composite material of the two-dimensional substance and fibrous substance which concerns on one Embodiment of this invention
  • SEM image of TRGO-SGCNT composite material obtained in Example 1 SEM image of TRGO-SGCNT composite material obtained in Example 2
  • SEM image of TRGO-SGCNT composite material obtained in Example 3 Graph showing charge / discharge characteristics of comparative capacitors (Comparative Cell 1 and Comparative Cell 2) produced in Examples 1 to 3
  • the “two-dimensional substance” refers to a single-layer or thin-layer solid in which atoms have a predetermined crystal structure.
  • the two-dimensional material include molybdenum (IV) (MoS 2 ), boron nitride (BN), and the like in addition to graphene, which is a representative example.
  • fibrous substance refers to a substance whose length is 100 times or more the average value of the outer diameter.
  • fibrous material include nanofibers having a nanoscale whose average outer diameter is in the range of 1 nm to 100 nm.
  • nanofiber include a nanotube having a hollow structure, a nanorod having no hollow structure, and a nanowire having a conductive or semiconductive property. More specifically, examples of nanofibers used in the present embodiment include carbon nanotubes, cellulose nanofibers, and metal nanowires.
  • the average particle size in the plane direction of the two-dimensional material is not particularly limited, but from the viewpoint of obtaining the effect of combining with the fibrous material with higher accuracy, the average particle size in the plane direction of the two-dimensional material. Is preferably 200 ⁇ m or less, and more preferably, the average particle size in the plane direction of the two-dimensional substance is 100 ⁇ m or less. Even if the average particle size in the plane direction of the two-dimensional material is 200 ⁇ m or more, the composite effect according to the present embodiment can be obtained.
  • the method for producing graphene used in the present embodiment as a two-dimensional material is not particularly limited, and graphene produced according to a generally known method can be used.
  • a method for producing graphene a method of exfoliating graphite is generally used, and a typical example is a method of exfoliating graphite oxide oxidized under strong oxidation conditions (Hammers method).
  • a method for producing graphene that does not require a strong oxidation treatment step for example, ultrasonically treating a graphite dispersion solution, inserting a stirring blade or the like into the graphite dispersion solution, and rotating the graphite at high speed, A method of delamination is known.
  • the average value of the outer diameter of the fibrous substance is not particularly limited, but from the viewpoint of more efficiently combining with the two-dimensional substance, the average value of the outer diameter is 0.4 to 5.0 nm. Is preferably considered, and more preferably in the range of 1.0 to 3.0 nm.
  • the average value of the outer diameter of the fibrous material is observed with an arbitrary magnification using, for example, a transmission electron microscope, and a plurality of fibrous materials arbitrarily extracted from a visual field in which a certain proportion of the visual field area is the fibrous material. It can be an arithmetic average value when the outer diameter of the substance is measured.
  • the carbon nanotubes used in the present embodiment as the fibrous material are aggregates in which a plurality of carbon nanotubes are present, and the form of the carbon nanotubes is not particularly limited, and each may exist independently or a bundle. May exist in a form such as a shape, entanglement, or a mixed form thereof. Various layers and outer diameters may be included.
  • the method for producing the carbon nanotubes used in the present embodiment is not particularly limited, and is produced according to a generally known method such as a chemical vapor deposition (CVD) method, a super growth (SG) method, a laser ablation method, or an arc discharge method. Carbon nanotubes can be used.
  • CVD chemical vapor deposition
  • SG super growth
  • laser ablation method or an arc discharge method.
  • Carbon nanotubes can be used.
  • the purity of the carbon nanotube is not particularly limited, but in this embodiment, even when a higher purity carbon nanotube (for example, purity> 99.5%, purity> 99.98%) is used, A composite material in which carbon nanotubes are inserted between layers of a two-dimensional substance can be obtained while suppressing damage.
  • a higher purity carbon nanotube for example, purity> 99.5%, purity> 99.98%
  • a dispersion medium used for preparing a suspension of a two-dimensional substance and a fibrous substance can be appropriately selected.
  • examples include alcohols, amides such as dimethylformamide, N-methyl-2-pyrrolidone (NMP), and mixed solvents thereof.
  • the dispersion medium is, for example, dodecylbenzene, for the purpose of more uniformly dispersing in consideration of the affinity between the two-dimensional substance and the fibrous substance and the dispersion medium within a range not inhibiting the purpose and effect of the present invention.
  • Sodium sulfonate, sodium dodecyl sulfate, sodium cholate, sodium deoxycholate and the like may be added as a dispersant, and other additives may be added according to the required purpose.
  • the target composite material is a composite material of graphene and carbon nanotubes, in principle, it is not necessary to add an additive such as a dispersant to the dispersion medium.
  • the concentration of the two-dimensional substance in the raw material suspension is not particularly limited, and is, for example, 0.1 to 100 mg / mL, preferably 0.5 to 50 mg / mL, more preferably 1 to 10 mg / mL. .
  • concentration of the two-dimensional substance is within the above range, the effect of combining with the fibrous substance in the dispersion medium can be obtained more efficiently.
  • concentration of the two-dimensional substance exceeds 100 mg / mL, the efficiency of complexing with the fibrous substance may be inferior.
  • the concentration of the fibrous substance in the raw material suspension is not particularly limited, but is, for example, 0.01 to 5.0 mg / mL, preferably 0.05 to 1.0 mg / mL, more preferably 0.1 ⁇ 0.5 mg / mL.
  • concentration of the fibrous substance is within the above range, the complexing effect with the two-dimensional substance in the dispersion medium can be obtained more efficiently.
  • concentration of a fibrous substance exceeds 5.0 mg / mL, the compounding efficiency with a two-dimensional substance may be inferior.
  • the mass ratio of the two-dimensional substance and the fibrous substance in the raw material suspension is not particularly limited.
  • the mass ratio of the two-dimensional substance and the fibrous substance is within the above range, the composite effect of the two-dimensional substance and the fibrous substance in the dispersion medium can be obtained more efficiently, and the composite material can be obtained more efficiently. High yield can be obtained.
  • the composite apparatus according to the present embodiment has a configuration without the nozzle part as described later. Therefore, even when the viscosity of the raw material suspension is high, the target composite material can be obtained by combining the two-dimensional substance and the fibrous substance.
  • the fibrous material may be suspended together with the two-dimensional material in the dispersion medium without performing any special pretreatment, and may be used as a raw material suspension.
  • a dispersion of a fibrous substance that has been dispersed may be mixed with a suspension in which a two-dimensional substance or a two-dimensional substance is suspended to form a raw material suspension.
  • a carbon nanotube dispersion liquid dispersed in a desired dispersion medium can be used.
  • the raw material suspension can be prepared by adding graphene as a two-dimensional substance to the carbon nanotube dispersion.
  • FIG. 1 is a schematic diagram showing an apparatus for producing a composite material of a two-dimensional substance and a fibrous substance (hereinafter also referred to as “compositing apparatus”) according to an embodiment of the present invention.
  • the compounding apparatus 1 includes a raw material introduction unit 2, a compounding module 3, and a recovery unit 4 as main components.
  • the method for producing a composite material of a two-dimensional substance and a fibrous substance according to this embodiment performed using such a compounding apparatus 1 is a suspension in which a two-dimensional substance and a fibrous substance are suspended in a dispersion medium.
  • the high pressure treatment and supplying from the raw material introduction unit 2, the suspension supplied from the raw material introduction unit 2 is passed through the composite module 3, and the fibrous material is formed between the layers of the two-dimensional material in the dispersion medium.
  • a suspension obtained by suspending a two-dimensional substance and a fibrous substance in a dispersion medium is subjected to high pressure treatment and supplied to the composite module 3. More specifically, in the raw material introduction unit 2, as shown in FIG. 1, the raw material suspension stored in the solution tank 21 is subjected to high pressure treatment by the high pressure pump 22 and supplied to the composite module 3.
  • the pressure applied to the raw material suspension by the high-pressure pump 22 is the average particle size in the surface direction of the two-dimensional material, the average value of the outer diameter of the fibrous material, the concentration of the two-dimensional material and the fibrous material in the raw material suspension, It can be set as appropriate according to the intended use of the composite material.
  • the pressure is, for example, 5 to 150 MPa, preferably 10 to 125 MPa, and more preferably 20 to 100 MPa.
  • the pressure may be adjusted within the above range each time.
  • the molecules of the dispersion medium are aggregated between the layers of the two-dimensional material and the fibrous materials to form a bundle structure.
  • the force penetrating the dispersion medium molecules exceeds the force acting between the layers of the two-dimensional material and the fibrous material (for example, van der Waals force)
  • the dispersion medium molecules move between the layers of the two-dimensional material.
  • the bundle structure of the fibrous material can be successively inserted (intercalated).
  • the raw material suspension supplied from the raw material introduction unit 2 is passed, and the fibrous material is inserted between the layers of the two-dimensional material.
  • the composite module 3 has a structure in which two or more liquid passing members are connected in series.
  • the composite module 3 includes three liquid passing members 31, 32, and 33. The form which has the structure connected in series is illustrated.
  • liquid passing members 31, 32, 33 for example, straight tubes, spiral tubes and the like used as absorption cells in conventional high-pressure emulsification apparatuses can be applied.
  • the inner diameter is configured to be large. That is, when the inner diameters of the liquid passages of the liquid passage members 31, 32, and 33 are D31, D32, and D33, respectively, the relationship of D31 ⁇ D32 ⁇ D33 is established.
  • the lengths of the fluid-permeable members 31, 32, 33 are appropriately determined according to the average particle size in the plane direction of the two-dimensional substance, the concentration of the two-dimensional substance and the fibrous substance in the raw material suspension, the intended use of the composite material, and the like Can be set.
  • the two-dimensional material is graphene, for example, a range of 5 to 100 cm can be used as a rough standard.
  • the lengths of the liquid passing members 31, 32, and 33 are preferably considered as appropriate depending on the liquid passing time and the number of times of passing through which will be described later.
  • Table 1 below shows an example of the configuration of the composite module 3.
  • the inner diameter of the flow path through which the raw material suspension flows is 0.15 mm or more, preferably in the range of 0.15 mm to 1 mm.
  • the raw material introduction part 2 and the composite module 3 do not have a liquid passage having an inner diameter of less than 0.15 mm. That is, in the compounding apparatus 1 according to the present embodiment, it is not intended with respect to the surface direction of the two-dimensional substance by adopting a configuration that does not have the nozzle part that is an essential component in the conventional high-pressure emulsification apparatus. The application of an impact force is suppressed, and further, the application of an unintended impact force in the length direction of the fibrous material is also suppressed.
  • a shearing force is applied according to the fluid dynamics.
  • This shear force acts on the gap formed between the layers of the two-dimensional material and the gap formed between the bundle structures of the fibrous material in the above-described high-pressure treatment process, and thereby the interlayer of the two-dimensional material and the fibrous material.
  • the interaction that is working between is further weakened.
  • the two-dimensional material is dispersed in the dispersion medium as a single-layer or several-layer flake-like structure, and is stabilized by the rapid adsorption of the dispersion medium molecules on the surface. Thus, lamination is suppressed.
  • one or several fibrous substances are dispersed in the dispersion medium such that the fibrous substances are lifted and unraveled from the aggregate formed by aggregating the fibrous substances.
  • the dispersed fibrous material is stabilized by quickly adsorbing the dispersion medium molecules on the surface thereof, and the fibrous materials are prevented from aggregating again to form a bundle structure.
  • the fibrous material is inserted between the layers of the two-dimensional material to generate a composite material. More specifically, the fibrous substance is inserted into a mesopore (gap) formed by sandwiching a fibrous substance between two layers of a single layer or between several layers of two-dimensional substances. As a result, the two-dimensional material and the fibrous material are combined.
  • a mesopore mesopore
  • the two-dimensional substance is obtained by continuously performing the high-pressure treatment process of the raw material suspension and the subsequent composite process.
  • the fibrous material is efficiently inserted between the layers, and the target composite material can be obtained in high yield.
  • the flow rate of the raw material suspension when passing through the composite module 3 is the average particle size in the surface direction of the two-dimensional material, the average value of the outer diameter of the fibrous material, the two-dimensional material and the fibrous material in the raw material suspension.
  • the concentration can be appropriately set according to the intended use of the composite material.
  • it is preferable to consider that the speed of the raw material suspension when passing through the composite module 3 is appropriately adjusted according to the liquid passing time and the number of times of liquid passing described later.
  • the composite module 3 since a large shearing force is applied to the raw material suspension, the temperature of the suspension may rise during the flow of liquid. Therefore, the composite module 3 can be cooled by the cooling means 34 for the purpose of preventing deterioration and peeling due to excessive heating of the raw materials, preventing the suspension from boiling in the recovery unit 4, and the like.
  • the recovery unit 4 recovers the dispersion liquid of the composite material after passing through the composite module 3.
  • the recovered dispersion can be taken out and used as it is as a dispersion of the desired composite material, and can be made to a desired concentration by diluting or concentrating. Further, the two-dimensional substance and fibrous substance of the raw material remaining in the recovered raw material suspension can be removed by a generally known separation method such as centrifugation. Moreover, the target composite material can be obtained by drying the recovered dispersion after solid-liquid separation by filtration or centrifugation, and the like.
  • the composite material dispersion recovered by the recovery unit 4 can be supplied again to the raw material introduction unit 2 and allowed to pass through the composite module 3. In this way, by passing the composite module 3 a plurality of times, the composite accuracy of inserting and combining the fibrous substance between the layers of the two-dimensional substance is further improved, and the target composite material can be obtained at a higher yield. Obtainable.
  • the compounding apparatus 1 since the compounding apparatus 1 according to the present embodiment has a configuration that does not include the nozzle portion, even if the raw material suspension is passed through the compounding module 3 multiple times, The two-dimensional substance and the fibrous substance can be combined while suppressing an unintended impact force from being applied to the surface direction of the two-dimensional substance of the two-dimensional substance and the length direction of the fibrous substance.
  • the time for passing the raw material suspension through the composite module 3, that is, the time for performing the composite process (liquid passing time) is the average particle size in the surface direction of the two-dimensional material, the two-dimensional material and fiber in the raw material suspension. It can be set as appropriate according to the concentration of the substance, the intended use of the composite material, and the like.
  • the two-dimensional material is graphene, it is, for example, 15 seconds to 180 minutes, preferably 30 seconds to 150 minutes, and more preferably 1 to 120 minutes. It is understood that the number of times of performing the compounding step (number of times of liquid passing) is appropriately adjusted with the liquid passing time.
  • a fibrous substance for example, carbon
  • layers of the two-dimensional substance for example, graphene
  • the two-dimensional substance has suppressed the destruction of the two-dimensional structure in the plane direction, and the damage and cutting of the fibrous substance are suppressed. Therefore, for example, when graphene is used as the two-dimensional material and carbon nanotubes are used as the fibrous material, the electrical conductivity, transparency, mechanical properties, etc. inherent to the composite graphene and carbon nanotubes, etc. Is expected to be applied more effectively, and is expected to be applied as electronic materials such as transparent electrodes, wiring materials, and capacitor members that realize high-speed charging, high output, and large capacity.
  • the manufacturing method and composite device 1 of the composite material of the two-dimensional substance and the fibrous substance according to the present embodiment are limited to the case where graphene is used as the two-dimensional substance and the case where the carbon nanotube is used as the fibrous substance. It can be applied to other two-dimensional materials and fibrous materials.
  • the various conditions described above can be appropriately designed in accordance with the types and properties of the two-dimensional material and the fibrous material used.
  • SGCNT thermally reduced graphene oxide
  • TRGO used in the present Example was produced as follows. First, graphene oxide obtained by oxidizing a commercially available graphite (manufactured by Shin-Etsu Chemical Co., Ltd., scaly graphite BF-5A) is dispersed in water at a concentration of 2 mg / mL, and the solvent is freeze-dried (freeze-dried). A uniform graphene oxide foam was obtained. Next, this graphene oxide foam was thermally reduced at 400 ° C. for 1 minute to obtain TRGO.
  • a commercially available graphite manufactured by Shin-Etsu Chemical Co., Ltd., scaly graphite BF-5A
  • a uniform graphene oxide foam was obtained.
  • this graphene oxide foam was thermally reduced at 400 ° C. for 1 minute to obtain TRGO.
  • FIGS. 2 to 4 The SEM observation results of the composite materials obtained in Examples 1 to 3 are shown in FIGS. 2 to 4, respectively.
  • a sample for SEM observation was prepared by dropping several mL of a dispersion of a composite material on a Si wafer. SEM observation was performed using a field emission scanning electron microscope (FE-SEM, JSM-6500, JEOL).
  • FE-SEM field emission scanning electron microscope
  • the composite material and poly (tetrafluoroethylene) (PTFE) were mixed in NMP at a mass ratio of 90:10. Next, this solution was subjected to suction filtration on a porous membrane (Hydrophilic, 0.2 ⁇ m PTFE) to form an electrode membrane. This electrode film was vacuum-dried at 25 ° C. for 24 hours and then cut to a diameter of 15 mm to produce an electrode having a weight of about 0.8 mg.
  • test cell 1-ethyl-3-methylimidazolium-tetrafluoroborate (EMI-BF4) is used as the electrolyte solute, glass fiber is used as the separator, and carbon is applied as a conductive material to the current collector.
  • the aluminum foil (Exopack TM 0.5 mil double-sided coating) was used.
  • the test cell was assembled in a glove box under an argon gas atmosphere. In the following, test cells using the electrodes prepared using the composite materials of Examples 1, 2, and 3 are referred to as “test cell 1”, “test cell 2”, and “test cell 3”, respectively. Called.
  • a cell using an electrode produced using only TRGO as a raw material (comparison cell 1), and SGCNT were suspended in 100 mL of NMP at a concentration of 0.1 mg / mL and ultrasonicated for 30 minutes.
  • a cell (Comparative Cell 2) using an electrode manufactured using a dispersion treatment and adding 100 mg of TRGO soot (mass ratio SGCNT: TRGO 1: 10) was prepared.
  • Cyclic voltammetry was performed on the test cells 1 to 3 and the comparative cells 1 and 2 using a VMP3 multichannel potentiostat / galvanostat (Biologic).
  • FIG. 5 is a graph showing the charge / discharge characteristics of the comparative cell 1 and the comparative cell 2.
  • FIG. 6 is a graph showing the charge / discharge characteristics of the test cells 1 to 3.
  • the specific capacitances of the comparative cells 1 and 2 were 182 F / g and 162 F / g with 3.7 V charge, respectively (FIGS. 5A and 5B).
  • the test cells 1 to 3 achieved capacities of 234 F / g, 250 F / g, and 236 F / g, respectively, with 3.7 V charge (FIG. 6A).
  • the test cells 1 to 3 achieved capacities of 276 F / g, 286 F / g, and 271 F / g, respectively, with 4.0 V charge (FIG. 6B).
  • a single-walled carbon nanotube (manufactured by Nippon Zeon Co., Ltd .; hereinafter also referred to as “SGCNT”) produced by the super-growth method is suspended in 100 mL of NMP at a concentration of 0.1 mg / mL, and sonicated for 30 minutes.
  • SGCNT single-walled carbon nanotube
  • This raw material suspension was supplied from the raw material introduction section at a pressure of 100 MPa using a compounding device having the same compounding module as in Example 1, and the compounding module was continuously passed through the compounding module five times to perform compounding. A dispersion of the material was obtained.
  • SEM observation it was confirmed that the carbon nanotubes were inserted between the graphene layers in the composite material obtained in this example, like the composite materials obtained in Examples 1 to 3.
  • the composite of graphene and carbon nanotubes is effectively performed without depending on the type (manufacturing method) of the raw graphene. .
  • exfoliated graphene one produced in accordance with a generally known method can be used.
  • a compounding device including a compounding module similar to that of Example 1 is applied as a device for exfoliating graphite.
  • exfoliated graphene can be produced as follows. First, a raw material suspension prepared by suspending commercially available graphite (manufactured by Shin-Etsu Chemical Co., Ltd., scaly graphite BF-5A) in NMP at a concentration of 10 mg / mL was supplied from the raw material introduction section at a pressure of 100 MPa. Then, the composite module (delamination module) is continuously passed for 120 minutes to perform delamination of graphite.
  • the flow rate of the raw material suspension at the time of passing is about 140 ml / min.
  • the raw material suspension recovered in the recovery unit is centrifuged at 6000 rpm for 60 minutes to remove the graphite precipitate that has not been delaminated, thereby obtaining a graphene dispersion.
  • the obtained dispersion is vacuum filtered to remove the dispersion medium, and the residue is dried at 120 ° C. to obtain graphene powder.
  • test cell 4 the test cell using the electrode manufactured using the composite material of Example 4 is referred to as “test cell 4”.
  • a cell using an electrode manufactured using only exfoliated graphene as a raw material (Comparative Cell 3), and SGCNT were suspended in 100 mL of NMP at a concentration of 0.1 mg / mL for more than 30 minutes.
  • a cell (comparative cell 4) was prepared using an electrode produced by using 200 mg of exfoliated graphene soot as a raw material after being subjected to sonic dispersion treatment (mass ratio SGCNT: exfoliated graphene 1: 20).
  • Cyclic voltammetry was performed on the test cell 4 and the comparative cells 3 and 4 using a VMP3 multichannel potentiostat / galvanostat (Biologic).
  • FIG. 7 is a graph showing the charge / discharge characteristics of the comparative cell 3 and the comparative cell 4.
  • FIG. 8 is a graph showing the charge / discharge characteristics of the test cell 4.

Abstract

L'invention concerne un procédé de fabrication d'un matériau composite à base d'une substance bidimensionnelle et d'une substance fibreuse, lequel procédé permet de combiner la substance bidimensionnelle et la substance fibreuse tout en supprimant les fissures ou les entailles dans les différentes structures respectivement à base de substance bidimensionnelle et de substance fibreuse, et est approprié à une production industrielle à grande échelle. Le procédé de fabrication d'un matériau composite à base d'une substance bidimensionnelle et d'une substance fibreuse selon la présente invention est caractérisé en ce qu'il comprend une étape de traitement à haute pression d'une suspension, la substance bidimensionnelle et la substance fibreuse étant mises en suspension dans un milieu de dispersion, et d'acheminement de la suspension à partir d'une unité d'introduction de matière première 2 ; une étape de passage de la suspension en provenance de l'unité d'introduction de matière première 2 à travers un module de composition 3 et l'obtention d'une dispersion d'un matériau composite, la substance fibreuse étant, à l'intérieur du milieu de dispersion, intercalée entre des couches de la substance bidimensionnelle ; et une étape de recueil de la dispersion de matériau composite à l'aide d'une unité de recueil 4 après le passage de la dispersion à travers le module de composition 3 ; le diamètre interne des passages d'écoulement de liquide dans l'unité d'introduction de matière première 2 et le module de composition 3 à travers lesquels s'écoule la suspension étant au moins égal à 0,15 mm et l'unité d'introduction de matière première 2 et le module de composition 3 ne présentant pas de passages d'écoulement de liquide d'un diamètre interne inférieur à 0,15 mm.
PCT/JP2016/083540 2015-12-24 2016-11-11 Procédé de fabrication d'un matériau composite à base d'une substance bidimensionnelle et d'une substance fibreuse WO2017110295A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017557786A JP6573262B2 (ja) 2015-12-24 2016-11-11 二次元物質と繊維状物質の複合材料の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-251138 2015-12-24
JP2015251138 2015-12-24

Publications (1)

Publication Number Publication Date
WO2017110295A1 true WO2017110295A1 (fr) 2017-06-29

Family

ID=59090421

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/083540 WO2017110295A1 (fr) 2015-12-24 2016-11-11 Procédé de fabrication d'un matériau composite à base d'une substance bidimensionnelle et d'une substance fibreuse

Country Status (2)

Country Link
JP (1) JP6573262B2 (fr)
WO (1) WO2017110295A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108597906A (zh) * 2018-06-13 2018-09-28 常熟理工学院 一种纤维/石墨烯/硫化铜柔性电极材料的制备方法
WO2019065004A1 (fr) 2017-09-27 2019-04-04 国立研究開発法人物質・材料研究機構 Électrode contenant du graphène, son procédé de fabrication, et dispositif accumulateur d'électricité l'utilisant
KR20190133496A (ko) * 2018-05-23 2019-12-03 전남대학교산학협력단 고압 셀 및 기능성 첨가제를 이용한 저두께 그래핀 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014009151A (ja) * 2012-07-03 2014-01-20 Harima Chemicals Group Inc 薄層黒鉛または薄層黒鉛化合物の製造方法
JP2014505650A (ja) * 2010-12-30 2014-03-06 オーシャンズ キング ライティング サイエンス アンド テクノロジー シーオー．，エルティーディー グラフェン誘導体−カーボンナノチューブ複合材料と、その作製方法
EP2769960A1 (fr) * 2013-02-22 2014-08-27 Samsung Electronics Co., Ltd Composite de graphène-nanomatériau, électrode et dispositif électrique le comprenant et procédé de fabrication du composite de graphène-nanomatériau
WO2015015758A1 (fr) * 2013-07-31 2015-02-05 日本ゼオン株式会社 Procédé de production d'une dispersion de nanotubes de carbone, procédé de production d'une composition pour matériau composite, procédé de production d'un matériau composite, matériau composite et produit moulé en matériau composite
JP2015078096A (ja) * 2013-10-17 2015-04-23 独立行政法人物質・材料研究機構 水熱生成グラフェン／ｃｎｔ複合体エアロゲルの作成方法、水熱生成グラフェン／ｃｎｔ複合体エアロゲル及びｕａ、ｄａ、ａａ分離検出電極

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103896240B (zh) * 2012-12-26 2016-01-20 海洋王照明科技股份有限公司 一种石墨烯/碳纳米管复合材料的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014505650A (ja) * 2010-12-30 2014-03-06 オーシャンズ キング ライティング サイエンス アンド テクノロジー シーオー．，エルティーディー グラフェン誘導体−カーボンナノチューブ複合材料と、その作製方法
JP2014009151A (ja) * 2012-07-03 2014-01-20 Harima Chemicals Group Inc 薄層黒鉛または薄層黒鉛化合物の製造方法
EP2769960A1 (fr) * 2013-02-22 2014-08-27 Samsung Electronics Co., Ltd Composite de graphène-nanomatériau, électrode et dispositif électrique le comprenant et procédé de fabrication du composite de graphène-nanomatériau
WO2015015758A1 (fr) * 2013-07-31 2015-02-05 日本ゼオン株式会社 Procédé de production d'une dispersion de nanotubes de carbone, procédé de production d'une composition pour matériau composite, procédé de production d'un matériau composite, matériau composite et produit moulé en matériau composite
JP2015078096A (ja) * 2013-10-17 2015-04-23 独立行政法人物質・材料研究機構 水熱生成グラフェン／ｃｎｔ複合体エアロゲルの作成方法、水熱生成グラフェン／ｃｎｔ複合体エアロゲル及びｕａ、ｄａ、ａａ分離検出電極

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019065004A1 (fr) 2017-09-27 2019-04-04 国立研究開発法人物質・材料研究機構 Électrode contenant du graphène, son procédé de fabrication, et dispositif accumulateur d'électricité l'utilisant
CN111164716A (zh) * 2017-09-27 2020-05-15 国立研究开发法人物质材料研究机构 含石墨烯的电极、其制造方法及使用该电极的蓄电装置
JPWO2019065004A1 (ja) * 2017-09-27 2020-11-12 国立研究開発法人物質・材料研究機構 グラフェンを含有する電極、その製造方法およびそれを用いた蓄電デバイス
US11283065B2 (en) 2017-09-27 2022-03-22 National Institute For Materials Science Graphene-containing electrode, method for manufacturing same, and power storage device using same
CN111164716B (zh) * 2017-09-27 2022-06-03 国立研究开发法人物质材料研究机构 含石墨烯的电极、其制造方法及使用该电极的蓄电装置
KR20190133496A (ko) * 2018-05-23 2019-12-03 전남대학교산학협력단 고압 셀 및 기능성 첨가제를 이용한 저두께 그래핀 제조방법
KR102091760B1 (ko) 2018-05-23 2020-03-20 전남대학교산학협력단 고압 셀 및 기능성 첨가제를 이용한 저두께 그래핀 제조방법
CN108597906A (zh) * 2018-06-13 2018-09-28 常熟理工学院 一种纤维/石墨烯/硫化铜柔性电极材料的制备方法
CN108597906B (zh) * 2018-06-13 2020-02-14 常熟理工学院 一种纤维/石墨烯/硫化铜柔性电极材料的制备方法

Also Published As

Publication number Publication date
JPWO2017110295A1 (ja) 2018-09-13
JP6573262B2 (ja) 2019-09-11

Similar Documents

Publication Publication Date Title
Le Ba et al. Review on the recent progress in the preparation and stability of graphene-based nanofluids
Zhuang et al. Flexible graphene nanocomposites with simultaneous highly anisotropic thermal and electrical conductivities prepared by engineered graphene with flat morphology
TWI558661B (zh) 石墨烯複合體及其製造方法
TWI732986B (zh) 具有碳同素異形體之無晶種粒子
Russo et al. Single-step synthesis of graphene quantum dots by femtosecond laser ablation of graphene oxide dispersions
US7785492B1 (en) Mass production of nano-scaled platelets and products
KR101700355B1 (ko) 탄소 나노 튜브의 제조 방법과, 탄소 나노 튜브의 분산 조성물
Ye et al. Green fabrication of cellulose/graphene composite in ionic liquid and its electrochemical and photothermal properties
JP6573262B2 (ja) 二次元物質と繊維状物質の複合材料の製造方法
You et al. Preparation of high concentration graphene dispersion with low boiling point solvents
TWI607967B (zh) 用以製備石墨烯的方法
Nam et al. Green, fast, and scalable production of reduced graphene oxide via Taylor vortex flow
Wu et al. 2D boron nitride nanosheets for smart thermal management and advanced dielectrics
KR102091760B1 (ko) 고압 셀 및 기능성 첨가제를 이용한 저두께 그래핀 제조방법
JP6474077B2 (ja) 層状物質を層間剥離する方法およびそのための装置
Kim et al. Graphene for Water-Based Nanofluid Preparation: Effect of Chemical Modifications on Dispersion and Stability
WO2016189873A1 (fr) Film de carbone et son procédé de production, ainsi que dispersion de nanostructures de carbone fibreux et son procédé de production
JP2016183082A (ja) 炭素膜の製造方法および炭素膜
CN113891853A (zh) 制备片状石墨烯的方法
JPWO2016002254A1 (ja) グラフェン複合体及びその製造方法
CN108430917B (zh) 纤维状碳纳米结构体分散液
JP6805440B2 (ja) 層状物質を改質する方法およびそのための装置、ならびに改質されたグラファイトおよびそれを用いた二次電池用電極材料
CN102442659B (zh) 一种由n, n-二甲基甲酰胺与乙二醇组合无损伤分散双壁碳纳米管的方法
US11577961B2 (en) Methods for producing graphene-based materials from graphite
Ekdahl Progress in top-down production of graphene

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16878192

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017557786

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16878192

Country of ref document: EP

Kind code of ref document: A1