WO2011111499A1 - Structure de nanotubes de carbone et son procédé de production - Google Patents

Structure de nanotubes de carbone et son procédé de production Download PDF

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WO2011111499A1
WO2011111499A1 PCT/JP2011/053522 JP2011053522W WO2011111499A1 WO 2011111499 A1 WO2011111499 A1 WO 2011111499A1 JP 2011053522 W JP2011053522 W JP 2011053522W WO 2011111499 A1 WO2011111499 A1 WO 2011111499A1
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carbon nanotubes
carbon
aggregate
nanotube aggregate
carbon nanotube
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PCT/JP2011/053522
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English (en)
Japanese (ja)
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裕治 瀧本
井上　崇
理恵 田尾
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東洋炭素株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • 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
    • 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
    • C01B32/158—Carbon nanotubes
    • 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
    • C01B32/158—Carbon nanotubes
    • C01B32/159—Carbon nanotubes single-walled

Definitions

  • the present invention relates to a carbon nanotube used as, for example, an electrode material for a battery or an electric double layer capacitor, a probe for a scanning tunneling microscope, a conductive material, or a material for reinforcing resin or ceramics.
  • the carbon nanotubes have a structure in which a network of six-membered rings of carbon elements is rolled up into a cylindrical shape.
  • the carbon nanotubes are sorted by the number of graphene sheets (number of layers) constituting the carbon nanotubes, single-walled carbon nanotubes and multi-walled carbon nanotubes (In the case where the number of layers is two or three, it may be referred to as a double-walled carbon nanotube or a triple-walled carbon nanotube, respectively).
  • the carbon nanotube is a fine fibrous powder, but has a cohesive property. Therefore, the carbon nanotube is required to have dispersibility when mixed with a resin or a solvent.
  • the following proposals have been made for such dispersibility.
  • a proposal for granulating carbon nanotubes to produce a spherical carbon nanotube aggregate having a substantially spherical shape (see Patent Document 1 below).
  • C Proposal for a nano-unit carbon material having a large bulk density (see Patent Document 3 below).
  • an arc discharge method As a method for synthesizing the carbon nanotube, an arc discharge method, a laser evaporation method, a CVD method and the like are known so far.
  • the arc discharge method is expected to be a method for synthesizing carbon nanotubes because it can synthesize a large amount of carbon nanotubes compared to the laser evaporation method and has excellent crystallinity compared to the CVD method. Yes.
  • carbon nanotubes synthesized by the various methods described above contain a large amount of impurities immediately after synthesis. For this reason, in order to isolate only the carbon nanotubes by removing impurities and improve the basic physical properties of the carbon nanotubes for a wide range of applications, it is necessary to sufficiently purify the carbon nanotubes.
  • Various methods are known as such purification means. Among them, the method of vaporizing and removing impurities with dry chlorine has the advantage that it can be easily scaled up with simple equipment, and mass-produces carbon nanotubes at low cost. It is suitable for.
  • the synthesized carbon nanotubes are purified as they are, there are the following problems.
  • Carbon nanotubes immediately after synthesis are bulky, resulting in poor packing efficiency when loaded into a purification apparatus.
  • carbon nanotubes are extremely thin fibers, a large amount of fine dust is generated and handling properties are reduced.
  • Carbon nanotubes have been studied for many uses such as fuel cell electrodes and composite materials. When used in such applications, the carbon nanotubes are molded after being dispersed in a resin or binder. There are many cases. However, since carbon nanotubes are extremely thin fibers, the dispersibility of the carbon nanotubes in the resin or binder decreases.
  • the techniques (a) to (c) described in the background art have the following problems. Problem of the technique of (a) By granulating, the improvement of the packing efficiency in the case of loading in a refiner
  • the bulk density of the granulated product is not specified, it is not certain whether the dispersibility of the carbon nanotubes when added to a binder or the like can be drastically improved.
  • the bulk density of the granulated product is not specified, it is not clear whether the carbon nanotubes can be sufficiently purified because the proportion of the space in the granulated product is unknown.
  • the bulk density is the bulk density of carbon nanotubes (powdered) that have not been granulated. Therefore, since the bulk density after granulating the carbon nanotube is unknown, whether the dispersibility of the carbon nanotube can be dramatically improved and whether the carbon nanotube can be sufficiently purified. Not sure. Moreover, since it is a powder-like thing, handling property is not favorable.
  • the present invention takes the above-mentioned problems into consideration, and improves the packing efficiency when it is loaded into a refining device, improves handling by suppressing the generation of dust, and leap in dispersibility when added to a binder or the like.
  • An object of the present invention is to provide a carbon nanotube aggregate or the like that can improve the efficiency and remove impurities reliably.
  • the present invention is characterized by being granular and having a bulk density of 0.25 g / cm 3 or less.
  • the carbon nanotube aggregate is granular, the generation of dust can be suppressed, so that handling is improved and handling in a continuous processing furnace such as a rotary kiln is also possible. Efficiency in manufacturing and cost reduction are possible.
  • the bulk density is regulated to 0.25 g / cm 3 or less, an appropriate space exists in the carbon nanotube aggregate. Therefore, since the contact with various gases is sufficiently performed during the purification treatment, the ash can be surely removed and the disintegration is improved, so that the dispersibility in various solvents and polymers is improved.
  • the bulk density is preferably regulated to 0.01 g / cm 3 or more. Thereby, the improvement of the packing efficiency in the case of loading to a refiner
  • purifier can be aimed at.
  • the bulk density is particularly preferably 0.03 g / cm 3 or more and 0.20 g / cm 3 or less.
  • the particle size is desirably 1 mm or more. This is because when the particle size is less than 1 mm, the handling property in transportation or the like is lowered.
  • the particle size is desirably 20 mm or less. When the particle diameter exceeds 20 mm, the particulate aggregate is likely to be broken and may generate dust. Furthermore, since the space between the particles becomes large, the packing efficiency in the case of loading into the purification apparatus may not be sufficiently improved.
  • the particle size is more preferably 10 mm or less. This makes it more difficult to break and facilitates manufacture.
  • the porosity is 80% by volume or more.
  • the porosity is less than 80% by volume, the space inside the carbon nanotube aggregate becomes small, and in the purification process, the contact between various gases and the carbon nanotubes is not sufficient, and the ash is not sufficiently removed. is there. Moreover, the disintegration property is lowered, and the dispersibility in various solvents and polymers may be lowered.
  • the porosity is 90% by volume or more in order to obtain the above effect.
  • the porosity is preferably 99% by volume or less. If the porosity exceeds 99% by volume, the space inside the carbon nanotube aggregate becomes too large, so that the particulate aggregate can be easily broken and dust may be generated. In some cases, it cannot be improved sufficiently.
  • the bulk density, particle size, and porosity may be an average value in a plurality of carbon nanotube aggregates (about 10).
  • a granular carbon nanotube aggregate having a bulk density of 0.25 g / cm 3 or less is produced by adding unpurified carbon nanotubes in a solvent, stirring, granulating, and drying. And By such a production method, the carbon nanotube aggregate can be produced.
  • a granular carbon nanotube aggregate while keeping the bulk density low can be produced by removing only the solvent without agglomerating the granulated product. For example, if the solvent is to be removed rapidly at a high temperature of 100 ° C. or higher, the agglomerates are likely to aggregate and the bulk density is likely to increase.
  • the drying is freeze-drying.
  • freeze-drying only the solvent can be removed in a short time while suppressing aggregation of the nanotubes during drying, so that the carbon nanotube aggregate can be produced in a short time, and the quality of the carbon nanotube aggregate can be improved. Cost reduction can be achieved.
  • the solvent is preferably a mixed solvent of water and methanol. If a mixed solvent of water and methanol is used, the effect on the purity of the carbon nanotubes is small, and vaporization and removal can be easily performed, so that the purification efficiency can be prevented from decreasing.
  • the porosity is desirably 90% by volume or more.
  • the carbon nanotube aggregate obtained by the above-described method is characterized by being highly purified (purified). High purity because carbon nanotubes containing impurities such as amorphous carbon may be granulated as they are and then purified (ie, there is no need to granulate carbon nanotubes containing impurities once after purification) The aggregate of carbon nanotubes can be easily manufactured.
  • the high purity treatment is preferably a halogen gas treatment and / or an oxygen gas treatment.
  • a carbon nanotube aggregate is dry-purified with halogen gas or oxygen gas, impurities can be removed while suppressing damage and cutting of the carbon nanotubes and solidification of the carbon nanotubes in a lump. .
  • the present invention it is possible to improve packing efficiency when carbon nanotubes are loaded into a purification apparatus and to improve handling by suppressing generation of dust, and dispersion when carbon nanotubes are added to a binder or the like. It is possible to drastically improve the properties and to reliably remove impurities from the carbon nanotubes.
  • FIG. 1 is a longitudinal cross-sectional view
  • FIG. 2 is a side view
  • 3 is a photograph of the nanotube aggregate A of the present invention when observed by FE-SEM.
  • 6 is a photograph of the comparative nanotube aggregate Z when observed by FE-SEM. It is an external appearance when the nanotube aggregate A of the present invention is dispersed in a solvent. It is an external appearance when the comparative nanotube aggregate Z is dispersed in a solvent. It is a graph when an absorption spectrum is measured with a UV meter.
  • FIG. 1 shows an apparatus for producing single-walled carbon nanotubes by an arc discharge method (hereinafter sometimes referred to as a carbon nanotube producing apparatus).
  • the carbon nanotube manufacturing apparatus has an upper chamber 1 and a lower chamber 2, and both the chambers 1 and 2 are communicated with each other through a conduit 3.
  • An anode 4 and a cathode 5 are arranged in the lower chamber 2 so as to face each other, and a distance L1 between these two electrodes 4 and 5 is arranged to be 5 mm.
  • the cathode 5 is made of graphite and has a cylindrical shape with a diameter of 30 mm and a length of 50 mm.
  • a cold trap 6 is provided in the upper chamber 1, and a conduit (not shown) for flowing liquid nitrogen is provided in the cold trap 6.
  • FIG. 2 is a conceptual diagram showing a halogen treatment apparatus that manages one step for purifying a carbon nanotube aggregate after granulating unpurified carbon nanotubes produced by the above apparatus.
  • the halogen treatment apparatus according to the present embodiment is provided with a carbon fiber felt heat insulating material layer 12 inside a stainless steel chamber 11, and a carbon heater inside the carbon fiber felt heat insulating material layer 12. 13 and a susceptor 14 made of carbon is provided inside the heater 13. Inside the susceptor 14, a carbon crucible 15 containing an unpurified carbon nanotube aggregate 9 is installed.
  • the susceptor 14 and the crucible 15 are preferably purified in advance in order to prevent impurities from entering the unpurified carbon nanotube aggregate 9.
  • the chamber 11 is a vacuum vessel, and a gas exhaust line 16 communicating with the inside of the chamber 11 is provided on the upper part thereof.
  • the vacuum pump 18 provided in the gas exhaust line 16 reduces the pressure of the chamber 11. The state can be maintained.
  • a gas supply line 17 that communicates with the inside of the chamber 11 and introduces a chlorine gas-containing inert gas into the chamber 11 is provided below the chamber 11. Then, the chlorine gas-containing inert gas is subjected to chlorination treatment of the unpurified carbon nanotube aggregate, and then passes through a dust catcher 19 provided in the gas discharge pipe 16 and the vacuum pump 18, and finally Specifically, it is neutralized with caustic soda in the scrubber 20, rendered harmless, and opened to the atmosphere.
  • reference numeral 21 in FIG. 2 denotes a mesh-like bottom plate. By making the mesh in this way, it is possible to smoothly introduce the chlorine gas-containing inert gas into the susceptor 14.
  • FIG. 3 is a conceptual diagram showing an oxidation treatment apparatus that controls one step for further purifying the aggregate of carbon nanotubes primarily purified by the halogen treatment apparatus.
  • the oxidation processing apparatus includes a cylindrical oxidation processing furnace 31 whose both ends are sealed by stainless seal ports 32 and 33.
  • a first cylinder 34 storing argon gas therein and a second cylinder 35 storing argon gas and oxygen gas therein are connected to the gas introduction path 33 a of the seal port 33 through a pipe line 38.
  • argon gas or a mixed gas of argon gas and oxygen gas can be introduced into the oxidation treatment furnace 31.
  • Reference numerals 34a and 35a are gas flow meters.
  • a pipe 39 for discharging the gas introduced into the oxidation treatment furnace 31 to the outside is connected to the gas discharge path 32 a of the seal port 32.
  • a heater 36 for heating the inside of the oxidation treatment furnace 31 is provided outside the oxidation treatment furnace 31, while a quartz crucible 37 is provided inside the oxidation treatment furnace 31.
  • the crucible 37 has a cylindrical main body portion 37a, and a side wall 37b is provided at one end of the main body portion 37a.
  • a number of holes 37c are provided in the side wall 37b, and the gas described above passes through the holes 37c, so that the gas can be uniformly applied to the aggregate of carbon nanotubes that has been subjected to the halogen treatment in the apparatus of FIG. become. In order to exert such an action, it is desirable to provide two crucibles 37 together.
  • This arc discharge evaporates carbon components, catalyst metal, and the like from the anode 4, and the evaporated material is transported along with the helium gas to the cold and lap 6 surfaces of the upper chamber 1. Then, the evaporant is cooled in the cold trap 6, thereby generating unpurified carbon nanotubes 9. Next, after the arc discharge was completed, the interiors of the upper and lower chambers 1 and 2 were sufficiently cooled, and further opened to the atmosphere, whereby unpurified carbon nanotubes deposited in the upper chamber 1 were recovered.
  • Purification of carbon nanotube aggregate subjected to the vacuum freeze-drying treatment was performed through the following three steps (1) to (3).
  • (1) Halogen treatment step The aggregate of carbon nanotubes subjected to the vacuum freeze-drying treatment was placed in the crucible 15, and the crucible 15 was placed in the halogen treatment apparatus shown in FIG. Next, the inside of the chamber 11 was evacuated to 1 Torr or less, and the carbon heater 13 was energized to raise the temperature inside the chamber 11 to 1000 ° C. Next, argon gas is introduced into the chamber 11 from the gas supply line 17, and the pressure inside the chamber 11 is adjusted to 70 Torr. After the pressure is reached, 1 L of argon gas is added to the chamber 11 per minute.
  • the reason why the argon gas is included in addition to the oxygen gas is that the aggregate of the carbon nanotubes is gently oxidized by the presence of the argon gas, that is, the oxidation rate can be controlled. After maintaining such a state for 30 minutes, the crucible 37 was taken out from the oxidation furnace 31 and further cooled in the crucible 37. In this way, the carbon nanotube aggregate after the halogen treatment was oxidized.
  • Example As an example, an aggregate of carbon nanotubes produced in the best mode was used.
  • the carbon nanotube aggregate thus produced (carbon nanotube aggregate that has undergone another halogen treatment step) is hereinafter referred to as the present invention nanotube aggregate A.
  • Comparative example An aggregate of carbon nanotubes was produced in the same manner as in the above example, except that the unpurified carbon nanotubes were granulated and then dried with a circulating hot air dryer without being frozen (temperature: 80 ° C.).
  • the carbon nanotube aggregate thus produced is hereinafter referred to as a comparative nanotube aggregate Z.
  • reference example As a reference example, an unpurified carbon nanotube before granulation was used.
  • the carbon nanotube thus produced is hereinafter referred to as reference nanotube X.
  • Example 1 The weight, volume, specific volume, bulk density, particle size, porosity, and presence / absence of scattering of the above-described nanotube aggregate A of the present invention and comparative nanotube aggregate Z were examined, and the results are shown in Table 1.
  • values for the reference nanotube X are also shown.
  • the porosity in Table 1 is calculated using the following equation (1) after calculating the volume (Vcnt) of only the carbon nanotubes constituting the carbon nanotube aggregate, assuming the true density of the carbon nanotubes to be 1 g / cm 3. did.
  • V is the total volume of the carbon nanotube aggregate.
  • the weight, volume, specific volume, bulk density, and porosity of the nanotube aggregate A of the present invention and the comparative nanotube Z in Table 1 are the sampled samples (17 in the nanotube aggregate A of the present invention, The average value of 14 grains in the body Z).
  • the nanotube aggregate A of the present invention and the comparative nanotube aggregate Z have a bulk density higher than that of the reference nanotube X. Therefore, a large amount of carbon nanotubes can be arranged in a limited space in the furnace during purification treatment such as chlorination and oxidation. As a result, since the throughput per batch can be increased, the productivity of carbon nanotubes with high purity is remarkably improved.
  • the nanotube aggregate A of the present invention and the comparative nanotube aggregate Z have substantially no carbon nanotube scattering, and the handling property is greatly improved. It is recognized that
  • the nanotube aggregate A of the present invention had a particle size of 2 to 8 mm, which was the same as that immediately after granulation, and was easily deformed when pressed with a finger.
  • the comparative nanotube aggregate Z had a particle size of 0.7 to 19.8 mm, contracted compared to immediately after granulation, and did not easily deform even when pressed with a finger.
  • the comparative nanotube aggregate Z contracted, it is recognized that the porosity, volume, and specific volume are smaller than those of the present nanotube aggregate A, but the bulk density is increased.
  • the peak at 1570 to 1610 cm ⁇ 1 is the in-plane contraction vibration of the six-membered ring network of graphite and is called G-Band.
  • G-Band 1320 ⁇ 1360cm -1 peak observed in is called D-Band is due to the defect. Therefore, the G / D ratio, which is the ratio of peak intensities of G-Band and D-Band, can be used for quality evaluation of carbon nanotubes in carbon materials containing carbon nanotubes.
  • the comparative nanotube aggregate Z is the nanotube aggregate A of the present invention at any stage after the first chlorination treatment, after the oxidation treatment, and after the second chlorination treatment. It can be seen that the recovery rate is higher than that. Further, it is recognized that the nanotube aggregate A of the present invention is substantially equivalent to the reference nanotube X at any stage.
  • the nanotube aggregate A of the present invention is smaller than the reference nanotube X, it is recognized that it is much larger than the comparative nanotube aggregate Z.
  • the nanotube aggregate A of the present invention is smaller than the reference nanotube X, and the ash is sufficiently removed, whereas the comparative nanotube aggregate Z is a reference nanotube. It is recognized that the ash is not sufficiently removed because it is larger than X.
  • FIG. 5 is a photograph of the nanotube aggregate A of the present invention observed by FE-SEM
  • FIG. 6 is a photograph of the comparative nanotube aggregate Z observed by FE-SEM.
  • the nanotube aggregate A of the present invention has almost no amorphous carbon or catalytic metal particles
  • the comparative nanotube aggregate Z has amorphous carbon or catalyst. It can be seen that a large number of metal particles are present. This is because, in the comparative nanotube aggregate Z, the space in the particles becomes small due to shrinkage during hot air drying, and the passage of chlorine gas and oxygen gas becomes poor. For this reason, the contact between the carbon nanotube and the gas is not performed smoothly, and the purification does not proceed efficiently.
  • the nanotube aggregate A of the present invention does not shrink during drying, the space in the particles is not reduced, and the passage of chlorine gas or oxygen gas can be suppressed. For this reason, the contact between the carbon nanotube and the gas is performed smoothly, and the purification proceeds efficiently.
  • Example 3 Since the dispersibility in the nanotube aggregate A of the present invention and the comparative nanotube aggregate Z was examined, the results are shown in FIGS.
  • 5 mg of each of the nanotube aggregates A and Z was added to 100 ml of 1% SDS aqueous solution, and the appearance after 1 minute irradiation with an ultrasonic homogenizer was observed.
  • FIG. 7 shows the appearance of the nanotube aggregate A of the present invention
  • FIG. 8 shows the appearance of the comparative nanotube aggregate Z.
  • the ultrasonic homogenizer was further irradiated for 5 minutes to advance the dispersion.
  • the particles were visually observed. Dispersion progressed to the extent that it could not be confirmed.
  • FIG. 9 shows a measurement example. Since the light absorption depending on the chirality of the carbon nanotube contained was confirmed and the light absorption derived from the carbon nanotube was confirmed at 720 nm, the absorbance was measured at the wavelength.
  • the prepared dispersion (dispersion obtained by adding 5 mg of each of the nanotube aggregates A and Z to 100 ml of 1% aqueous solution of sodium dodecyl sulfate (SDS)) was collected, and centrifuged at 5000 g for 10 minutes. The absorbance of the centrifuged supernatant was measured with a UV meter. Next, the remaining 50 ml of the dispersion was further irradiated with ultrasonic waves for 10 minutes to completely disperse the carbon nanotube aggregates A and Z, and the absorbance was measured. From these measured absorbance values, the carbon nanotube concentration was calculated according to Lambert Beer's law.
  • the concentration of carbon nanotubes added was 50 ppm, whereas the concentration of carbon nanotubes in the nanotube aggregate A of the present invention was 40 ppm, whereas that of the comparative nanotube aggregate Z was 17 ppm. Therefore, it can be seen that the nanotube aggregate A of the present invention exhibits higher dispersibility than the comparative nanotube aggregate Z. As a result, the freeze-dried nanotube aggregate A of the present invention rapidly disintegrates in a solvent, but the powder of the comparative nanotube aggregate Z that is hardly shrunk by hot air drying hardly disintegrates in the solvent. I understood it.
  • the nanotube aggregate A of the present invention is granular. Therefore, it is possible to improve handling by suppressing the generation of dust, so handling becomes easy and handling in a continuous processing furnace such as a rotary kiln is also possible, so efficiency and cost reduction in mass production are possible. Is possible.
  • the bulk density is higher than that of the reference nanotube X that has not been subjected to the granulation treatment, the packing efficiency in the case of loading in the purification apparatus is improved as compared with the reference nanotube X.
  • the comparative nanotube aggregate Z is the same.
  • the nanotube aggregate A of the present invention can remove ash in the purification process without causing any problem in crystallinity, whereas the comparative nanotube aggregate Z has a problem in crystallinity and sufficiently removes ash. I can't. This is because the nanotube aggregate A of the present invention has an appropriate space in the particle, so that the carbon nanotube can sufficiently contact with chlorine gas or oxygen gas, whereas the comparative nanotube aggregate Z has an appropriate amount in the particle. This is because the carbon nanotubes cannot sufficiently contact with chlorine gas or oxygen gas because there is no space.
  • nanotube aggregate A of the present invention a moderate space exists in the particles, and the dispersibility in various solvents and polymers is improved due to the excellent crushability, while the comparative nanotube aggregate In the body Z, an appropriate space does not exist in the particles, and dispersibility in various solvents, polymers, and the like does not improve due to poor crushability.
  • carbon nanotubes are granulated and then freeze-dried.
  • the present invention is not limited to such a method, and when the granulated product is dried, the granulated product is aggregated. Without removing the solvent alone, a granular carbon nanotube aggregate while keeping the bulk density low may be produced.
  • An example is a method of drying at a low temperature (solvent evaporation temperature, volatilization temperature, etc.) at which the solvent can be removed under normal pressure or reduced pressure.
  • the solvent for granulating the carbon nanotubes is not limited to a mixed solution of water and ethanol, but a lower alcohol such as methanol, propanol, or butanol, a lower ketone such as acetone, methyl ethyl ketone, or diethyl ketone. It may be.
  • the carbon material is produced by the arc discharge method.
  • the present invention is not limited to such a method, and the present invention can be applied even if produced by using a laser evaporation method, a CVD method or the like.
  • a direct current arc discharge method using a carbon electrode containing a NiY binary catalyst as an anode may be used, but the method is not limited to this method.
  • an AC arc discharge method may be used.
  • the catalyst other than NiY may be an alloy containing any of Fe, Ni, and Co.
  • the discharge atmosphere may be an Ar atmosphere or an N 2 atmosphere, but is preferably a He atmosphere in order to improve the yield of carbon nanotubes.
  • the CVD method is used for the production of carbon nanotubes, it is possible to use a hydrocarbon, alcohol, or biomass-derived carbon source as the carbon source, and the catalyst metal is mainly one of Fe, Ni, and Co. It may be synthesized by a fluidized bed method or a substrate method using fine particles containing.
  • the present invention includes, for example, a negative electrode material for a fuel cell and a lithium secondary battery, a high-strength resin composed of a composite material with a resin and an organic semiconductor, a conductive resin, a material for an electromagnetic shielding material, a probe for a scanning tunnel microscope, a field electron It can be preferably applied as a release source, nanotweezer material, adsorbent material, and medical nanocapsule material.

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Abstract

La présente invention concerne : une structure de nanotubes de carbone dont l'efficacité d'empilement peut être améliorée lorsqu'elle est chargée dans un dispositif de purification, ne générant pas de poussières et présentant ainsi des caractéristiques de manipulation améliorées, présentant une dispersibilité largement améliorée lorsqu'elle est ajoutée à un liant, etc., et dont les impuretés peuvent être éliminées de façon fiable ; etc. La présente invention concerne spécifiquement une structure de nanotubes de carbone caractérisée en ce qu'elle présente une forme particulière et une densité apparente de 0,25 g/cm3 ou moins. De façon préférentielle, la structure de nanotubes de carbone présente une granulométrie de 1 mm ou plus et une porosité de 80 % en volume ou plus.
PCT/JP2011/053522 2010-03-12 2011-02-18 Structure de nanotubes de carbone et son procédé de production WO2011111499A1 (fr)

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WO2018178929A2 (fr) 2017-03-31 2018-10-04 HYDRO-QUéBEC Procédé de purification de nanotubes de carbone bruts
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CN109880344A (zh) * 2019-01-30 2019-06-14 中北大学 一种低反射高屏蔽水性聚氨酯电磁屏蔽复合泡沫的制备方法
EP4151688A4 (fr) * 2020-05-11 2023-11-01 Panasonic Holdings Corporation Feuille stratifiée de blindage contre les ondes électromagnétiques

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JPWO2017146218A1 (ja) * 2016-02-26 2018-12-20 学校法人早稲田大学 金属粒子を含むカーボンナノチューブ混合物から金属粒子を除去する除去方法、除去装置、および、それらによって得られるカーボンナノチューブと中空炭素粒子との複合体
WO2017146218A1 (fr) * 2016-02-26 2017-08-31 学校法人早稲田大学 Procédé et dispositif d'élimination des particules métalliques d'un mélange de nanotubes de carbone contenant des particules métalliques, et composite constitué de particules de carbone creuses et de nanotubes de carbone ainsi obtenus
JP7044372B2 (ja) 2016-02-26 2022-03-30 学校法人早稲田大学 金属粒子を含むカーボンナノチューブ混合物から金属粒子を除去する除去方法、除去装置、および、それらによって得られるカーボンナノチューブと中空炭素粒子との複合体
CN109219575B (zh) * 2016-06-10 2022-06-14 Lg化学株式会社 碳纳米管结构体及其制造方法
CN109219575A (zh) * 2016-06-10 2019-01-15 Lg化学株式会社 碳纳米管结构体及其制造方法
EP3372557A4 (fr) * 2016-06-10 2018-12-05 LG Chem, Ltd. Structure de nanotubes de carbone et leur procédé de préparation
US10815126B2 (en) 2016-06-10 2020-10-27 Lg Chem, Ltd. Carbon nanotube structure and method for manufacturing same
JP2020515497A (ja) * 2017-03-31 2020-05-28 ハイドロ−ケベック 粗カーボンナノチューブの精製のための方法
CN110662715A (zh) * 2017-03-31 2020-01-07 魁北克电力公司 粗制碳纳米管的提纯方法
WO2018178929A2 (fr) 2017-03-31 2018-10-04 HYDRO-QUéBEC Procédé de purification de nanotubes de carbone bruts
JP7171608B2 (ja) 2017-03-31 2022-11-15 ハイドロ－ケベック 粗カーボンナノチューブの精製のための方法
US11661344B2 (en) 2017-03-31 2023-05-30 Hydro-Quebec Method for the purification of raw carbon nanotubes
CN110662715B (zh) * 2017-03-31 2023-10-27 魁北克电力公司 粗制碳纳米管的提纯方法
JP7429760B2 (ja) 2017-03-31 2024-02-08 ハイドロ－ケベック 粗カーボンナノチューブの精製のための方法
CN109880344B (zh) * 2019-01-30 2021-02-23 中北大学 一种低反射高屏蔽水性聚氨酯电磁屏蔽复合泡沫的制备方法
CN109880344A (zh) * 2019-01-30 2019-06-14 中北大学 一种低反射高屏蔽水性聚氨酯电磁屏蔽复合泡沫的制备方法
EP4151688A4 (fr) * 2020-05-11 2023-11-01 Panasonic Holdings Corporation Feuille stratifiée de blindage contre les ondes électromagnétiques

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