JP2002356317A - Graphite ribbon and its producing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new technology relating to new carbon materials such as a graphite ribbon and a graphite ribbon containing a heterogeneous element and the like. SOLUTION: The graphite ribbon has a 2-70 layered structure with ribbon graphen sheets.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a graphite ribbon, a carbon material containing the graphite ribbon, and a method for producing a graphite ribbon.

[0002]

2. Description of the Related Art In MO calculation and the like, it is predicted that a carbon material having a graphite end exhibits functionality (for example, K. Wakabayashi, Mol Cryst Liq Crys
t, 340,379-382, 2000, etc.).

[0003] However, no attempt has been made to synthesize a functional carbon material such as a graphite ribbon, and at present, such graphite has not yet been actually manufactured.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel technique relating to a novel carbon material such as a graphite ribbon and a graphite ribbon containing a different element.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art, and as a result of conducting research, it has been found that cyclic carbon halides and / or their reduced products are used as raw materials for carbon materials such as graphite ribbons. To complete a new technology for synthesizing

In the present invention, a specific carbon material is used as a precursor, and light (eg, laser light), X
Beam, electron beam, plasma and ion beam
By irradiating one kind, or by heating such a carbon material, or by irradiating and heating such a carbon material, a graphite ribbon, a graphite ribbon containing a different element, It is possible to obtain a carbon material containing a mixture of two or more species (hereinafter sometimes referred to as “target product”).

That is, the present invention provides a graphite ribbon, a carbon material and a method for producing the same as described below; A graphite ribbon having a structure in which two to 70 layers of ribbon-like graphene sheets are stacked. 2. 2. The graphite ribbon according to 1 above, wherein the graphene sheets are stacked in parallel with the length direction of the ribbon. 3. 3. The graphite ribbon according to 1 or 2, wherein the graphene sheet includes a graphite ribbon having a bent portion or a branched portion. 4. The above graphene sheet, wherein the graphene sheet contains a different element.
3. The graphite ribbon according to any one of 3. 5. 5. The graphite ribbon according to any one of the above items 1 to 4, wherein at least one of a metal salt and a metal is contained between layers of the graphene sheet. 6. A carbon material comprising the graphite ribbon according to any one of the above 1 to 5. 7. By irradiating at least one of light, X-ray, electron beam, plasma and ion beam to the cyclic carbon halide and / or its reduced product, or by heating the carbon material, A method for producing a graphite ribbon, which is subjected to irradiation treatment and heat treatment.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a graphite ribbon having a structure in which about 2 to 70 layers of ribbon-like graphene sheets are stacked.

The graphite ribbon of the present invention has a developed graphite structure, and has a structure in which ribbon-like graphene sheets having graphite ends are laminated. In the graphite ribbon of the present invention, the graphene sheet is usually laminated in about 2 to 70 layers, preferably in about 2 to 50 layers, more preferably in about 2 to 30 layers. The manner of lamination is not particularly limited. For example, as shown in FIG. 1, a mode in which graphene sheets are laminated in parallel with the length direction of the ribbon can be exemplified.

[0010] In the graphite ribbon of the present invention, the graphene sheet may include a graphite ribbon having a bent portion, a branched portion, and the like. FIG. 2 schematically illustrates one embodiment of a graphite ribbon having a bent portion, and FIG. 3 schematically illustrates one embodiment of a graphite ribbon having a branch portion.

[0011] The size of the graphene sheet is not particularly limited. Graphene sheet length is usually 10nm ~ 10μm
Degree, preferably about 10 nm to 5 μm, more preferably 10 nm
About 1 μm. Graphene sheet width is typically 0.4n
It is about m-100 nm, preferably about 1-50 nm, more preferably about 2-30 nm.

[0012] The size of the graphite ribbon is not particularly limited. The length of graphite ribbon is usually 10nm ~ 10
μm, preferably about 10 nm to 5 μm, more preferably 1 μm
It is about 0 nm to 1 μm. The width of the graphite ribbon is usually about 0.4 nm to 100 nm, preferably about 1 nm to 50 nm, and more preferably about 2 nm to 30 nm.

The interlayer distance of the graphene sheet in the graphite ribbon of the present invention is not particularly limited, but is usually about 3.35 ° to 4.5 °, preferably about 3.35 to 4.3 °, more preferably about 3.35 to 4.5 ° as measured by X-ray diffraction. It is about 4Å.

The thickness of the graphite ribbon is not particularly limited, but is usually about 0.4 nm to 31 nm, preferably 0.4 nm to 22 nm.
It is about nm, more preferably about 0.4 nm to 13 nm.

The graphite ribbon of the present invention may contain a different element in a part of the graphene sheet constituting the ribbon. That is, a different element may be present in the graphene sheet structure. The different element is not particularly limited, and examples thereof include nitrogen, sulfur, oxygen, and silicon. Of these, nitrogen is preferred.

The content of the different elements (when two or more kinds are contained, the total amount) is not particularly limited. The lower limit of the content of the different elements is usually 0.01 to the entire graphite ribbon.
% By weight. The upper limit of the content of the different element is generally about 60% by weight, preferably about 30% by weight, more preferably about 10% by weight, based on the entire graphite ribbon.
The content of the different element is usually about 0.01 to 60% by weight, preferably about 0.1 to 30% by weight, more preferably about 1 to 10% by weight, based on the entire graphite ribbon.

The graphite ribbon of the present invention may contain at least one of a metal salt and a metal between layers of the graphene sheet. The metal is not particularly limited, but iron,
Examples thereof include cobalt, copper, platinum, palladium, rubidium, strontium, cesium, vanadium, manganese, nickel, aluminum, silver, lithium, sodium, and magnesium. Examples of the metal salt include halides such as fluoride, chloride, bromide and iodide of these metals; and organic salts such as acetylacetonate salt. As the metal salt, a halide such as chloride, bromide and iodide is preferable. Among these, magnesium, iron, lithium, magnesium chloride,
Iron chloride, lithium chloride, magnesium fluoride, iron fluoride and lithium fluoride are preferred, and magnesium, iron, magnesium chloride and iron chloride are particularly preferred.

The contents of the metal salt and the metal (when two or more kinds are contained, the total amount thereof) are not particularly limited. The lower limit of the content of the metal salt and metal is usually about 0.01% by weight based on the entire graphite ribbon. The upper limit of the content of the metal salt and the metal is usually about 60% by weight, preferably about 30% by weight, more preferably about 10% by weight based on the entire graphite ribbon. The content of the metal salt and metal is usually about 0.01 to 60% by weight, preferably about 0.1 to 30% by weight, more preferably about 1 to 10% by weight, based on the entire graphite ribbon.

The macroscopic shape of the graphite ribbon of the present invention (an embodiment in which the graphite ribbon is innumerably aggregated) is not particularly limited, and examples thereof include a powdery shape and a thin film shape. When formed into a thin film, the thickness is not particularly limited, but is usually about 0.3 nm to 300 μm, preferably about 5 nm to 50 μm, and particularly preferably about 5 nm to 30 μm.

The graphite ribbon of the present invention is, for example,
It can be suitably used as a carbon material. For example, methane storage materials, hydrogen storage materials, electron beam radiation emitters,
Diamond semiconductors, wear-resistant materials, battery electrode materials, magnetic recording media, magnetic fluids, nanodevices, nanosolid lubricants,
It is useful as other electronic materials. Furthermore, the carbon material of the present invention is also useful as a photoelectric conversion material, a light-to-light conversion material, a nano-conductive material, and the like.

The graphite ribbon of the present invention is, for example,
It can be obtained by using a cyclic carbon halide and / or its reduced product as a raw material carbon material. More specifically, subjecting the cyclic carbon halide and / or its reduced product to irradiation treatment of irradiating at least one of light, X-ray, electron beam, plasma and ion beam, heating the carbon material Or by subjecting the carbon material to irradiation treatment and heat treatment.

Cyclic carbon halides and / or their reduced products as raw materials for graphite ribbons and methods for synthesizing them are known (for example, JP-A-2000-26985).

As the cyclic carbon halide, fluorine,
Compounds having an aromatic ring moiety halogenated by chlorine, bromine, iodine, etc. can be exemplified. As a specific example of the compound having a halogenated aromatic ring site, pitch fluoride
(For example, naphthalene pitch, quinoline pitch, etc.), heavy oil fluoride, fluoride of mesocarbon microbeads, carbon fluoride, graphite fluoride, activated carbon fluoride, activated carbon fluoride, aromatic fluoride Hydrocarbon compounds (naphthalene fluoride, quinoline fluoride, hexafluorobenzene,
Octafluoronaphthalene, decafluoroanthracene, decafluorophenanthrene, decafluoropyrene, etc.) wherein at least one of the substituents, fluorine, is selected from the group consisting of chlorine, bromine and iodine.
Some are changed depending on the species. Examples of the compound having a halogenated aromatic ring moiety include pitch fluoride such as coal tar pitch fluoride, petroleum petroleum pitch, and synthetic pitch fluoride, in which fluorine as a substituent is chlorine, bromine or iodine. And those modified by at least one selected from the group consisting of: The raw carbon material such as pitch fluoride and fluorinated aromatic hydrocarbon compound may contain different elements. As the raw carbon material, pitch fluoride is preferable. One type of raw carbon material may be used alone, or two or more types may be used in combination.

The fluorinated pitch can be prepared by a known method such as fluorination of the pitch with fluorine gas (for example, Japanese Patent Application Laid-Open No.
Publication No.). Raw materials used for producing pitch fluoride include common aromatic hydrocarbon compounds; petroleum-based or coal-based heavy oil (eg, petroleum distillation residue, naphtha pyrolysis residue, ethylene bottom oil, coal liquefaction) (Oil, coal tar), etc., by removing low boiling components having a boiling point of less than 200 ° C., those synthesized by condensation of naphthalene, quinoline, anthracene, methyl naphthalene, etc., which were further heat-treated and hydrogenated. And the like.

When producing the desired pitch fluoride using these raw materials, for example, a method of directly reacting the raw materials with fluorine gas can be exemplified. The temperature during the reaction is
The temperature is preferably set to about 0 to 350 ° C., and more preferably to the softening point of the raw material or lower. When fluorinating carbons such as coke and graphite, it is necessary to react at a predetermined temperature or higher (coke is about 300 ° C. or more, and graphite is about 600 ° C. or more). The pressure of the fluorine gas during the reaction is not particularly limited, but is usually about 0.07 to 1.5 atm. Note that a fluorine gas diluted with an inert gas such as nitrogen, helium, argon, or neon may be used.

The pitch replaced by a halogen atom other than fluorine can be produced by the same method as described above using a desired halogen gas instead of fluorine gas, but is not limited to the above method.

The reduced product of the cyclic carbon halide is, for example, electrolytic reduction of the above-mentioned cyclic carbon halide,
It is obtained by reduction by a known method such as chemical reduction.

By using a cyclic carbon halide containing a different element (for example, nitrogen, sulfur, oxygen, silicon, etc.) such as quinoline fluoride (or its pitch) and / or its reduced product as a raw carbon material, graphene can be obtained. A graphite ribbon containing a different element in a part of the sheet can be manufactured.

The target product is synthesized by irradiating the raw material carbon material with at least one kind of light such as laser light, X-ray, electron beam (electron beam), plasma, ion beam, or the like. By heat-treating the material, or by irradiating and heating the raw carbon material (irrespective of the order of both processes), and causing a reaction in the raw material,
It can be carried out.

[0030] When the raw carbon material to perform light irradiation, usually about a wavelength 300 to 1200 nm, output: 0.1 to 10 / cm ² or so, more preferably about wavelength 400 to 800 nm, output 0.5~5mJ
Use a laser beam of about / cm ² . The type of laser light can be any of those commonly used, and is not particularly limited.For example, Nd: YAG laser, Ti: Sa laser, Dye laser, Dye + SHG laser, Ar ⁺ laser, Kr ⁺ Laser and the like.

When the raw carbon material is irradiated with an electron beam, an acceleration voltage of 1 to 10 ⁻² to 10 ⁻⁷ torr is usually applied.
Irradiation is performed at about 2000 kV (more preferably about 50 to 1000 kV).

[0032] When performing the ion beam irradiation, the raw carbon material placed in a vacuum chamber (typically 10 ^{0 -} 10 about ^-4 torr) inside, using a He ion or Ar ions were ionized,
Irradiation is performed under the conditions of an acceleration voltage of about 100 V to 10 kV (more preferably, about 200 V to 1 kV) and an ion current of about 0.01 to 100 mA / cm ² (more preferably, about 0.1 to 10 mA / cm ² ).

When the irradiation is performed to impart reaction energy to the raw carbon material, it is more preferable to use a laser beam as the irradiation source.

When performing excitation by plasma, the raw material carbon material is placed in an inert gas atmosphere or a reducing gas atmosphere, and this is brought into contact with a plasma fluid in a high energy state, whereby the intended graphite ribbon is formed. obtain. To generate a plasma fluid, an electromagnetic excitation source is used. Conditions for generating plasma can be appropriately selected according to the type of gas, gas pressure, excitation voltage, excitation current, excitation power supply frequency, electrode shape, and the like.

With respect to gases, there are some gases whose characteristics make it difficult to form a plasma state. Even in such a case, it is possible to form a plasma state by increasing the input amount of the excitation electromagnetic. Examples of the gas used in the present invention include Ar, He, Kr, and N ₂ . Among these gases, Ar, He and the like are more preferable.

The gas pressure needs to be selected in relation to the amount of excitation electromagnetic field to be supplied. That is, as the gas pressure increases, the number of gas molecules increases and the energy required to excite each gas molecule also increases, so that a large amount of excitation electromagnetic is required. For example, it is possible to generate plasma even when the gas pressure is 10 atmospheres or more, but a large power source is required, and the equipment cost is significantly increased. Also, the higher the excitation voltage and the higher the excitation current, the more plasma can be generated. However, if the input electric energy is too high or the pressure is too low, the transmission of electromagnetic energy to the gas can be performed smoothly. As a result, discharge occurs between the electrodes, and sufficient plasma particles are not generated. On the other hand, when the gas pressure is low, plasma is generated with a relatively small input excitation electromagnetic quantity, but when the pressure is too low, a sufficient amount of plasma cannot be obtained. In consideration of these factors, in the present invention, the gas pressure at the time of plasma generation is preferably in the range of 10 ⁻³ torr to atmospheric pressure (1 atm).

The electromagnetism may be either direct current or alternating current, and the material and shape of the electrodes are selected according to the type of electromagnet to be applied. As the alternating current, a low frequency of about 50 to 60 Hz, about 1 to 10 KHz and a high frequency of about 10 to 100 GHz are usually used. As industrial high frequency, 1
3.56 MHz, 40 MHz, 915 MHz, 2.45 GHz and the like are generally used. As the electrode material, stainless steel, aluminum and its alloys, ordinary steel, etc. are usually used, and the shape is a capacitive coupling type, a parallel plate type, a hollow cathode type,
It is selected from a coil or the like.

As an example of a method of generating a conveniently plasma at low cost, Ar, He, Kr, inert gases such as N _2, 1 × 10 a reducing gas or a mixture of these gases, such as hydrogen
^A desired plasma can be formed by applying a power of about 100 to 900 W to the coiled electrode by using a 13.56 MHz high frequency power supply under a reduced pressure of about ^{−3 to} 600 torr.

When heating the raw carbon material, usually 10
0 kg / cm ² to 10 ^-8 torr, preferably about 760 to 10 ^-6 torr under normal pressure to reduced pressure (more preferably under pressure of about 10 ^-1 to 10 ^-3 torr), usually 100 to 3000 ° C. Degree, preferably 10
About 0 to 2000 ° C, more preferably about 200 to 2000 ° C, particularly preferably about 200 to 1800 ° C, most preferably 200 to 1500 ° C.
Heat at about ° C. Or N ₂ , He of about 760 to 10 ^-4 torr
Alternatively, in an Ar atmosphere, usually about 100 to 3000 ° C., preferably 1
About 00 to 2000 ° C., more preferably about 200 to 2000 ° C., particularly preferably about 200 to 1800 ° C., most preferably 200 to 15 ° C.
The carbon material may be heated at about 00 ° C.

Further, in processing the raw carbon material,
At least one of the above irradiation treatments and the heat treatment may be used in combination.

The time for subjecting the raw carbon material to the irradiation treatment is as follows:
There is no particular limitation as long as the graphite ribbon is generated, and it can be appropriately set according to the irradiation means and the like. The irradiation time after reaching the predetermined condition is usually about 1 second to 100 hours, preferably about 1 minute to 200 minutes.

The time for the heat treatment is not particularly limited as long as the graphite ribbon is formed, and can be appropriately set according to the heating temperature and the like. The heating time after reaching the predetermined condition is usually about 1 second to 100 hours, preferably about 1 minute to 200 minutes.

When both the irradiation treatment and the heat treatment are performed, the treatment time is not particularly limited as long as the graphite ribbon is formed, and can be appropriately set according to the irradiation means, the heating temperature and the like. The processing time after reaching the predetermined condition is usually about 1 second to 100 hours, preferably 1 minute to 200 hours.
Minutes.

The raw carbon material synthesized by the electrolytic reduction method contains a trace amount of metal eluted from the anode.
By using such a raw material and performing a heat treatment and / or an irradiation treatment under conditions in which the metal does not evaporate, a graphite ribbon containing at least one of a metal salt and a metal between layers without performing a metal dispersion operation. Obtainable.

[0045]

According to the present invention, the following remarkable effects are achieved. (1) Light, electron beam (electron beam), irradiation treatment to irradiate ion beam, etc. to specific raw carbon material,
Alternatively, a graphite ribbon, a different element-containing graphite ribbon, or the like can be manufactured by heat-treating such a carbon material, or by irradiating and heating such a carbon material. (2) By using a different element-containing cyclic carbon halide and / or its reduced product as a raw material carbon material, a different element-containing graphite ribbon can be selectively produced. (3) The carbon material according to the present invention is a methane storage material, a hydrogen storage material, an electron beam radiation emitter, a diamond semiconductor,
Wear-resistant materials, battery electrode materials, magnetic recording media, magnetic fluids,
Useful as nanodevices, nanosolid lubricants, and other electronic materials. Furthermore, the carbon material of the present invention is also useful as a photoelectric conversion material, a light-to-light conversion material, a nano-conductive material, and the like.

[0046]

EXAMPLES Test Example 1 A reduced form of a cyclic carbon halide was synthesized by an electrolytic reduction method and a chemical reduction method.

First, a reduced form was synthesized by electrolytically reducing naphthalene pitch with a reactive anode according to the method described in JP-A No. 12-16806 except that naphthalene pitch was used as a raw material.

That is, 3 g of naphthalene fluoride pitch was charged into a flask together with the following solvent. Tetrahydrofuran 30 ml Lithium chloride 1.2 g Iron (III) chloride 1.0 g Then, after replacing the inside of the flask with nitrogen gas, a current of up to 150 mA was passed between the anode (magnesium) and the cathode (stainless steel) installed in the flask, and at room temperature. , Until the amount of electricity reached 8400C. The naphthalene fluoride pitch which became black due to the formation of -C≡C- was washed with diethyl ether, and then dried under vacuum.

On the other hand, in the chemical reduction method, the internal volume is 100 m
l Granular Mg2.8 in an eggplant flask (hereinafter referred to as reactor)
g, 0.8 g of lithium chloride, 2.0 g of iron (III) chloride and 1.0 g of naphthalene fluoride pitch and a stirrer chip, and after heating and reducing the pressure to 1 mmHg at 50 ° C. to dry the raw material,
Nitrogen gas was introduced into the reactor, and 45 ml of THF was further added.
The mixture was stirred at room temperature with a magnetic stirrer for about 20 hours. After completion of the stirring, the product was washed with diethyl ether and dried under vacuum.

When the samples obtained by the electrolytic reduction method and the chemical reduction method were observed by Raman spectrum,
In each case, 2100 cm ^-1 attributed to C≡C and
A band at 1500 cm ^-1 attributed to C = C was observed. From the above results, it was clarified that a reduced product of a cyclic carbon halide was similarly obtained by both the electrolytic reduction method and the chemical reduction method.

Example 1 A sample of a reduced product of a cyclic carbon halide prepared by the electrode reduction method of Test Example 1 was embedded in an epoxy resin, and a transmission electron microscope (TEM: HITACHI H71) was used with a microtome.
After cutting for electron beam irradiation treatment according to (00), 10 ^-6 t
The sample holder was heated to 800 ° C. under a high vacuum of orr, and irradiated with an electron beam at an acceleration voltage of 200 kV under the heating. The irradiation time was 90 minutes.

As a result of analyzing the obtained sample by electron beam diffraction and X-ray diffraction, it was confirmed that a graphite ribbon was formed. More specifically, as a result of observation by TEM, a graphene sheet (length: about 0.5 μm, width: about 5 n
m) was confirmed to form a graphite ribbon (length: about 0.5 μm, width: about 5 nm) by laminating about 10 sheets. Graphite ribbons were obtained with near 100% field of view. X-ray diffraction revealed that the interlayer spacing of the graphene sheet was 3.4 °.

Example 2 A reduced sample of a cyclic carbon halide prepared in the same manner as in Test Example 1 was placed in a reduced pressure chamber (4 × 10 ^-2 tor
r) with an ion beam (Kauffman-type ion source: argon ion beam, acceleration voltage: 500 V, ion current density:
1 mA / cm ² ) for 10 minutes.

Observation of the obtained sample using a TEM revealed that a graphene sheet (length: about 0.1 μm, width: about 3 nm)
However, it was confirmed that a graphite ribbon (length: about 0.1 μm, width: about 3 nm) was formed by laminating about seven sheets. Graphite ribbons were obtained with near 100% field of view. A part of the obtained graphite ribbon was a graphite ribbon having a bent part or a branched part in a graphene sheet as shown in FIGS. 2 and 3. Also, the result of X-ray diffraction revealed that the interlayer spacing was 3.4 °. The widths of the graphene sheet and the graphite ribbon are approximate values obtained by TEM observation.

Example 3 To a reduced sample of a cyclic carbon halide prepared in the same manner as in Test Example 1, a laser beam (Nd: YAG Laser: 632 nm, 2 mJ / pulse.cm) was applied under reduced pressure (10 ^-5 torr). ² , 10 Hz). The irradiation time was 60 minutes.

As a result of analyzing the sample by electron beam diffraction and X-ray diffraction, it was confirmed that a graphite ribbon was formed. More specifically, as a result of TEM observation, a graphene sheet (length: about 0.3 μm, width: about 7 nm)
However, it was confirmed that a graphite ribbon (length: about 0.3 μm, width: about 7 nm) was formed by laminating about 15 sheets. Graphite ribbons were obtained with near 100% field of view. Also, from the results of X-ray diffraction, the interlayer spacing was 3.
It turned out to be 4Å.

Example 4 A reduced sample of a cyclic carbon halide prepared in the same manner as in Test Example 1 was placed in a heating holder in a vacuum vessel and heated to 800 ° C. under reduced pressure (10 ⁻⁵ torr). Irradiation with laser light (Nd: YAG Laser: 632 nm, ² mJ / pulse · cm ² , 10 Hz) was performed. The irradiation time was 60 minutes. As a result of analyzing this sample by electron beam diffraction and X-ray diffraction, it was confirmed that a graphite ribbon was generated. More specifically, as a result of TEM observation, a graphene sheet (length: about
It was confirmed that a graphite ribbon (length: about 1 μm, width: about 10 nm) was formed by laminating about 20 sheets (1 μm, width: about 10 nm). Graphite ribbons were obtained with near 100% field of view. Also, the result of X-ray diffraction revealed that the interlayer spacing was 3.4 °.

Test Example 2 Except that the raw carbon material was changed to quinoline fluoride pitch,
By the electrolytic reduction method and the chemical reduction method as in Test Example 1,
A reduced product of a cyclic carbon halide was synthesized.

First, except that quinoline fluoride fluoride was used as a raw material, the reduction of cyclic carbon halide was carried out by electrolytically reducing quinoline fluoride with a reactive anode according to the method described in JP-A No. 12-16806. Was synthesized.

That is, 3 g of quinoline fluoride pitch was charged into a flask together with the following solvent. Tetrahydrofuran 30 ml Lithium chloride 1.2 g Iron (III) chloride 1.0 g Then, after replacing the inside of the flask with nitrogen gas, a current of up to 150 mA was passed between the anode (magnesium) and the cathode (stainless steel) installed in the flask, Current 8
Reduced to 400C. The quinoline fluoride pitch, which became black due to the formation of -C≡C-, was washed with diethyl ether and dried in vacuo.

On the other hand, in the chemical reduction method, the internal volume is 100 m
l Granular Mg2.8 in an eggplant flask (hereinafter referred to as reactor)
g, 0.8 g of lithium chloride, 2.0 g of iron (III) chloride and 1.0 g of fluorinated quinoline pitch and a stirrer chip,
After heating and reducing the pressure to 1 mmHg at 50 ° C. to dry the raw materials, nitrogen gas was introduced into the reactor, 45 ml of THF was further added, and the mixture was stirred at room temperature with a magnetic stirrer for about 20 hours. After completion of the stirring, the product was washed with diethyl ether and dried under vacuum.

When the samples obtained by the electrolytic reduction method and the chemical reduction method were observed by Raman spectrum,
In each case, 2100 cm ^-1 attributed to C≡C and
A band at 1500 cm ^-1 attributed to C = C was observed.

From the above results, it was clarified that a reduced product of a cyclic carbon halide was similarly obtained by both the electrolytic reduction method and the chemical reduction method.

Example 5 The sample of Test Example 2 was subjected to electron beam irradiation in the same manner as in Example 1. As a result of analyzing this sample by XPS analysis, electron beam diffraction and X-ray diffraction, it was confirmed that a nitrogen-containing graphite ribbon was generated.

As a result of observation by TEM, the graphene sheet
(Length: about 0.5 μm, width: about 7 nm), but by laminating about 7 sheets, graphite ribbon (length: about 0.5 μm, width:
(About 7 nm). Graphite ribbons were obtained with near 100% field of view. X-ray diffraction revealed that the interlayer spacing was 3.8 °.

Example 6 The sample of Test Example 2 was subjected to ion beam irradiation in the same manner as in Example 2. As a result of analyzing this sample by XPS analysis, electron beam diffraction and X-ray diffraction, it was confirmed that a nitrogen-containing graphite ribbon was generated.

As a result of observation by TEM, the graphene sheet
(Length: about 0.1 μm, width: about 3 nm), but by stacking about 5 sheets, a graphite ribbon (length: about 0.1 μm, width:
(About 3 nm). Graphite ribbons were obtained with near 100% field of view. X-ray diffraction revealed that the interlayer spacing was 3.8 °.

Example 7 The sample of Test Example 2 was irradiated with a laser beam in the same manner as in Example 3. As a result of analyzing this sample by XPS analysis, electron beam diffraction and X-ray diffraction, it was confirmed that a nitrogen-containing graphite ribbon was generated.

As a result of observation by TEM, the graphene sheet
(Length: about 0.3 μm, width: about 5 nm), by laminating about nine sheets, graphite ribbon (length: about 0.3 μm, width:
(About 5 nm). Graphite ribbons were obtained with near 100% field of view. X-ray diffraction revealed that the interlayer spacing was 3.8 °.

Example 8 The sample of Test Example 2 was irradiated with laser light under reduced pressure while heating to 800 ° C. in the same manner as in Example 4. As a result of analyzing this sample by XPS analysis, electron beam diffraction and X-ray diffraction, it was confirmed that a nitrogen-containing graphite ribbon was generated.

As a result of observation by TEM, the graphene sheet
(Length: about 1 μm, width: about 10 nm), but by stacking about 16 sheets, the graphite ribbon (length: about 1 μm, width: about 1
0 nm). Graphite ribbons were obtained with near 100% field of view. X-ray diffraction revealed that the interlayer spacing was 3.8 °.

Comparative Example 1 A carbon material was produced in the same manner as in Example 3 of WO99 / 43613. That is, except for using a product obtained by electrolytic reduction or chemical reduction of a PTFE (polytetrafluoroethylene) film as a raw material,
A carbon material was manufactured in the same manner as in Example 1.

The product obtained by electrolytic reduction or chemical reduction of a PTFE (polytetrafluoroethylene) film had a structure in which the = C = structure or -C≡C- structure was linearly arranged. .

As a result of observing the obtained carbon material using a TEM, it was confirmed that carbon nanotubes had been formed, but no graphite ribbon had been formed.

Example 9 A sample of a reduced product of a cyclic carbon halide prepared in the same manner as in Test Example 1 was placed in a vacuum carbonizing furnace, and
^-5 torr) at 800 ° C. for 60 minutes.

As a result of analyzing the obtained sample by electron beam diffraction and X-ray diffraction, it was confirmed that a graphite ribbon was formed. More specifically, as a result of TEM observation, a graphene sheet (length: about 0.2 μm, width: about 10 n
m) was confirmed to form a graphite ribbon (length: about 0.2 μm, width: about 10 nm) by laminating about 10 sheets. Graphite ribbons were obtained with approximately 15% field of view.

Example 10 A reduced sample of a cyclic carbon halide prepared in the same manner as in Test Example 1 was placed in a vacuum carbonization furnace and heated at 800 ° C. for 60 minutes in a nitrogen atmosphere.

As a result of analyzing the obtained sample by electron beam diffraction and X-ray diffraction, it was confirmed that a graphite ribbon was formed. More specifically, as a result of TEM observation, a graphene sheet (length: about 0.2 μm, width: about 10 n
m) was confirmed to form a graphite ribbon (length: about 0.2 μm, width: about 10 nm) by laminating about 10 sheets. Graphite ribbons were obtained with approximately 15% field of view.

Example 11 A sample of a reduced product of a cyclic carbon halide prepared in the same manner as in Test Example 1 was placed in a vacuum carbonizing furnace, and
^-5 torr) and heated at 1200 ° C. for 60 minutes.

As a result of analyzing the obtained sample by electron beam diffraction and X-ray diffraction, it was confirmed that a graphite ribbon was formed. More specifically, as a result of TEM observation, a graphene sheet (length: about 0.2 μm, width: about 10 n
m) was confirmed to form a graphite ribbon (length: about 0.2 μm, width: about 10 nm) by laminating about 16 sheets. Graphite ribbons were obtained with approximately 30% field of view.

Example 12 A sample of a reduced product of a cyclic carbon halide prepared in the same manner as in Test Example 1 was placed in a vacuum carbonization furnace and heated at 1600 ° C. for 60 minutes in a nitrogen atmosphere.

As a result of analyzing the obtained sample by electron beam diffraction and X-ray diffraction, it was confirmed that a graphite ribbon was formed. More specifically, as a result of TEM observation, a graphene sheet (length: about 0.2 μm, width: about 10 n
m) was confirmed to form a graphite ribbon (length: about 0.2 μm, width: about 10 nm) by laminating about 30 sheets. Graphite ribbons were obtained with near 100% field of view.

Example 13 A reduced sample of a cyclic carbon halide prepared in the same manner as in Test Example 2 was placed in a vacuum carbonizing furnace, and
^-5 torr) at 800 ° C. for 60 minutes.

As a result of analyzing the obtained sample by electron beam diffraction and X-ray diffraction, it was confirmed that a nitrogen-containing graphite ribbon was produced. More specifically, as a result of observation by TEM, a graphene sheet (length: about 0.4 μm,
It was confirmed that a graphite ribbon (length: about 0.4 μm, width: about 15 nm) was formed by laminating about 9 sheets (width: about 15 nm). About 15% of graphite ribbon
Was obtained with a visual field ratio of

Example 14 A reduced sample of a cyclic carbon halide prepared in the same manner as in Test Example 2 was placed in a vacuum carbonization furnace and heated at 1600 ° C. for 60 minutes in a nitrogen atmosphere.

As a result of analyzing the obtained sample by electron beam diffraction and X-ray diffraction, it was confirmed that a nitrogen-containing graphite ribbon was formed. More specifically, as a result of observation by TEM, a graphene sheet (length: about 0.4 μm,
It was confirmed that a graphite ribbon (length: about 0.4 μm, width: about 10 nm) was formed by laminating about 23 sheets of about 10 nm in width. The graphite ribbon is 100
% Field of view.

[Brief description of the drawings]

FIG. 1 is a view schematically showing one embodiment of a graphite ribbon of the present invention.

FIG. 2 is a diagram schematically showing one embodiment of a graphite ribbon in which a graphene sheet has a bent portion.

FIG. 3 is a diagram schematically showing one embodiment of a graphite ribbon in which a graphene sheet has a branched portion.

FIG. 4 is a high-resolution transmission electron microscope image of the graphite ribbon obtained in Example 1.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Katsuhiro Sasaki, Osaka Gas Co., Ltd. 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka (72) Rikusei Kyoya 6-407, Sakaemachi, Ushiku-shi, Ibaraki 72) Inventor Yoshiki Koga 2-11-5 Funato, Abiko-shi, Chiba (72) Inventor Akiko Goto 2-2-14-105 Ninomiya, Tsukuba-shi, Ibaraki F-term (reference) 4G046 AA08 CA07 CB01 CC01 CC06

Claims (7)

[Claims] 1. A graphite ribbon having a structure in which 2 to 70 layers of ribbon-like graphene sheets are laminated. 2. The graphite ribbon according to claim 1, wherein the graphene sheets are stacked in parallel with the length direction of the ribbon. 3. The graphite ribbon according to claim 1, wherein the graphene sheet includes a graphite ribbon having a bent portion or a branched portion. 4. The graphite ribbon according to claim 1, wherein the graphene sheet contains a different element. 5. The graphite ribbon according to claim 1, wherein at least one of a metal salt and a metal is contained between layers of the graphene sheet. 6. A carbon material comprising the graphite ribbon according to claim 1. 7. A light, an X-ray, an electron beam, a cyclic carbon halide as a raw material carbon material and / or its reduced product
By subjecting the carbon material to an irradiation process of irradiating at least one of plasma and ion beams, or to a heating process of heating the carbon material, or by subjecting the carbon material to the irradiation process and the heating process, How to manufacture.