JP2003342013A - Method for manufacturing graphite-like substance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a nano-size graphite-like substance with excellent heat resistance characteristics and the like at a lower temperature, with better efficiency and at a low cost. <P>SOLUTION: The nano-size graphite-like substance is manufactured by converting a solid organic polymer (a polyacetylene type polymer and the like) whose structure is controlled by a molecular orientation into graphite with heat treatment or pyrolysis. A molecular orientated organic polymer can be obtained by using an orientation field such as a liquid crystal field, a magnetic field or the like, or the orientation field in which they are combined. The shape of the organic polymer can be a film, a thin film, a sheet, a powder or the like. The heat treatment can be performed in vacuum or in an inert gas atmosphere. The organic polymer may be irradiated with high energy rays (an electron beam or a laser beam) while heat treated. The heat-treating temperature is about 500-1,800°C. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a graphite-like carbon material, particularly a nano-sized graphite-like carbon material.

[0002]

2. Description of the Related Art Graphite has excellent properties such as thermal conductivity, heat resistance, chemical resistance, and electrical conductivity.
It is widely used industrially as a heat conductor, an electrode, a heating element, a heat insulating material, an electric field shield material, a sputtering target material, and other electronic materials.

With respect to graphite, it has been predicted that a carbon material having a graphite end will exhibit functionality in calculation of molecular orbital (MO) and the like (for example,
M.Fujita, K.Wakabayashi, K.Nakada, K.Kusakabe, JP
hys.Soc.Jpn.65, 1920, 1996, and K. Wakabayashi, Mol
Cryst Liq Cryst, 340, 379, 2000 etc.).

Further, graphite has been applied to electronic devices in recent years, and its use as an electronic material has been attracting attention. In particular, since the easy electron emission property of carbon nanotubes was discovered as a cold cathode electron source, it was applied to electron sources of electronic devices, such as field emission cold cathodes, light source lamp electron sources, and flat panels. Attention is focused on application to electron sources. For example, Japanese Patent Laid-Open No. 2000-12371
No. 2 discloses an electrolytic radiation cold cathode including an electron emitting portion and an electrode for applying a voltage to the electron emitting portion, wherein the electron emitting portion emits a conductive carbon material and electrons. A field emission cold cathode composed of a mixture with a carbon material is disclosed. This document also discloses that the electron-emitting carbon material is a fullerene or a carbon nanotube.

As a method for producing such graphite,
A method of obtaining a graphite film by heat-treating a polymer material as a starting material is known. Specifically, Japanese Patent Application Laid-Open No. 61-275114 discloses, as a polymer material, polyphenylene oxadiazole (PO).
A method of converting D) into graphite by heat-treating it at a temperature of 1600 ° C. or higher (preferably 1800 ° C. or higher, more preferably 2000 ° C. or higher) is disclosed. This document describes that a film formed by casting POD has high crystallinity and orientation. JP-A-61-27
5115 discloses at least one polymer selected from polybenzothiazole, polybenzobisthiazole, polybenzoxazole, polybenzobisoxazole, and polythiazole at 1800 ° C. or higher (preferably 2 ° C.).
It is disclosed that the graphite is heated at a temperature of 000 ° C. or higher, more preferably 2500 ° C. or higher to convert it into graphite. It is also described in this document that the coating or fiber obtained by casting or spinning the polymer has high crystallinity, and that the carbon material has orientation due to this crystallinity. Japanese Patent Laid-Open No. 2000-169125 discloses that a sheet-shaped polymer material selected from aromatic polyimide, aromatic polyamide and polyoxadiazole is heated at 400 to 800 ° C. under an inert atmosphere.
At a heating rate of 10 ° C./min and at least 24
A method of heating to 00 ° C. to produce an expanded graphite material is disclosed.

However, since these methods mainly aim to obtain graphite having a large area or large crystals, all of them are polymer materials composed of polycyclic aromatic compounds suitable for a large area. Is the starting material. Further, in these documents, no particular attention is paid to nano-sized graphite and the like. Further, in order to graphitize a polymer material composed of these polycyclic aromatic compounds and the like, heat treatment at a high temperature (for example, 2000 ° C. or higher) is performed because a carbon condensed ring is formed by elimination of a hetero atom. is necessary.

[0007]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a method for producing a graphite-like substance excellent in heat resistance and the like at a lower temperature and at a lower cost.

Another object of the present invention is to provide a method for producing a nano-sized graphite-like substance more efficiently.

[0009]

Means for Solving the Problems The inventors of the present invention have made extensive studies on the above-mentioned method for producing graphite, and as a result, have controlled the solid structure of an organic polymer substance (eg, molecular orientation) as a precursor polymer of graphite. It has been found that when an organic polymer (for example, a non-aromatic or non-heterocyclic linear conjugated organic polymer) is heat-treated, a nano-sized graphite-like substance is efficiently produced even at a low heat-treatment temperature. Was completed.

That is, according to the method of the present invention, the solid organic polymer having a controlled structure is subjected to heat treatment or thermal decomposition to be converted into graphite to produce a graphite-like substance. That is, the organic polymer substance is subjected to solid structure control (for example, molecular orientation) and then heat-treated to be converted into graphite.
The organic polymer may be a non-aromatic or non-heterocyclic conjugated organic polymer such as polyacetylene-based polymer, and the form of the organic polymer is film, thin film, sheet, powder, etc. May be The structure-controlled solid organic polymer is a molecularly oriented organic polymer, for example,
It may be an organic polymer which is molecularly aligned by various alignment fields (a liquid crystal field, a magnetic field, etc. or an alignment field combining these fields). Specifically, for example, the organic polymer may be aligned in a specific direction by preparing or synthesizing the organic polymer with an alignment field composed of liquid crystal (an alignment field utilizing the characteristics of liquid crystal). The organic polymer may be molecularly aligned by (alignment method using magnetic field), or the organic polymer may be molecularly aligned by liquid crystal field (alignment method using both liquid crystal field and magnetic field) on which magnetic field acts. Good. The heat treatment can usually be performed in a vacuum or in an inert gas atmosphere, and the heat treatment may be performed together with irradiation with a high energy beam (electron beam, light such as laser beam). The heat treatment temperature is, for example, 500
C. to 1800.degree. C., particularly 600.degree. C. to 1500.degree. In the present invention, a nano-sized graphite-like substance can be produced by heat-treating a conjugated organic polymer molecularly oriented by an orientation field at a temperature of 500 ° C to 1800 ° C.

The present invention also includes the graphite-like substance obtained by the above production method. This graphite-like material
It may be a nano-sized graphitic carbon material.

In the present invention, since an organic polymer substance having a controlled solid structure (preferably molecular orientation) (polyacetylene polymer etc.) is used as a starting substance, at least 200
Compared with the conventional manufacturing method that requires high temperature treatment of 0 ° C. or higher, the heat treatment temperature can be remarkably lowered and nano-sized graphite can be efficiently manufactured.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an organic polymer having a controlled solid structure, preferably an organic polymer having a molecular orientation, is used as a graphite precursor. Organic polymers are usually
It can be carbonized or graphitized by heat treatment.
Examples of such polymers include thermosetting polymers (such as aromatic polyimide), aromatic thermoplastic polymers (such as aromatic polyamide), conductive polymers (polyacetylene-based polymers, polyphenylene, polyphenylene vinylene, polynaphthalene vinylene, poly Polyphenylene-based polymers such as thienylenevinylene, polyphenylenebenzobisthiazole, polyphenylenebenzobisoxazole, etc., heterocyclic systems such as polybenzothiazole, polybenzobisthiazole, polybenzoxazole, polybenzobisoxazole, polythiazole, polyoxadiazole Polymer, polypyrrole, polyaniline, etc.), liquid crystalline polymer (aromatic polyester liquid crystalline polymer, polyesteramide liquid crystalline polymer, etc.), orientation component (liquid crystal, DN)
Linear polymer such as polyene having a carbon / carbon double bond or polyyne having a carbon / carbon triple bond in the molecule (for example, polyacetylene,
Polyacetylene-based polymers such as polydiacetylene or polyacetylene-based polymers) and the like. In addition,
The liquid crystal and the liquid crystalline polymer have an alignment structure, and when the alignment component (liquid crystal polymer, DNA) is bonded to the polymer, the molecular alignment of the polymer can be improved. Examples of the liquid crystal include smectic liquid crystal, nematic liquid crystal, cholesteric liquid crystal (chiral nematic liquid crystal), discotic liquid crystal, and the like, and may be thermotropic liquid crystal or lyotropic liquid crystal. These graphite precursors can be used alone or in combination of two or more.

Among these graphite precursors, conjugated organic polymers (for example, linear conjugated organic polymers or non-aromatic or non-heterocyclic linear conjugated organic polymers), especially polyene or polyyne. A conjugated organic polymer having a structure (polyacetylene-based polymer that is relatively easy to synthesize) is preferable.

The polyacetylene-based polymer includes homopolymers or copolymers of acetylene-based monomers. Further, the polyacetylene-based polymer may be a polyacetylene derivative having a substituent other than polyacetylene, and examples of the substituent include a halogen atom such as chlorine and a fluorine atom, a hydroxyl group, and a C _1-4 alkoxy group. C, C _1-4 alkyl group, C _3-10 cycloalkyl group, phenyl group, etc.
Examples thereof include _6-12 aryl groups and aralkyl groups such as benzyl groups. As typical polyacetylene derivatives,
For example, polyphenylacetylene, polyphenylchloroacetylene, polyfluoroacetylene and the like can be exemplified.

Incidentally, a normal linear thermoplastic polymer (for example, a polymer such as polyethylene or polypropylene) is
When carbonized at a temperature of 1000 ° C or lower, it becomes amorphous,
Does not form a graphite structure.

Method of controlling solid structure (method of molecular orientation)
Is not particularly limited, and the organic polymer can be molecularly oriented in various orientation fields. As a method of controlling the solid structure (method of molecular orientation), usually, stretching (for example, uniaxial stretching with a draw ratio of about 1.2 to 10 times in one direction), liquid crystal field, magnetic field (for example, about 1 to 10 Tesla). ) Etc. can be illustrated. Further, in order to improve the orientation of the graphite precursor, an epitaxial polymerization method or the like may be used. These control methods may be used alone or in combination, and may be, for example, a combination of a liquid crystal field and a magnetic field (for example, preparation of an organic polymer in the presence of liquid crystal aligned in the magnetic field). The molecular orientation of the organic polymer in the liquid crystal field (orientation field composed of liquid crystals) includes, for example, aligning the organic polymer along the orientation of the liquid crystal by polymerizing monomers in the liquid crystal field in which the liquid crystal is oriented. Examples thereof include a method of mixing, a method of mixing a liquid crystal and an organic polymer, and aligning the organic polymer with the alignment of the liquid crystal. In this method, a magnetic field may be applied to align the liquid crystal. As a method of molecularly orienting an organic polymer by a magnetic field, a method of orienting the conjugated organic polymer (particularly an organic polymer in a solution-like state in which the viscosity is reduced) by applying a magnetic field, while applying a magnetic field Examples thereof include a method of polymerizing the monomer of the conjugated organic polymer. In a preferred method, the organic polymer can be molecularly aligned in a liquid crystal field under the action of a magnetic field. Among these control methods, in order to uniformly control the alignment at the molecular level, alignment by a liquid crystal field or a combination of a liquid crystal field and a magnetic field is preferable. For example, by polymerizing a conjugated organic polymer (polyacetylene polymer, etc.) monomer in a liquid crystal field (in the presence of an aligned liquid crystal) while applying a magnetic field, a molecularly aligned organic polymer can be efficiently produced. Can be generated.

In the above method, the use of a magnetic field is effective because liquid crystal molecules tend to be oriented in the magnetic field direction. In particular, since the low-molecular liquid crystal is likely to be aligned in the magnetic field direction in a shorter time, the polymer molecule synthesized in this reaction field is likely to be aligned in parallel with the alignment direction of the liquid crystal molecule to be polymerized.

When the organic polymer constituting the graphite precursor is molecularly oriented, the molecules are easily bonded to each other and the graphitization is promoted. Therefore, it becomes possible to prepare graphite at a lower temperature. In addition, since it can be prepared at a lower temperature, it is advantageous in terms of energy and
The selection range of the shape of the graphite-like substance becomes wider, for example, ribbon shape, plate shape, hollow circular or oval shape (elliptical shape), hollow polygonal shape, hollow short rod shape (nanotube shape), hollow elliptical shape. It is possible to obtain a graphite-like substance such as a body. Moreover, high-purity nanographite can be obtained. When the oriented polymer and the non-oriented polymer are heat-treated at the same heating temperature, when the oriented polymer is used as a raw material, the crystallinity of nanographite increases and The size in the specific direction can be relatively large, and elongated nano-sized graphite is produced.

The shape of the graphite precursor (organic polymer) is not particularly limited, and may be a two-dimensional structure (film, thin film, sheet), one-dimensional structure (linear), powder or powder. It may have an amorphous shape or the like. A preferable organic polymer has a two-dimensional structure or a granular shape, and is usually a thin film or a sheet. The size of the organic polymer is not particularly limited and can be appropriately selected depending on the shape. For example, in the case of an organic polymer having a two-dimensional structure, the thickness is 500 μm or less (for example, 10 to 200 μm, preferably 10 to 10 μm).
0 μm). In the case of a powdery organic polymer, the average particle size is 1 to 500 μm, preferably 5 to 10 μm.
It may be about 0 μm.

The heat treatment or pyrolysis is performed in vacuum (vacuum degree 20).
It is preferably carried out under an atmosphere of 0 Pa or less) or an inert gas (for example, nitrogen, helium, argon, etc.). When the heat treatment is carried out in an inert gas atmosphere, the pressure may be normal pressure, reduced pressure or increased pressure, but it is slightly higher than the normal pressure (for example, 0.1% or less) in order to prevent gas from flowing into the heat treatment system from the surroundings. It is preferable to set the pressure to about 1 MPa, especially about 0.1 to 0.5 MPa).

Since the present invention uses the above-mentioned unique raw materials,
It has a feature that the heat treatment temperature (or graphitization temperature) can be reduced without requiring a high temperature of 2000 ° C. or higher as in the conventional case. The heat treatment temperature (or thermal decomposition temperature) is, for example, 500 ° C to 1800 ° C, preferably 600 ° C to 15 ° C.
00 ° C, more preferably about 700 ° C to 1400 ° C,
In particular, it can be selected from a temperature range of about 800 ° C to 1200 ° C. For example, a conjugated organic polymer molecularly oriented by an orientation field (such as a conjugated linear polymer such as a polyacetylene polymer) is treated at 500 ° C to 1800 ° C (for example, 750 ° C to 13 ° C).
A nano-sized graphite-like substance can be produced by heat treatment at a temperature of about 00 ° C. The rate of temperature increase is not particularly limited, and is, for example, 1 to 25 ° C./minute (for example,
3 to 15 ° C./minute).

The heat treatment time is not particularly limited as long as the graphite-containing material is produced, and can be appropriately set according to the heating temperature and the like. Usually, after reaching a predetermined temperature, 1
It can be selected from the range of about seconds to 100 hours. The heat treatment time is usually 1 minute to 500 minutes, preferably 1 minute to 200 minutes (for example, 10 minutes to 200 minutes), and more preferably 20 minutes to 180 minutes.

In order to further reduce the graphitization temperature, it is preferable to combine the action or irradiation of high energy rays with heat treatment. As the high-energy ray (or electromagnetic wave), for example, X-ray, electron beam, laser light, etc. can be used. Irradiation with electron beams or laser light enables graphitization at a lower heating temperature. These high energy rays may be combined and irradiated.

In the preparation of the graphite-like substance, the order of the heat treatment and the irradiation treatment with the high energy ray is not particularly limited, and the high energy ray may be applied to the organic polymer,
The carbonaceous material (including graphitized carbon material) produced from the organic polymer may be irradiated. For example, the above raw material organic polymer may be subjected to heat treatment by irradiating or irradiating with a high energy ray, or may be irradiated with high energy ray in the heat treatment process from the raw material organic polymer to the graphite-like substance. A carbon material (raw carbon material that may be graphitized) generated from an organic polymer may be irradiated with a high energy ray while being heat-treated as necessary. Usually, by subjecting a carbon material (non-graphitized raw material carbon material or graphitized raw material carbon material) generated from a molecularly oriented organic polymer to irradiation treatment and heat treatment and reacting in the raw material organic polymer. Graphitization takes place. The order of the irradiation treatment and the heat treatment is not particularly limited in the carbon substance generated from the organic polymer (particularly, the non-graphitizing raw material carbon substance which has not been heat-treated at the predetermined temperature for the predetermined time), and the irradiation treatment and the heat treatment are simultaneously performed. Or you may go in parallel.

When the organic polymer material is irradiated with light, laser light can be usually used. The wavelength of laser light is 100 to 1200 nm, preferably 300 to 120.
0 nm (for example, 400 to 800 nm), and output is 0.1 to 10 mJ / cm ² , preferably 0.5.
It may be about 5 mJ / cm ² . The type of laser light is not particularly limited, and a conventional laser light can be used. For example, a solid-state laser (Nd: YAG laser, Ti: Sa laser), a gas laser (He-Ne laser; Ar ⁺ laser,
Rare gas ion lasers such as Kr ⁺ lasers) and excimer lasers (rare gas excimer lasers such as Ar ₂ lasers, Kr ₂ lasers, Xe ₂ lasers; ArF lasers, Kr
Rare gas halide lasers such as F lasers, KrCl lasers, XeF lasers, and XeCl lasers; nitrogen lasers), dye lasers, and dye + SHG lasers.

The electron beam irradiation is usually 10 ^-2 to 10 ^-7 to
It can be performed under reduced pressure of about rr at an acceleration voltage of about 2000 kV (preferably about 50 to 1000 kV). X-ray irradiation can be performed by a conventional method.

The irradiation time of the high energy ray is not particularly limited as long as the graphite-containing material is produced, and can be set appropriately according to the irradiation means. The irradiation time can be selected from the range of about 1 second to 100 hours, and usually 1 minute to 2 hours.
00 minutes (for example, 10 minutes to 200 minutes), preferably 20 minutes
Minutes to 150 minutes.

When the irradiation treatment and the heat treatment are combined, the treatment time (irradiation time and heating time) is not particularly limited as long as the graphite-containing material is produced, and depending on the irradiation means, the heating temperature, etc., 1 second to 50 seconds. The time can be selected from a range of about 1 minute to 200 minutes (for example, 10 minutes to 15 minutes).
0 minutes).

With such a method, a graphite-like substance can be efficiently obtained. In particular, a nano-sized graphitic carbon material can be obtained.

The form of the nano-sized graphite-like substance (nano-sized graphite) is not particularly limited, and has a three-dimensional structure (such as polygonal thrust or cone shape which may be hollow) or two-dimensional structure (ribbon-like, Plate shape, circular shape or oval shape that may be hollow, polygonal shape that may be hollow), one-dimensional structure (short rod shape that may be hollow (nanotube shape), etc.), particle shape, etc. Various forms, and these forms may be mixed. Although the nano size of the graphite-like substance is not particularly limited, the average diameter of the nano size graphite is, for example, 0.7 to 300 nm, preferably 1 to 100 n in a planar shape.
m, more preferably 1 to 50 nm (for example, 5 to 50 nm).
nm).

Graphite material (carbon material) of the present invention
Can be used in various applications, for example, electron beam emitters, methane storage materials, hydrogen storage materials, diamond semiconductors, abrasion resistant materials, battery electrode materials, magnetic recording media, magnetic fluids, nano devices, nano solid lubrication. It is useful for agents and other electronic materials. Furthermore, the carbon material of the present invention is also useful as a photoelectric conversion material, an electro-optical conversion material, a nano conductive material, and the like.

[0033]

According to the present invention, since a specific organic polymer is heat-treated to be graphitized, a graphite-like substance having excellent heat resistance can be manufactured at a lower temperature and at a lower cost. Further, a nano-sized graphite-like substance can be efficiently produced.

[0034]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

Example 1 A polyacetylene (hereinafter simply referred to as PA) thin film was synthesized from acetylene gas in a nematic liquid crystal field oriented using a Ziegler / Natta catalyst and in a magnetic field (5 Tesla). This PA thin film had a structure in which the fibril structure constituting the PA thin film was oriented in a specific direction as a whole, reflecting the structure of the oriented nematic liquid crystal field. This oriented PA thin film is about 8 ° C / in vacuum (vacuum degree about 100Pa).
The temperature was raised to 1000 ° C. at a rate of min, and pyrolysis was performed at this temperature for 1 hour to carbonize and graphitize the PA thin film. When the nanostructure of the produced carbon material was examined by an electron microscope, the results shown in FIG. 1 were obtained. From FIG. 1, a ribbon-shaped graphite structure having a width of 50 nm or less and a thickness of 5 to 10 nm is observed. A large number of nanographite structures having such a shape were formed in the generated carbon substance.

Example 2 The PA thin film sample used in Example 1 was subjected to 600 ° C. at a rate of about 8 ° C./min in vacuum (vacuum degree of about 100 Pa).
The temperature was raised to 1, and pyrolysis was performed at this temperature for 1 hour to carbonize and graphitize the PA thin film.

When the nanostructure of the produced carbon material was observed with an electron microscope, various forms of layered structures, for example,
In addition to a ribbon-like or plate-like form in which a large number of graphite nets overlap each other, a layered structure such as a circular or polygonal form was observed. From the results of layer spacing and electron diffraction, the structures of these morphologies were confirmed to be fine graphite crystals. In the structure (or graphite crystal) of the above-mentioned form, the size of the small crystal was about several nm.

Example 3 The PA thin film sample used in Example 1 was embedded in an epoxy resin, and the sample was subjected to electron beam irradiation treatment by a transmission electron microscope (TEM: HITACHI H7100) using a microtome. After cutting, the sample holder was heated to 500 ° C. under a high vacuum of 10 ⁻⁶ torr and heated to 2
The electron beam was irradiated at an acceleration voltage of 00 kV. Irradiation time is 9
It was 0 minutes.

When the nanostructure of the produced carbon material was observed with an electron microscope, the width was 50 nm or less and the thickness was 5 to 10 n.
A ribbon-like graphite structure of about m was observed. A large number of nanographite structures having such a shape were formed in the generated carbon substance.

Example 4 For the PA thin film sample used in Example 1, a laser beam (Hd: YAG laser :) was produced under reduced pressure (10 ⁻⁵ torr).
It was irradiated with 632 nm, ² mJ / pulse · cm ² , 10 Hz). The irradiation time was 60 minutes.

When the nanostructure of the produced carbon material was observed with an electron microscope, the width was 50 nm or less and the thickness was 5 to 10 nm.
A degree of ribbon-like graphite structure was observed. A large number of nanographite structures having such a shape were formed in the generated carbon substance.

[Brief description of drawings]

FIG. 1 is a transmission electron micrograph of the graphite-like substance obtained in Example 1.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Chiharu Yamaguchi             4-1-2 Hirano-cho, Chuo-ku, Osaka City, Osaka             Gas Co., Ltd. (72) Inventor Kuji Matsui             4-1-2 Hirano-cho, Chuo-ku, Osaka City, Osaka             Gas Co., Ltd. (72) Inventor Yoshinori Koga             2-11-5 Funato, Abiko City, Chiba Prefecture F-term (reference) 4G146 AA02 AB04 AC03B AD05                       AD22 AD23 BA13 BA42 BA43                       BB01 BC04 BC15 BC18

Claims (13)

[Claims] 1. A method for producing a graphite-like substance, which comprises subjecting a solid organic polymer having a controlled structure to a heat treatment to convert it into graphite. 2. The method according to claim 1, wherein the organic polymer having a molecular orientation is heat-treated. 3. The method according to claim 1 or 2, wherein the organic polymer molecularly oriented by the orientation field is heat-treated. 4. An organic polymer is prepared in an alignment field composed of liquid crystal, and the organic polymer is aligned in a specific direction.
3. The production method according to any one of item 3. 5. The production method according to claim 1, wherein the organic polymer is molecularly oriented by a magnetic field. 6. The manufacturing method according to claim 1, wherein the organic polymer is molecularly aligned in a liquid crystal field under the action of a magnetic field. 7. The production method according to claim 1, wherein the organic polymer is a polyacetylene-based polymer. 8. The production method according to claim 1, wherein the organic polymer is in the form of a film, a thin film, a sheet or a powder. 9. The manufacturing method according to claim 1, wherein the heat treatment is performed in a vacuum or in an inert gas atmosphere. 10. The manufacturing method according to claim 1, wherein the heat treatment and the irradiation with high energy rays are performed. 11. The production method according to claim 1, wherein the conjugated organic polymer molecularly oriented by the orientation field is heat-treated at a temperature of 500 ° C. to 1800 ° C. to produce a nano-sized graphite-like substance. 12. A graphite-like substance obtained by the manufacturing method according to claim 1. 13. The graphite-like carbon material according to claim 12, which is a nano-sized graphite-like carbon material.