JP2001019547A - Production of carbon/graphite compound molding product of complex shape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for inexpensively and efficiently producing a carbon/graphite compound molding product having characteristics required for fuel cell separator plate, such as flexural strength, electrical conductivity, gas permeability, etc., and complex shape. SOLUTION: In this method for producing a carbon/graphite compound molding product having a complex shape comprises kneading a heavy composition containing a carbonaceous precursor compound having self sinterability in carbonization such as tar or pitch with a graphitic carbon fine particle to give a complex composition, grinding and granulating the composition to give granulated powder, press molding the granulated powder to form a raw molding product, subjecting the raw molding product to mechanical processing and then carbonizing the mechanically processed material, the grinding and the mechanical processing are carried out while cooling a grinding jig and a processing jig to be used, the complex composition and the periphery of the raw molding product part to a temperature range not to melt the heavy composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a carbonaceous carbon precursor compound having self-sintering properties, which is obtained by coating the surface of at least one type of graphite carbon fine particles selected from the group consisting of artificial graphite and natural graphite. The present invention relates to a method for producing a carbon / graphite composite molded article having a complicated shape, which comprises pulverizing, granulating, molding, processing, and carbonizing a composite composition under specific conditions. The present invention relates to a carbon / graphite composite molding having a complex shape that satisfies the characteristics required for separator plates of solid polymer type and phosphoric acid type fuel cells such as bending strength, electrical conductivity, thermal conductivity, gas permeability, corrosion current and the like. A method for producing a body is provided.

Further, the present invention relates to a method for removing carbon products having a complicated shape, such as coal tar, petroleum heavy oil, coal tar pitch and petroleum pitch, which are found in grooved separator plates of polymer electrolyte fuel cells and phosphoric acid fuel cells. A γ-component (quinoline-soluble toluene-insoluble component) containing a self-sintering carbonaceous precursor that exhibits self-sintering properties at the time of carbonization, which can be easily obtained in the carbon industry, has a content of less than 5%, preferably less than 3%. Composition having an average particle size of 10 to 70 μm, preferably 15 to 60 μm
The surface of the graphitic carbon particles having a particle size distribution was coated, and the content of the light boiling point fraction in the heavy composition was adjusted by heating or vacuum heating after the coating step so as to be solid at room temperature. Conditions under which the composite composition obtained by pulverization in a temperature range where the composite composition does not melt (sometimes referred to as pulverization in the sense of performing pulverization that does not change the particle size distribution inherent to graphite particles as much as possible) is not melted After press forming the granulated powder obtained by granulation at room temperature, the binder component is melted by the heat generated by the friction between the processing jig and the formed product, and the formed product is deformed or a fine work shape is formed. As a method for avoiding the loss, the complicated shape required for the separator plate is stamped at high speed while cooling the processing jig and the periphery of the formed body in contact therewith to a temperature range where the heavy composition does not melt. Fuel cell There is provided a method of producing a carbon-graphite composite molded article having a complicated shape typified by regulator.

[0003]

2. Description of the Related Art Various methods for producing a composite material comprising carbonaceous carbon and graphitic carbon have been proposed, and at least one type of carbonaceous carbon powder selected from organic carbon and carbonaceous carbon, artificial graphite, and natural carbon. Many use at least one kind of graphite carbon powder selected from graphite. There are various purposes for the composite of carbonaceous carbon and graphitic carbon, but in general, the combination of them can impart the characteristics of graphite to a molded product obtained by firing at about 1000 ° C. In addition, the weak point of graphite carbon can be compensated for by carbon carbon.

[0004] For example, JP-A-59-26907 discloses an example in which 20 parts by weight of a resole-based phenol resin is added at room temperature to 80 parts by weight of graphite fine powder containing 99% of particles having a particle size of 44 µm or less which has been previously heat-treated at 3000 ° C. The mixed paste is roll-formed (peripheral speed: 0.3 m / min) to form a sheet having a thickness of 4 mm. After this is cured, it is heat-treated to a maximum temperature of 1000 ° C. at a heating rate of 1000 ° C./10 hours to obtain a product. The product characteristics when pressure-cured (0.1 kg / cm ³ ) after roll forming are as follows: size: 300 mm × 400 mm × thickness 3.2 mm bulk density: 1.703 (g / cm ³ ) Specific resistance: 165 × 10 ^{− 5} (Ω · cm) Flexural strength: 323 (kg / cm ² ) Air permeability: 3.5 × 10 ^-5 (cm ² / sec)

[0005] In this publication, graphite carbon shares the low specific resistance required for a phosphoric acid type fuel cell separator plate for the purpose of compounding organic carbon and graphitic carbon, and the resorptive phenolic resin carbide, The goal is to provide the desired function by sharing glassy carbon. One of the present inventors discloses in Japanese Patent Application Laid-Open No. 61-199737 that a quinoline-insoluble content: 70% by weight or less, a mesophase content: 40%
As described above, the upper limit of the heat melting temperature; the carbonization yield at 400 ° C. and 1000 ° C .; the powder obtained by mixing the mesophase-containing pitch having at least 70% properties and the graphite powder is preferably at least the heat melting temperature of the pitch. After heating and press forming, baking at an appropriate temperature in an inert atmosphere to change the volume at the time of baking at 1000 ° C .; dimension of less than 1% of linear shrinkage between raw and baked products of 3% or less While having stability, volume resistivity: 5.0 mΩ · cm, bending strength:> 2
A method for producing a graphite-like molded product having a characteristic of 00 kg / cm ² suitable for a separator plate has been proposed.

In Japanese Patent Publication No. 7-35250,
Japanese Patent Application Laid-Open No. 61-199737 discloses a method for producing a graphitic molded article having the same characteristics as described above, in which a light fraction in a tar fraction containing a mesophase pitch precursor in which graphite fine powder is suspended is converted into an inert gas. And heating to 350 to 500 ° C. to distill off the solution, and discloses a method using a carbonaceous precursor in which a mesophase-containing pitch containing 5 to 90% by weight of a quinoline-soluble component is precipitated on the surface of the graphite fine powder. .

In Japanese Patent Publication No. 4-75189,
(1) a step of suspending graphite powder in a tar fraction containing a mesophase pitch precursor, and (2) a step of suspending the suspension in an inert gas (eg, nitrogen gas, carbon dioxide gas, argon, etc.).
A step of heat-treating at 0 to 500 ° C. to obtain a carbonaceous precursor in which mesophase pitch is generated on graphite particles, and (3) a step of pressure-forming the carbonaceous precursor at 400 to 800 ° C. to form a formed body (4) discloses a method for producing a graphitic molded body, which comprises a step of carbonizing or graphitizing the formed body under an inert atmosphere.

This manufacturing method discloses a method of hot pressing as a method for obtaining a formed product obtained by molding a carbonaceous precursor. (3) can reduce the distortion and residual stress of the carbonized product caused by the subtle difference in the linear shrinkage rate generated in the process of baking a raw product in which a carbonaceous precursor powder is formed into a complex shape such as a grooved separator plate. This can be solved by the hot pressing process shown. In Japanese Patent Publication No. 6-102530, the process (3) described in Japanese Patent Publication No. 4-75189 is omitted, and a graphite mold or the like is used, and under a vacuum or an inert gas atmosphere, at 800 to 3000 ° C. Discloses a method for producing a graphitic molded article by pressure molding.

According to the invention, a grooved separator having a large number of grooves orthogonal to the front and back can be formed by one shot. At the same time, the characteristics required for the fuel cell separator plate, such as gas impermeability, thermal conductivity, and electrical conductivity, can be satisfied. Japanese Patent Application Laid-Open No. 62-187167 discloses a method for producing a graphite-like molded article having excellent gas impermeability which can be used as a gas separator of a phosphoric acid type fuel cell in a simplified process by using coal tar and naphtha decomposition. 350 residues
Quinoline insolubles obtained by heat treatment at about 550 ° C .; 95
Wt% or less, mesophase content; 35 wt% or less, 1
Carbonization yield at 000 ° C .; Mesophase-containing pitch of 70% by weight or more is added in an amount of 5 to 60 parts by weight based on 100 parts by weight of graphite powder selected from scale-like natural graphite or artificial graphite. 700 to 3 at a heating rate of about 150 to 3000 ° C./hour under an inert gas atmosphere.
A method of heating to 000 ° C. and press-molding to a pressure of about 50 to 2000 kg / cm ² has been proposed.

Japanese Patent No. 2566589 discloses a carbon-based composite formed from one or more materials selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals and metal compounds, and a mesophase-containing pitch. In the method for producing a raw material, (1) one or more materials selected from graphitic carbon, carbonaceous carbon, inorganic compounds, metals and metal compounds are suspended in a tar fraction containing a mesophase pitch precursor. (2) aliphatic or alicyclic hydrocarbons having 5 to 20 carbon atoms and (ii) aliphatic or alicyclic ketones having 3 to 5 carbon atoms in the suspension slurry. One or more solvents selected from the group consisting of compounds are added at a solvent ratio (Sn) of 2 to 15 (solvent weight / raw material tar weight) and treated at 0 to 60 ° C. A polycyclic aromatic polymer containing a phase precursor is precipitated, and the treated solvent is separated and the treated slurry is subjected to a rinsing solvent ratio (Sr) of 1 to 15 (solvent weight / raw material tar weight) in a ratio of 0 to 60. Washing at a temperature of 360 ° C. to separate a mixture comprising the material and a polycyclic aromatic polymer containing a mesophase precursor; (3) heat treating the mixture at 360 to 520 ° C. in an inert gas atmosphere. A step of forming a ring-containing aromatic polymer into a mesophase-containing pitch.
Disclosed is a method for producing a raw material of a carbon-based composite molded product, which comprises using a process.

According to this method, the surface of powders such as SiC, AlN, B ₄ C, TiC and Si ₃ N _{4 as well as} graphitic carbon and carbonaceous carbon can be completely covered with the mesophase-containing pitch. Therefore, it has a feature that a uniform pitch coating can be performed on a plurality of composition-containing powder surfaces. Further, acetone, heptane and the like can be used as a solvent to be used. Also, Japanese Patent No. 2566595 discloses the above-mentioned Patent No. 256
For example, a composite powder composed of graphitic carbon coated with a mesophase-containing pitch prepared in Japanese Patent No. 6589 is used as an example. An essential carbon-based powder granulation method is disclosed.

The granulation method is a carbon-based powder containing a self-sintering carbon-based powder and, if desired, at least one powder selected from the group consisting of graphitic carbon, carbonaceous carbon, metals and inorganic compounds. A method in which a slurry in which water is dispersed in water in the presence of a binder and a wetting agent is spray-dried and granulated in heated air that may contain heated steam. No body and residual coal yield is 10
(2) The wetting agent has a cloud point of 25 ° C. or more, which is 0.01 to 5 parts by weight based on 100 parts by weight of the carbon-based powder. A nonionic surfactant having a range of from 0.01 to 3 parts by weight based on 100 parts by weight of the carbon-based powder.

The powder to be subjected to granulation can be any of the powders obtained by the above-mentioned prior invention of the present inventor. A granulated product having an average particle diameter of 114 μm obtained by granulating a carbon-based composition obtained by coating a flaky graphite surface with a mesophase pitch having a quinoline-insoluble content of 97% by weight has a bottom and a vertical length of 1.2 mm. Thus, a hollow box-shaped thin product having a horizontal cross-shaped partition could be continuously manufactured by a rotary press. The product obtained by carbonization at a heating rate of 9 hours up to 1000 ° C. was finished to the same size as the mold, no shrinkage cracks were observed at the bottom, and a yield rate of nearly 100% was obtained.

Further, Japanese Patent No. 2566589 and Japanese Patent No. 2
No. 566595 is annexed to the United Kingdom (308824; 9
2.12.23) Rice (4985184; 91.01.1)
5) German (P38769.13.1; 92.12.13) Registered in France (308824; 92.1.2.23) 4 countries. JP-A-6-192660 discloses that, when a pitch precursor composition or a mixture of the pitch precursor composition and an aggregate is produced by heat treatment, a special static A method for producing a pitch-containing composition in which an in-situ reaction vessel is treated in combination with a radiant heating technique is disclosed.

In this method, the affinity between a local hydrophilic material containing a large number of surface active sites such as hydroxyl groups and carboxyl groups on the crystal end faces found in graphite fine particles and a lipophilic mesophase-containing pitch can be adjusted to various types of dispersion suitable for the material. By using an agent, it can be dramatically improved, and the composite property is dramatically improved. In addition, by using radiant heating successfully, the variation in the heat treatment temperature, which is an important controlling factor of the strength of the composite molded body, within a large reactor can be suppressed to ± 2 ° C or less.
Mass production of homogeneous composite materials on an industrial scale has become possible.

The present inventors directly formed a composite composition obtained by mixing / granulating graphitic carbon particles of a specific particle size and a self-sintering carbonaceous compound into a complex shape, or forming a flat plate and then a high-speed machine. A method has been disclosed in which a complex shape required for a fuel cell separator plate is imparted by processing, and the complex shape product is inexpensively supplied by simultaneously imparting the same characteristics with the same dimensions of a formed body / carbonized molded body.

[0017]

The separator plate manufacturing technology satisfying the characteristics required for the grooved separator plate of the phosphoric acid type fuel cell disclosed in the prior patent of the present inventors has recently been spotlighted due to global environmental problems. Satisfying the characteristics of the grooved separator plate, which is a member used in solid polymer fuel cell loaded vehicles, requires that the operating temperature of the polymer electrolyte type is as low as around 80 ° C compared to 170-200 ° C of the phosphoric acid type. It is easy to understand from that.

However, the prior art is a production technology aimed at a grooved separator plate of a phosphoric acid type fuel cell as a large-sized power generator, and is therefore a solid polymer type as a power generator for an automobile or a stationary small generator for home use. Various hurdles had to be overcome to meet the low prices required for fuel cells and the enormous production expected to reach millions or more in the future.

In particular, of the prior art disclosed by the present inventor, the cost of producing mesophase-containing pitch-coated graphite composite powder suitable for a fuel cell separator plate has been a major obstacle.
Although mesophase-containing pitch-coated graphite exhibits preferable characteristics when hot-pressed at 800 to 900 ° C., it has problems in mass productivity and production equipment. Also, a granulation method suitable for mass automatic unmanned press molding is an epoch-making technique, but it requires an expensive spray drying apparatus with poor productivity, which has led to an increase in cost.

On the other hand, since a product made of a mixture of mesophase-containing pitch powder and graphite powder requires a hot press at 300 ° C. or higher, there are problems to be solved in terms of productivity and cost. The composite composition obtained by mixing / granulating the graphitic carbon particles having a specific particle size and the self-sinterable carbonaceous compound disclosed in the previous application is directly formed into a complicated shape. Alternatively, the technique of performing high-speed machining after forming a flat plate is revolutionary as an industrial manufacturing method as compared with the technique disclosed by the present inventors.

However, there are still matters to be improved, such as the process cost for pulverizing the self-sintering carbonaceous compound. That is, the problem to be solved by the present invention is to create a technology capable of supplying extremely inexpensive products required by the times without deteriorating the required characteristics.

[0022]

As the major premise of research and development, the following requirements relating to productivity and physical properties required for a grooved separator plate of a polymer electrolyte fuel cell must be satisfied. Productivity (a) Able to mass produce 200 to 500 mm square and 1 to 5 mm thick plates. (B) A fuel and air supply groove having a depth of 1 mm and a width of 1 to 2 mm can be easily provided on the plate surface or on both front and rear surfaces with through holes and various side holes and grooves for gas supply. Physical properties (c) Mechanical dimensions such as surface smoothness and warpage (d) Bending strength and compressive strength (e) Volume resistivity (f) Corrosion current (g) Gas permeability Clear the required values for each of the above. thing.

The present inventors thought that mass production of inexpensive products would be possible by satisfying the following items relating to materials and production techniques. (1) A product that combines materials that are mass-produced and supplied stably to the market (2) Granulated powder that can be used for automatic unmanned press operation (3) Build the entire process with equipment with high production efficiency

It is obvious to those skilled in the art that high cost is unavoidable in the cutting method of a graphite molded body having a complicated shape and the manufacturing method of a glassy carbon molded body in the prior art.
In the invention of the prior application, the present inventors directly formed a complex shape with graphite powder and self-sintering carbonaceous compound powder which were mass-produced and supplied abundantly on the market or supplied on demand. A solid polymer type and a phosphoric acid type fuel cell separator plate are manufactured by a simple method of obtaining a formed product having a complex shape or imparting a complicated shape to a plate-shaped formed product by high-speed machining, and carbonizing the obtained product. A method has been disclosed.

The above-described two methods for imparting a complicated shape to the carbon / graphite composite molded article are epoch-making techniques. Since the structure can also be easily processed, all the various shapes presumed from published patents and the like can be formed by the method. In the carbon industry, a method of giving various precise shapes to a carbonized or graphitized product by post-processing is commonly used.

This is because the self-sintering carbonaceous precursor compound used as a binder in the carbon industry is a tar pitch having a low melting point and a low ignition temperature obtained by distilling coal tar. Processing was considered difficult. It has been practiced to perform near net shaping after cooling the formed body as necessary. However, due to the characteristic that the compact formed by heating and extruding a kneaded material using a binder commonly used in the carbon industry undergoes linear shrinkage of about 10% during carbonization, the precision processing required for fuel cell separator plates is required. Even if it is applied to the green compact, the shape may be distorted at the carbonization stage and sometimes the carbonized compact may be destroyed.Therefore, machining with the precision required for carbonized and graphitized products at the green compact stage is required. It is common knowledge in the industry that it cannot be applied.

In the prior art for the graphite electrode, a product having a diameter such as a telephone pole is manufactured using needle coke particles as a main aggregate, whereas a fuel cell separator having a complicated shape which is an object of the present invention is used. The thickness is 1-5m
m, and furthermore, anisotropic molding in which graphitic carbon fine particles whose main feature is relatively large flatness of 10 to 70 μm as a main aggregate and which is arranged in parallel to the thin plate surface is a preferable choice. Since the bending strength required at the carbonized product stage is 5 kgf / m ^{2, which} is about 1/3 of the bending strength at the same stage of the electrode material, there is a high possibility that the amount of tar and distillation pitch used can be reduced. In view of the above, the present inventors use a very inexpensive binder used in the prior art as a self-sinterable carbonaceous precursor compound, and produce a fuel cell separator plate having a complicated shape in the category of the conventional production method. We considered that it was possible to develop it, and made intensive studies.

As a result, within the range of the particle size and the content of the graphitic carbon required to satisfy the physical properties such as the volume resistivity and the thermal conductivity required for the fuel cell separator plate, the graphitic carbon is within the range. When the granulated powder obtained by pulverizing (crushing) a composite composition whose surface is coated with a self-sintering carbon precursor and granulating the same is press-molded, a graphitic carbon having a flaky shape or a shape similar thereto is obtained. It has been found that a formed body having a strength that is not likely to be destroyed by the operation of movement and transfer, in which the flat surface is stacked in a form perpendicular to the pressing pressure, is obtained. That is, although it is a phenomenon that is remarkably expressed in flaky natural graphite, when a uniaxial or biaxial pressing pressure is applied to the composite composition granulated powder of the present invention, a dense molded body in which graphite flat surfaces are arranged in a certain direction. It has been confirmed that can be formed.

Further, the linear shrinkage rate of the formed product during carbonization is governed by the content of the self-sinterable carbonaceous material in the carbonized compact, and the shape of the self-sinterable carbonaceous precursor compound before carbonization is He also found that he was not dominated. That is, whether the self-sinterable carbonaceous precursor compound-containing heavy material is in the form of tar or distillation pitch, which is known as an inexpensive binder, the shrinkage ratio of the compact is controlled by the carbonaceous content during carbonization. Was found. Based on these facts, a carbon-graphite composite molded body that has the characteristic that the dimensions of the formed body and the carbonized molded body are the same as the mold and maintains the characteristic graphite laminated state that governs gas permeability and electrical conductivity , The specific γ disclosed in the prior application
It has been found that, similarly to the method of producing from a mixed system of heat-treated pitch fine particles containing components and graphitic carbon fine particles, it can be produced using a granulated powder of a composite composition coated with graphitic carbon fine particles by tar or distillation pitch.

The system in which the graphitic carbon fine particles are coated with a heavy substance containing a self-sintering carbonaceous precursor compound such as tar or distillation pitch is compared with a mixed system of heat treated pitch fine particles containing a specific γ component and graphitic carbon fine particles. It has to be slowed down in the range of 100 to 300 ° C. where the light-boiling fraction in the heavy component evaporates. In the practice of the present invention, the rate of temperature rise in the above temperature range is preferably in the range of 0.01 to 0.5 ° C./min. When performing long-term carbonization in a low-temperature region, particularly when continuous carbonization is essential for producing a large amount of separator plates as an object of the present invention, it is a problem whether the carbonization facility can cope with such carbonization.
This problem can be solved, for example, by carbonization in a long pusher furnace having a total length of 100 m or more, which is commonly used in the refractory brick manufacturing industry.

The problem with the furnace is the furnace atmosphere in which a large amount of oxygen is present. In the case of the product produced in the present invention, a gas-impermeable container is filled with a processed product and the upper part of the container is filled with, for example, 5%.
At least one compound selected from linseed oil, corn oil, raw coke, etc. as an antioxidant up to 00 ° C, and silica sand, boron carbide, iron powder, etc. as an antioxidant at 500 ° C or higher If carbonization is performed after filling the coke with a mixture of at least one inorganic compound, the same effect as carbonization in an oxygen-free state can be obtained. Furthermore, there is an advantage that the light-boiling fraction generated from heavy compounds can be burned in a high-temperature furnace by appropriately controlling the gas flow in the furnace.

For performing press molding, the composite composition is preferably a granulated powder. Prior to granulation, the composite composition must be ground to a predetermined particle size. In the pulverizing step, heat is generated, whereby the self-sintering precursor compound is melted, and not only the composite composition itself is deteriorated, but also the filter of the pulverizer may be clogged or the pulverizing line may be blocked. In this case, cooling pulverization is required. A method of cooling the pulverizer main body and, as a preferable method, a method of mixing dry ice fine particles with a material to be pulverized and subjecting them to pulverization together are effective for implementing the present invention. In the dry ice co-grinding method, an inert gas atmosphere is created by the vaporized carbon dioxide gas at the same time as the cooling, and a secondary effect of preventing oxidative deterioration of the precursor compound can be obtained.

The molding method usually employed in the graphite electrode manufacturing technique, that is, the composition ratio suitable for the hot extrusion press of the fluid material does not meet the purpose of the present invention. Composite compositions for such applications have a high self-sintering precursor compound content and
The requirement of the present invention that the dimensions of the carbonized molded body do not change within an allowable range cannot be satisfied. If the room temperature solid composite composition obtained by coating with tar softens / melts in any of the pulverization, granulation, and molding steps, the precursor compound is softened by heat treatment and / or vacuum treatment in the coating step. It is necessary to add a step of previously removing the light-boiling fraction contributing to the lowering of the point. As a means for simultaneously performing the coating and the light boiling point component removing step, a heating kneader can be mentioned.

The granulation is preferably wet granulation at room temperature. In spray granulation, the powder generally passes through a temperature range in which the heavy composition melts and softens, so that the powder is melted and granulated, and the physical properties required by the present invention cannot be satisfied. In the wet granulation, the composite composition powder is prepared by using water and an aqueous solution containing at least one kind of additive for mutual adhesion of particles selected from a compound group such as polyethylene glycol, sucrose, methylcellulose and a polymer flocculant. The mixture is subjected to stirring and mixing granulation to obtain a granulated product having a maximum granulation of 0.5 mm or less, which is dried and dehydrated in a temperature range where the heavy composition does not melt and soften to obtain a desired granulated powder. can get. In this case as well, a method of suppressing the softening / melting of the self-sinterable carbon precursor material by removing the heat generated during mixing and granulation by cooling the mixing and granulation tank by means such as water cooling. Can be.

In the method for imparting a complicated shape by machining of the formed body, which is the object of the present invention, since the main aggregate is graphitic carbon particles having excellent thermal conductivity, the heat generated during the cutting process is somewhat increased. Dissipated throughout. Therefore, at very low speed (for example, a groove having a width of 1 mm and a depth of 1 mm is cut at a cutting speed of <10
(cm / min) In the operation of cutting a groove, a desired shape can be obtained by a cooling operation that blows air to a cutting jig. However, high-speed and efficient machining aimed at by the present invention, for example, using a 100 mm 1 mm wide saw-shaped jig placed at 1 mm intervals to cut a 1 mm deep groove at a cutting speed of 100 cm
In the processing step of imprinting the raw plate surface in / min, heat is generated >> heat dissipation, and the self-sintering precursor material, specifically tar and distillation pitch are softened / melted, resulting in loss of the processed shape or its It has been found that the reliability of the processing accuracy is significantly impaired.

As a means for solving the above problems, the present inventors have attempted to bring cold water, liquefied carbon dioxide gas, liquid nitrogen gas, fine dry ice, etc., into contact with a cutting jig and the object to be cut, and aimed at high-speed cutting. We have found that processing is possible. The cooling medium used can be selected at the cutting speed. In the case of low speed, water or cold water can be selected. As the speed increases, an appropriate medium can be selected from liquefied carbon dioxide gas, liquid nitrogen gas, and fine dry ice. The cutting oil generally used for such a machine tool dissolves all or a part of the tar or the distillation pitch, and thus does not meet the purpose of the present invention and cannot be used. The complex shape of the fuel cell separator plate is made by high-speed machining on both sides of a thin plate-shaped formed body with a thickness of about 2 to 3 mm with a size of 20 cm square, at least 10 times the machining speed of the carbonized material used in the prior art. The method of the present invention made it possible to imprint at a speed of.

The formed form imprinted with a complex shape by the method of the present invention is formed into a product by carbonization. The method of the present invention is characterized in that the dimensions of the formed body and the carbonized molded body do not substantially change, and the carbonized molded body does not generate distortion or cracks due to shrinkage during carbonization in the carbonized molded body, and the fired product Can be used as a product as it is. The present invention is as follows if the above-mentioned present invention is summarized.

That is, the present invention comprises a self-sintering carbonaceous precursor compound exhibiting self-sintering properties during carbonization selected from the group consisting of coal tar, petroleum tar, coal pitch, and petroleum pitch. The weight ratio of at least one selected from the group consisting of a heavy composition having less than 5% of a γ component (quinoline-soluble toluene-insoluble), natural graphite, and artificial graphite is 1%.
A composite composition in a solid state at room temperature obtained by kneading 0 to 70 μm of graphitic carbon fine particles and coating the graphitic carbon fine particles with the heavy composition is pulverized (crushed) and granulated, The diameter of the obtained heavy composition-coated graphitic carbon fine particles is 0.1 mm.
In a method of press-molding a granulated powder consisting of particles of 5 mm or less and machining and carbonizing the resulting formed body to produce a carbon-graphite composite molded body having a complicated shape, the pulverization (pulverization) is performed. Crushing) and crushing (crushing) used in the machining process
A jig, the processing jig, and a complex shape characterized by grinding (crushing) and machining while cooling the periphery of the composite composition and the formed body portion in contact with the jig and the periphery of the formed body to a temperature range where the heavy composition does not melt. The gist of the present invention is a method for producing a carbon / graphite composite molded body.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. Embodiments will be roughly described in terms of raw materials, mixing / granulation, molding, processing, and firing systems. Raw material and composite system thereof (1) As the graphitic carbon fine particles, at least one type of graphitic carbon fine particles selected from the group consisting of flaky and earthy natural graphite and artificial graphite can be used. Artificial graphite is more preferred in terms of both physical properties and supply stability of graphite. Preferred artificial graphite is, for example, KS series manufactured by Timcal. Various artificial graphites supplied from the graphite molded body manufacturing industry can also be selected. Examples of natural graphite include CPB manufactured by Nippon Graphite Co., Ltd. and chemically refined products thereof.

(2) The particle size of the graphitic carbon fine particles can be selected widely from the viewpoint of moldability. However, the volume resistivity,
From the viewpoint of simultaneously satisfying various physical properties such as thermal conductivity, strength of the molded body, dimensional stability of the formed green body and the fired green body, and gas permeability, even if it is too large or small, the object of the present invention is not met. The average particle size of the graphite fine particles can be selected from the range of 10 to 70 μm, preferably 15 to 50 μm.
When the shape of the groove portion of the separator plate becomes fine, and the requirements for dimensional accuracy and gas permeability become strict, graphite having a small particle size is selected. As the graphite particle diameter becomes smaller, the amount of the self-sintering carbonaceous compound is increased or the average particle diameter is reduced from the strength development mechanism described later.

(3) The graphite content can be selected widely,
In order to set the dimensions of the formed article and the carbonized article to be the same, 90 to 50 parts by weight, preferably 8 parts by weight of the mixture are used.
5 to 60 parts by weight, more preferably 80 to 65 parts by weight can be selected. This graphite content range is also a factor governed by the sintering properties during carbonization of the self-sintering carbonaceous precursor compound, and is comprehensively determined based on the properties of the self-sintering carbonaceous precursor compound. Is done. As a matter of course, there is room for improving the graphite-derived properties such as electrical conductivity and thermal conductivity as the graphite carbon content increases. However, if the sintering characteristics of the self-sinterable carbonaceous precursor compound and the average particle diameter described below are inappropriate, the carbonized molded body may swell and may not be able to make full use of the characteristic properties of graphitic carbon. ,
Requires proper design.

(4) Various self-sintering carbonaceous precursor compounds that can be used in the present invention are commercially available. Coal-based and petroleum-based tars, and tar pitches obtained by distilling these tars, the γ content of which is less than 5%,
Preferably less than 3% of the product can be mentioned.

(5) When using tar or distilled tar containing a large amount of a low boiling point fraction among the self-sinterable carbonaceous precursor compounds, the composite obtained by coating the graphitic carbon fine particles with the precursor compound is used. The low boiling point fraction contained in the composition is removed so that the softening melting point of the composite composition is at least 50 to 70.
Set to be at least ° C. As a specific method, use of a heating type kneader can be mentioned. After kneading with the graphitic carbon fine particles under conditions in which the precursor compound is liquefied and coating the surface of the graphitic carbon fine particles with the precursor compound, the kneading temperature is increased to distill off the light boiling fraction contained in the precursor compound. The purpose is achieved by the thing. It is also within the technical scope of the present invention to blow air or nitrogen gas to promote the distillation of light boiling fractions. However, when air is blown, it is required that the temperature is not raised to a temperature range in which the precursor compound takes in oxygen. When the precursor compound takes in oxygen, the self-sintering property is impaired due to the thin film, and the object of the present invention cannot be achieved. Self-sintering is an important factor that governs the bending strength, gas permeability, and corrosion current value of the carbon / graphite composite molded article in the practice of the present invention. It is a matter to be done.

Pulverization / Granulation System The separator thickness is an important factor in the fuel cell system, and also an important factor in controlling the internal heat loss due to the volume resistivity. From the gist of the present invention, for example, cold isostatic pressing (Cold Isoact)
Embodiments may include a method of making a block with icPress (abbreviated as CIP) and cutting a thin plate. However, for applications requiring a large number of flat products, such as separator plates for solid polymer fuel cells for automobiles, the object of the present invention is to first press-mold a flat plate of the desired thickness and then perform high-speed machining. Is a preferred embodiment for achieving Therefore, in producing a flat plate having a desired thickness at a high speed and a uniform thickness by press molding, the flowability of the granulated powder is an important factor.

(6) In order to impart the flowability of the granulated powder, a composite composition composed of the graphitic carbon fine particles coated with the precursor compound is subjected to a pulverization (crushing) step in a step of crushing (crushing). After being adjusted to a particle size in consideration of the particle size distribution, it is subjected to a wet granulation process in which the self-sintering carbon precursor compound is operated in a temperature range in which the self-sintering carbon precursor compound is not melt-softened in the production process.
It is a more preferred embodiment of the present invention to convert to a granulated powder having a particle size of 5 mm or less, preferably 0.3 mm or less.

The pulverizing (crushing) machine can be selected from various models. The object of the present invention is achieved by selecting an appropriate model and operating conditions from a crusher represented by a hammer mill and a pin mill. The heat generated by the pulverization (crushing) causes the softening and melting of the self-sintering carbon precursor compound, which may make pulverization substantially impossible, and cooling pulverization (crushing) is preferred. As the cooling means, cooling the pulverizer jacket can be mentioned as a concrete method. As a more preferable countermeasure method, a method of co-milling dry ice fine particles can be given.

(7) The present inventors searched for granulation conditions with a high speed mixer (Fukae Powtech). Granulation is achieved by adding a granulation liquid to the powder that has been pulverized (crushed) with stirring. Various forms can be selected for the granulating liquid. The simplest granulating liquid is water. However, the granulated powder obtained after mixing and drying of the water granulation is apt to collapse. Therefore, it is unsuitable for a production mode in which granulated powder is transported in a large container, but a factory in which granulation, drying, and molding are systematized can obtain a desired function even by water granulation. Further, by adding various compounds having both water solubility and caking properties, such as a polymer flocculant, polyethylene glycol, methylcellulose, and sucrose, to water as a caking aid, a granulated powder having higher strength can be obtained. .

The purpose can be achieved by selecting a binding aid that does not contain an element that causes corrosion or heat generation by remaining in the separator and participating in the electrochemical reaction. However,
If the strength of the granulated powder obtained here is too high, the granules will not collapse even if molded at a predetermined pressure in the press molding step. In extreme cases, the cross section of the compact is observed as a combination of granulated particles. In such a case, desired physical properties represented by the gas permeability cannot be satisfied. Therefore, it is necessary to optimize the addition amount of the binding aid in accordance with the respective physical properties. Specifically, methyl cellulose, a polymer flocculant or a polyethylene glycol-based material is 0.05 to 1.0
%, Preferably 0.1-0.5%. In the case of sucrose, 0.1 to 10%, preferably 0.5 to 5%, and more preferably 1 to 3% is selected as an outer ratio.

The difference in the amount of addition is due to the fact that polyethylene glycol forms a strong film in a dry state, while sucrose forms a myriad of cracked films. That is, in the case of polyethylene glycol, a strong film acts in the direction of preventing the particles from collapsing at the time of pressurizing, so it is necessary to minimize the amount of addition. On the other hand, when polyethylene glycol is added, the particles are hardly disintegrated during normal handling, so that extremely stable flowability is secured. The granulated powder can sufficiently cope with a general material uniform filling method using an automatic press. The same effect can be expected with sucrose and methylcellulose. Furthermore, in these systems, a part of the carbon remains in the compact during carbonization and acts as a binder for carbon particles and graphite particles, thereby contributing to an improvement in the strength of the compact.

The granulated powder is subjected to press molding after passing through a drying / dehydrating step in a temperature range where the heavy composition does not melt and soften. It is obvious to those skilled in the art that the molding can be performed while containing moisture, but the form is not suitable for automatic molding. In a device such as a high-speed mixer, conditions for preventing the melt softening can be provided by controlling the jacket to an appropriate temperature. The granulated powder can be dried by providing a magnetron drying device. In this case, since water evaporates from the inside, countless pores can be formed inside the granulated powder, and the disintegration of the granules can be further promoted by pressurization during molding. The same effect can be obtained with a fluidized bed continuous dryer and a dryer having a magnetron dryer added thereto.

Molding / processing system It is obvious to those who handle carbon molding materials,
It is extremely difficult to form a complicated shape required for a fuel cell separator plate on a carbonized or graphitized plate, and the use of a machine tool for a long time results in an expensive product. Furthermore, mass production is extremely difficult for high-hardness materials mainly composed of glassy carbon. An object of the present invention is to form such a complex shape on a press-formed flat plate at high speed and efficiently by using a machine tool generally used in the carbon industry.

It is an object of the present invention to provide a molded product obtained from a composite composition comprising a graphitic carbon fine particle coated with a self-sintering carbon precursor compound, which usually softens and melts when subjected to machining. To provide means for high-speed and efficient machining. The machine tool includes an end mill, a lathe, and the like. Cutting can be performed while the processing jig and the workpiece are cooled. Examples of the cooling medium include water, liquid carbon dioxide gas, liquid nitrogen gas, atomized dry ice, and the like. The optimal cooling medium is selected in consideration of factors such as the number of processing jigs, processing speed, and processing depth. Machine oils used in machine tools cannot be used because they cause deformation of the green form.

In a processing machine using a plurality of saw-shaped cutting jigs having a large number of blades, an ordinary carbon product processing speed of 10 to 100 is used.
Double is obtained. According to the method of the present invention, ultra-precision machining of a large number of separator plates can be easily performed with a small number of machining machines,
The cost reduction effect becomes extremely large. Since holes and grooves on the side surface can be easily formed, a cost reduction effect similar to that of one-shot press molding can be expected. Also, when a level of thickness variation accuracy that cannot be reached by press molding is required, the raw plate is cut in a cooled state and the front and back sides are cut to a certain size by a planing device, and then put into the complex shape processing process,
Products with stable dimensional accuracy can be manufactured within the accuracy range of the plane machine tool. Also has a complicated shape by using a method to subdivide the filling of the mold into the granulated powder,
A green compact that does not cause shrinkage distortion during firing can also be obtained by press molding.

Firing System In the present invention, a product can be obtained by performing a heat treatment in an inert atmosphere until the self-sintering carbonaceous precursor compound becomes a carbonaceous carbon. It is generally known that a self-sintering carbonaceous precursor compound releases hydrogen at around 900 ° C. to terminate carbonization. Therefore, carbonization is completed by heating to 1000 ° C., which is known as a normal carbonization temperature. However, the carbonization temperature in the present invention is 1100-1.
800 ° C., preferably 1150 to 1600 ° C., more preferably 1200 to 1500 ° C.

The reason for selecting a temperature higher than the conventional carbonization temperature is to reduce the corrosion current. That is, in a proton type fuel cell, whether a phosphoric acid or a solid polymer type polymer in which a sulfate group is fixed to a polymer membrane, an electric current flows through the separator plate in an operating state, and water and protons coexist. Regardless of the temperature difference, an electrochemical reaction occurs at the functional group present on the end face of the graphite crystal or carbon crystal, which is observed as a corrosion current. In addition, the graphite or carbon crystal structure is destroyed by the corrosion current, and in extreme cases, the separator plate becomes ragged. In particular, it is well known that graphite crystal end faces have many functional groups, and this is a source of corrosion current. In addition, when carbonization of carbonaceous carbon is insufficient, a corrosion current reaction is caused by the remaining functional groups.

The following measures can be taken as measures against the corrosion current of the present invention. First, regarding the inhibition of the reaction of the graphite crystal end face functional groups, the graphite crystal end face is protected by carbonization sintering of the coating obtained by coating the graphite end face with a self-sintering carbonaceous precursor compound, and the reactivity is reduced. be able to. Next, by setting the carbonization temperature within the above range, the functional groups of the carbonaceous carbon crystal and the graphitic carbon crystal are removed in advance, and the acceleration of the electrochemical reaction that occurs when a large amount of functional groups remains is suppressed. Long-term stability can be ensured. When a particularly preferable temperature range of 1200 to 1500 ° C. is selected, the initial corrosion current value is drastically reduced to 1/10 or less of that at the time of sintering at 1000 ° C., and the current value changes within an allowable range even during long-time operation.

On the other hand, BN used at the time of molding can be cited as a cause of increasing the initial corrosion current value. Therefore, it is preferable not to use BN or to reduce the amount of BN used as much as possible. Since the heavy composition containing the self-sintering carbonaceous precursor compound in the composite composition of the present invention contains a large amount of light-boiling fraction, the formed form of the present invention has a carbonization temperature range of 50 to 500 ° C, particularly 70 to 500 ° C. 300 ℃
This generates a large amount of gas mainly composed of light-boiling fractions and decomposition products during carbonization. At this time, if the amount of gas generated per unit time, per unit area exceeds the amount of generated gas that escapes from the molded body, the gas pressure inside the molded body increases, which causes swelling of the molded body, bending strength, glass transmittance, In addition to deteriorating various physical properties such as electrical conductivity, the product sometimes loses its form.

When the self-sintering carbonaceous precursor compound itself is softened and melted by rapid temperature rise, complicated shape deformation or loss occurs. Therefore, the rate of temperature rise during carbonization is optimized taking into account factors such as the content of the light-boiling fraction of the self-sintering carbonaceous precursor compound, the content in the composite composition, the area of the compact, and the compacting pressure. Is done. Although these techniques are within the technical scope known to those skilled in the art, the rate of temperature rise of the formed product of the present invention is 50 to 50.
In the carbonization temperature range of 0 ° C, it is 0.01 to 3 ° C / min, preferably 0.02 to 2 ° C / min, more preferably 0.05 to
By setting the temperature in the range of 1 ° C./min, desired carbonization is achieved while avoiding softening and melting of the product itself.

It is necessary to reduce the rate of temperature rise in the temperature range of 50 to 500 ° C. in accordance with an increase in molding pressure and an increase in the area of the green body. At the time of carbonization in the temperature range of 200 to 400 ° C., when oxygen is contacted from the outside with the compact, the self-sintering carbonaceous precursor compound absorbs oxygen and is transformed into an oxygen-containing carbonaceous compound. become. In this case, a difference in linear shrinkage ratio at the time of carbonization can be caused between a compound which becomes carbonaceous carbon without being oxidized, resulting in distortion or breakage of the product. Therefore, it is necessary to suppress the contact between oxygen and the compact during carbonization in the temperature range. As a method for suppressing oxygen intrusion in this temperature range, there is a conventionally known technique, which includes carbonization in an inert gas (preferably nitrogen gas) atmosphere.

The commonly used carbonized packing material "Coke Please" does not have the ability to inhibit oxygen intrusion in this temperature range.
An oxygen permeation suppression layer obtained by mixing linseed oil with coke please, disclosed in Japanese Patent Publication No. 5 (1993) -5, is placed on the upper part of the vessel, and a method of substantially eliminating oxygen penetration up to the 500 ° C. region can also be used. The carbonization at 600 ° C. or higher can be arbitrarily selected from the heating rate in the range of 0.5 to 10 ° C./min according to the properties of the molded body. Here, desorption of hydrogen occurs at the final stage of carbonization, but it is at the stage where the strength has already been improved, and since the gas flow path is also secured, light boiling fraction gas and decomposition during carbonization The slow heating required at the time of gas generation is not required on the principle of carbonization. 500% for equipment with oxygen content of atmospheric gas of several% or more, such as refractory brick continuous firing furnace.
It is necessary to perform antioxidant treatment in the region above ℃, but the desired deterrent effect is imparted by covering the open upper part of the gas impermeable container with coke free containing boron carbide, borax, iron, etc. .

[0061]

EXAMPLES The contents of the present invention will be specifically described below with reference to examples. Example 1 15 kg of a kneading tank in which 3 kg of a coarsely crushed distilled tar pitch having a melting temperature of 70 ° C obtained by distillation of coal tar and 5 kg of CPB (natural graphite) manufactured by Nippon Graphite Co., were maintained at 90 ° C.
After the material temperature reaches 90 ° C. while replacing the inside of the tank with nitrogen gas, the mixture is further cooled to 15 ° C.
After kneading for 1 minute, the temperature of the kneading tank was raised to 130 ° C. and maintained for 2 hours. The crushed composite composition obtained by rotating the twin screw while forcibly cooling the kneading tank was discharged out of the kneading machine. 100 parts by weight of the obtained coarsely pulverized product was pulverized with a Yariya pulverizer while adding 3 parts by weight of dry ice fine particles to obtain a pulverized composite composition having an average particle size of 50 μm.

300 g of the composite composition was put into a high-speed mixer (LFS-GS-2J type) manufactured by Fukae Powtech Co., Ltd., in which the jacket temperature was set at 10 ° C. using a cold water circulator.
While stirring at an agitator rotation speed of 2000 rpm and a chopper rotation speed of 500 rpm on average, 2.5 g of sucrose and 50 g of water
Was poured over 2 minutes, and granulation was continued for 3 minutes. The obtained granulated powder was dried with a hot-air circulation dryer set at 50 ° C., and cooled to room temperature. 0.425 mesh
The screen was separated with a sieve of mm. More than 99% was recovered under the sieve. 200.0m vertical on a 2-axis 600-ton press
A mold of mx 200.0 mm in width was installed, and 216 g of under-sieve granules were charged using an upper and lower pressing die having a smooth surface. After degassing operation, molding was performed at a molding pressure of 1 ton / cm ² , A flat plate-shaped formed body having a thickness of 3.3 mm was obtained.

The green compact was subjected to end milling. A liquid carbon dioxide blowing nozzle that can move together with the processing blade is installed in the immediate vicinity of the processing blade, and while spraying liquid carbon dioxide gas around the processing blade and its surroundings, a two-blade 1 mm diameter drill is used at 2500 rpm and traveling speed is 320 mm / Min, the groove width 2mm, depth 1mm, width 1mm, leaving 30mm at both ends
Grooves were cut on both sides. The grooves used were orthogonal to the front and back. The processed green body weight was 187 g. The processed body was sandwiched between the upper and lower sides of a processed form by a 50 mm-thick graphite plate having a smooth surface placed in a stainless steel container, the periphery was covered with coke please, and the upper part was provided with an antioxidant layer obtained by mixing linseed oil with coke please. A container is set in a muffle furnace, and 0.05 ° C./min while supplying nitrogen at a supply rate of 5 L / min from an alumina pipe introduced into the please layer from above the lid.
Then, the temperature was raised from room temperature to 500 ° C. at a temperature rising rate of 500 ° C., maintained at 500 ° C. for 2 hours, heated to 1200 ° C. at a rate of 1 ° C./minute, maintained at 1200 ° C. for 2 hours, and then cooled in a furnace. The carbonization yield based on the distillation tar pitch was 60% by weight based on the obtained carbonized molded body weight. The carbonized molded article gave a linear shrinkage of 0.1% in the plane direction compared to the mold size. The groove formed by the end mill was carbonized as it was, and no distortion, bending, or partial fracture was observed.

100 mm long and 10 mm wide from the plane
Was cut out by cutting and subjected to a three-point bending test to obtain a bending strength of 3.5 kgf / mm ² . 5 from the plane
Cut a test piece of 0 mm square and use nitrogen to back pressure 1 kg /
The gas permeability is determined in cm ² and 3 × 10 ⁻⁵ Ncc / min / c
It was obtained m ^2. Further, the test piece was measured for volume resistivity using a LORESTA made by Yuka Denshi Co., Ltd., to obtain 1.3 mΩ · cm.
A 10 mm × 10 mm test piece was cut out from the plane portion, and the corrosion current was measured. After 1000 minutes, 60 μA / cm ² was obtained.

[0065]

According to the method of the present invention, since the formed body before carbonization does not change in size and shape due to carbonization, the fuel has flexural strength, electric conductivity, thermal conductivity, gas permeability and the like. A carbon / graphite composite molded article having a complicated shape satisfying various characteristics required for a battery separator plate can be efficiently manufactured at low cost.

Continued on front page F-term (reference) 4G032 AA04 AA09 BA04 GA01 GA02 GA03 GA04 GA06 GA08 GA12 GA14 4G046 EA02 EA05 EB04 EB06 EC01 EC05 4H058 DA02 DA03 DA06 DA13 EA32 EA33 EA34 EA35 FA08 FA18 FA22 HA04 HA13 5H0BB BB01 EE06 EE18 HH01 HH05 HH08

Claims (14)

[Claims] 1. A γ component containing a self-sintering carbonaceous precursor compound exhibiting self-sintering properties during carbonization selected from the group consisting of coal-based tar, petroleum-based tar, coal-based pitch, and petroleum-based pitch. 5% (quinoline soluble toluene insoluble component)
The average particle size of at least one selected from the group consisting of a heavy composition, natural graphite, and artificial graphite having a particle size of less than 10 μm to 70 μm
m, and then pulverizing (crushing) a composite composition in a solid state at room temperature obtained by kneading the graphite carbon fine particles of m and coating the graphitic carbon fine particles with the heavy composition, granulating, and granulating. Pressed granulated powder consisting of particles having a diameter of 0.5 mm or less composed of heavy composition coated graphite carbon fine particles, and the resulting formed body was machined and carbonized to form carbon / graphite having a complex shape. In the method for producing a composite molded body, the pulverization (crushing)
And a pulverizing (crushing) jig used in the machining step, the processing jig, the composite composition in contact with the processing jig, and the periphery of the formed body while being cooled to a temperature range where the heavy composition does not melt (crushing). Crushing) and machining. 2. The method for producing a complex-shaped carbon / graphite composite according to claim 1, wherein the γ component content of the heavy composition is less than 3%. 3. The light-boiling fraction contained in the heavy composition before the pulverization (crushing) of the composite composition obtained by coating the graphitic carbon fine particles with the heavy composition is reduced to a required amount. The method for producing a complex-shaped carbon / graphite composite according to claim 1, wherein the removing operation is performed. 4. The granulating operation uses water or an aqueous solution containing at least one kind of particle binding additive selected from a polymer flocculant, polyethylene glycol, sucrose and methyl cellulose, and the heavy composition is softened / Under a temperature condition that does not melt, the mixture is stirred and mixed to obtain a granulated powder having a maximum particle diameter of 0.5 mm or less, and then subjected to a water removing operation in a temperature range in which the heavy composition does not soften / melt. 2. The method for producing a complex-shaped carbon / graphite composite according to claim 1, wherein the composite is formed into a dry granulated powder. 5. The press molding is a uniaxial press, a biaxial press,
Using one molding machine selected from rotary press,
The method for producing a complex-shaped carbon / graphite composite article according to claim 1, wherein molding accompanied by near-net shape molding is performed as necessary. 6. The method according to claim 1, wherein the operation of pulverizing (crushing) while cooling is performed by cooling the pulverizing equipment. 7. The method according to claim 1, wherein the operation of pulverizing (crushing) while cooling is co-grinding (crushing) of the composite composition and fine-particle dry ice. 8. The complex-shaped carbon according to claim 1, wherein at least one selected from the group consisting of water, liquefied carbon dioxide gas, liquefied nitrogen gas, and atomized dry ice is used as a cooling medium in the step of processing while cooling. A method for producing a graphite composite molded article. 9. The carbon / graphite composite molded article having a complex shape comprises 10 to 40 parts by weight of carbonaceous carbon derived from a self-sinterable carbonaceous precursor and 90 to 60 parts by weight of graphite carbon derived from fine graphite carbon particles. The method for producing a complex-shaped carbon / graphite composite molded article according to claim 1, which is constituted. 10. A carbon / graphite composite molded article having a complex shape comprising 15 to 30 parts by weight of carbonaceous carbon derived from a self-sinterable carbonaceous precursor and 85 to 70 parts by weight of graphitic carbon derived from graphitic carbon fine particles.
The complex-shaped carbon according to claim 1, which is composed of parts by weight.
A method for producing a graphite composite molded article. 11. The method according to claim 1, wherein the carbonization is performed in a non-oxygen atmosphere. 12. The graphitic carbon fine particles have an average particle size of 15 to
The method for producing a complex-shaped carbon / graphite composite according to claim 1, which has a thickness of 50 µm. 13. The maximum temperature of carbonization is from 1200 to 160.
The method for producing a complex-shaped carbon / graphite composite article according to claim 1, wherein the temperature is 0 ° C. 14. The method according to claim 11, wherein the carbonization in a non-oxygen atmosphere is carried out in a system in which the formed product is embedded in a coke breath of a gas-impermeable container and the upper portion of the container is covered with linseed oil-impregnated coke breath. Manufacturing method of carbon / graphite composite molded body with complicated shape.