JP2006188366A - Composite carbonized material, its manufacturing method, composite activated carbon, conductive resin composition, electrode for secondary battery and polarizable electrode for electric double layer capacitor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite carbonized material wherein different kinds of carbonized components are uniformly distributed so that an effect produced by combining of the carbonized components can be increased. <P>SOLUTION: A composite material of a cured resin and a porous particulate is prepared through a step wherein a resin material is polymerized in the presence of a reaction catalyst while being mixed with the porous particulate. The resin material incorporates the porous particulate as it flocculates and polymerizes to yield the composite material wherein the porous particulate is uniformly dispersed in the thermosetting resin. Meanwhile, the resin material with a small molecular weight penetrates the pores of the porous particulate as it undergoes polymerization to yield the composite material wherein the resin penetrates the porous particulate. Then, the composite material is subjected to a heat-treatment in a non-oxidizing atmosphere and carbonized to yield the composite carbonized material which uniformly contains the carbonized component made of a carbonized product of the porous particulate and the carbonized component made of a carbonized product of the thermosetting resin. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a composite carbonized material made of a resin and porous particles and a method for producing the same, and to an activated carbon using the composite carbonized material, and further using the composite carbonized material and activated carbon. The present invention relates to a conductive resin composition, an electrode for a secondary battery, and an electric double layer capacitor polarizable electrode.

  Hardening a mixture of thermosetting resin and organic powder such as wood powder, crushed rice husk and coconut husk and carbonizing it to produce a composite carbonized material further activates this composite carbonized material It has been proposed to produce activated carbon (see Patent Document 1).

  According to this patent document 1, phenol and formalin are polymerized to prepare a 1000 to 20000 cps liquid resol type phenol resin, and this is a lipophilic liquid compound such as liquid paraffin having a boiling point of 100 ° C. or higher, polyethylene glycol A compound that is hydrophilic and has a boiling point of 100 ° C. or higher, such as a liquid compound at normal temperature, and an organic powder are mixed, and the mixture is heated and cured to prepare a composite material of a phenol resin and an organic substance. A composite carbonized material can be obtained by heat-treating and carbonizing the composite material in a non-oxidizing atmosphere. Moreover, activated carbon can be obtained by activating this composite carbonized material.

The composite carbonized material thus obtained is a composite of a carbonized component made of a carbide of organic powder and a carbonized component made of a carbide of resin, and has excellent properties such as conductivity. In addition, activated carbon is useful as an electrode for a double layer capacitor.
Japanese Patent Laid-Open No. 5-43345

  However, when preparing a composite material by mechanically mixing a thermosetting resin and organic particles as described above, the thermosetting resin and organic particles are uniformly distributed due to the poor wettability of both. It is difficult to mix. In the composite material, only the thermosetting resin is attached around the organic powder particles, and the thermosetting resin and the organic powder particles are not uniformly present from a microscopic viewpoint.

  Therefore, the composite carbonized material obtained from such a composite material and activated carbon are those in which the carbonized component composed of the carbide of the organic powder and the carbonized component composed of the carbide of the resin are not contained uniformly, There is a problem that the effect of combining the components cannot be sufficiently obtained.

  The present invention has been made in view of the above points, and provides a composite carbonized material capable of obtaining a high effect of combining different types of carbonized components by homogenizing different types of carbonized components and a method for producing the same. In addition, the present invention aims to provide activated carbon using this composite carbonized material, and further, a conductive resin composition using this composite carbonized material and activated carbon, and an electrode for a secondary battery. An object of the present invention is to provide an electric double layer capacitor polarizable electrode.

  The composite carbonized material according to claim 1 of the present invention includes a cured resin, a porous granular material, and a cured resin obtained through a step of performing a polymerization reaction in the presence of a reaction catalyst while mixing a resin raw material with a porous granular material. The composite material is carbonized by heat treatment in a non-oxidizing atmosphere.

  The invention of claim 2 is characterized in that, in claim 1, the resin raw material is a phenol and an aldehyde, and the composite material is a composite material of a phenol resin and a porous granular material.

  The invention of claim 3 is characterized in that, in claim 1, the resin raw material is furans and aldehydes, and the composite material is a composite material of furan resin and porous particles.

  According to a fourth aspect of the present invention, in any one of the first to third aspects, the porous granular material is an uncarbonized organic substance.

  The invention according to claim 5 is the invention according to claim 4, wherein the porous granular material made of uncarbonized organic material has a carbide yield of 0.5% by mass or more when heated in a non-oxidizing atmosphere at 800 ° C. It is characterized by being.

  Further, the invention of claim 6 is the invention according to claim 4 or 5, wherein the porous granular material made of uncarbonized organic substance is coconut shell, coffee bean, lignin, wood powder, cellulose, sawdust, plastic powder, rubber powder, rice husk It is characterized by being selected from bamboo.

  The invention of claim 7 is characterized in that in any one of claims 1 to 3, the porous powder is a carbide.

  In the method for producing a composite carbonized material according to claim 8 of the present invention, a cured resin and porous particles are obtained through a step of performing a polymerization reaction in the presence of a reaction catalyst while mixing a resin raw material with porous particles. The composite material of the body is prepared, and the composite material is heat-treated in a non-oxidizing atmosphere to be carbonized.

  The composite activated carbon according to claim 9 of the present invention is characterized in that the composite carbonized material according to any one of claims 1 to 7 is activated.

  A conductive resin composition according to claim 10 of the present invention is a resin in which at least one of the composite carbonized material according to any one of claims 1 to 7 and the composite activated carbon according to claim 9 is used as a conductive filler. It is characterized by blending.

  An electrode for a secondary battery according to claim 11 of the present invention uses at least one of the composite carbonized material according to any one of claims 1 to 7 and the composite activated carbon according to claim 9 as an electrode material. It is characterized by being formed.

  An electric double layer capacitor polarizable electrode according to claim 12 of the present invention uses at least one of the composite carbonized material according to any one of claims 1 to 7 and the composite activated carbon according to claim 9 as an electrode material. It is formed by using.

  By mixing the resin raw material with the porous powder and polymerizing it in the presence of the reaction catalyst, the resin raw material aggregates and polymerizes while taking in the porous powder, and is porous in the thermosetting resin. A composite material in which the porous particles are uniformly dispersed can be obtained, and the resin raw material composed of a monomer having a low molecular weight is polymerized in a state where it penetrates into the pores of the porous particles, and is a thermosetting resin. It is possible to obtain a composite material in which not only the porous particles are dispersed but also the resin penetrates into the porous particles. Therefore, the composite carbonized material obtained by carbonizing this composite material, and the composite activated carbon further activated by the composite carbonized material are a carbonized component composed of a carbide of a porous granular material and a carbonized component composed of a carbide of a thermosetting resin. Is uniformly contained, and by homogenizing different types of carbonized components, the effect of combining different types of carbonized components can be enhanced.

  Hereinafter, the best mode for carrying out the present invention will be described.

  In the present invention, a composite material composed of a resin and porous particles can be obtained by polymerization reaction in the presence of a reaction catalyst while mixing the resin raw material with the porous particles. As this resin, a thermosetting resin in general can be used. In the present invention, a phenol resin or a furan resin is particularly desirable.

  In the present invention, a porous organic material that is carbonized by heating and baking can be used as the porous granular material. For example, coconut shell, coffee bean, lignin, wood powder, cellulose, sawdust, rice husk, bamboo, plastic powder, rubber powder and the like can be mentioned. Coconut husk, coffee beans, lignin, wood powder, cellulose, sawdust, rice husk, bamboo, etc. are made porous by conduit etc., and plastic powder and rubber powder are porous formed from foam plastic and foam rubber Can be used. Of course, although not limited thereto, it is desirable that the carbide yield when heated in a non-oxidizing atmosphere at 800 ° C. is 0.5% by mass or more. In order to become activated carbon by activation treatment as described later, the carbide yield needs to be 0.5% by mass or more. As the porous granular material, in addition to the porous organic material described above, a carbide obtained by heating and calcining such a porous granular material in advance, such as coconut shell activated carbon or charcoal powder, can also be used. The particle size of the porous granular material is not particularly limited, but is preferably in the range of 0.1 to 500 μm.

  First, the case where a composite material is prepared using a phenol resin as a thermosetting resin will be described. Using phenols and aldehydes as resin raw materials, while mixing the phenols and aldehydes with porous granules, By performing a condensation reaction in the presence of a reaction catalyst, a composite material in which a phenol resin and a porous granular material are combined can be obtained.

  Here, as phenols, phenol derivatives can be used in addition to phenol. Examples of phenol derivatives include trifunctional compounds such as m-cresol, resorcinol and 3,5-xylenol, tetrafunctional compounds such as bisphenol A, bisphenol S, and dihydroxydiphenylmethane, o-cresol, p-cresol, List bifunctional o- or p-substituted phenols such as p-ter-butylphenol, p-phenylphenol, p-cumylphenol, p-nonylphenol, 2,4- or 2,6-xylenol In addition, halogenated phenols substituted with chlorine or bromine can also be used. As phenols, one type can be selected and used, or a plurality of types can be mixed and used.

  As the aldehydes, formalin, which is an aqueous formaldehyde solution, is optimal, but paraformaldehyde, acetaldehyde, benzaldehyde, trioxane, tetraoxane, and other aldehydes may be used. It is also possible to use those in which is replaced with furfural or furfuryl alcohol.

Further, as a reaction catalyst, a basic substance that reacts phenols and aldehydes to form a = NCH ₂ -bond between the benzene nucleus and the benzene nucleus, such as hexamethylenetetramine, ammonia, methylamine, dimethylamine, Primary and secondary amines such as ethylenediamine and monoethanolamine can be used. Also, alkali metal oxides such as sodium, potassium, lithium, hydroxides, carbonates, or alkaline earth metal oxides such as calcium, magnesium, barium, hydroxides, carbonates, tertiary amine compounds, etc. Can also be mentioned. Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate, magnesium oxide, calcium oxide, trimethylamine, triethylamine, triethanol. Amines, 1,8-diazabicyclo [5,4,0] undecene-7.

  Then, the phenols, aldehydes, and reaction catalyst are placed in a reaction vessel such as a reaction kettle, and the phenols and aldehydes are subjected to addition condensation reaction. At this time, the porous particles are further reacted. An additive such as a dispersant or a coupling agent is added to a reaction container as required, and a reaction between phenols and aldehydes is performed in the presence of these. Here, the blending amount of the aldehyde with respect to the phenol is preferably in the range of 1.0 to 3.0 mol of the aldehyde with respect to 1 mol of the phenol. Moreover, although the compounding quantity of a reaction catalyst changes greatly with the kind of reaction catalyst, the range of 0.05-10 mass% with respect to phenols is preferable.

  The above condensation reaction is carried out with stirring in a liquid such as water sufficient to stir the reaction system. At the beginning of the reaction, the porous granular material may float on the liquid surface. Incorporated into the liquid as the reaction of phenols and aldehydes proceeds. When the addition condensation reaction further proceeds, the condensation reaction product of phenols and aldehydes begins to separate from the water in the system while embracing the porous particles. The phenol resin produced by the condensation reaction of phenols and aldehydes can be aggregated into granules, and the phenol resin particles with porous powder particles dispersed inside can be obtained in a dispersed state in the system. it can. Porous particles are not mechanically mixed with phenolic resin, but phenols and aldehydes undergo a condensation reaction while embedding the porous particles, and the porous particles are taken into the interior. Resin particles are prepared, and phenol resin particles in which porous powder particles are uniformly dispersed can be obtained. Porous granules have many fine pores, but phenols and aldehydes are monomers and have a low molecular weight, so phenols and aldehydes penetrate into the pores of porous granules, An addition condensation reaction occurs in the small pores, and a phenol resin is produced in a state of permeating into the small pores. Therefore, at the same time that the porous powder is dispersed in the phenol resin, the phenol resin penetrates into the porous powder.

  When the reaction is further advanced to the desired degree and the mixture is cooled and then stirred, the particles are precipitated and separated from water. These particles are fine water-containing particles, and can be easily separated from water by filtration. By drying the particles, phenol resin and porous powder are obtained as free-flowing particles. A composite material of granules can be obtained.

  Next, a case where a composite material is prepared using a furan resin as a thermosetting resin will be described. Furans and aldehydes are used as resin raw materials, and the furans and aldehydes are mixed with a porous granular material. On the other hand, by carrying out the condensation reaction in the presence of the reaction catalyst, a composite material in which the furan resin and the porous granular material are combined can be obtained.

  As the furans, furfuryl alcohol, furfural, and the like can be used, and the aldehydes described above can be used. An acid such as phosphoric acid can be used as the catalyst. Thereafter, in the same manner as in the case of the above-described phenol resin, a composite material in which a furan resin and a porous granular material are combined can be obtained.

  As described above, particles of a composite material composed of a thermosetting resin such as a phenol resin or a furan resin and a porous powder are dispersed in the thermosetting resin, and the porous powder Since the thermosetting resin penetrates into the inside of the particles, a composite material in which the thermosetting resin and the porous particles are uniformly present in each particle can be obtained.

  Here, since the porous granular material is mixed with the reaction liquid when the polymerization reaction of the resin raw material is performed, in the case of mechanically mixing the thermosetting resin and the porous granular material Thus, a porous granular material can be mixed by arbitrary compounding quantities, without depending on both wettability etc. The compounding amount of the porous granular material is desirably 1% by mass or more based on the total amount of the composite material. When the blending amount of the porous granular material is less than 1% by mass, it is not possible to sufficiently obtain the effect of combining the carbonized components as described later. The upper limit of the amount of the porous granular material is not particularly set, but if it exceeds 90% by mass with respect to the total amount of the composite material, the porous granular material is impregnated with the thermosetting resin. As a result, it becomes difficult to obtain a composite material in which the thermosetting resin and the porous particles are present uniformly.

  In preparing a composite material of a thermosetting resin and porous particles as described above, after the polymerization reaction of the resin raw material is continued until the thermosetting resin to be produced becomes insoluble and infusible. By stopping, particles of the composite material in a state where the thermosetting resin is completely cured can be obtained. Alternatively, when the polymerization reaction of the resin raw material is stopped in a state where the generated thermosetting resin has thermosetting properties, and an uncured composite material is prepared, heating is performed thereafter. By curing the curable resin until it becomes insoluble and infusible, particles of the composite material in a state where the thermosetting resin is completely cured can be obtained.

  Furthermore, when the composite material is produced by mixing the resin raw material with the porous particles and carrying out the polymerization reaction in the presence of the reaction catalyst as described above, the porous particles are reacted from the beginning of the polymerization reaction. The reaction can be carried out by introducing it into the system. Also, at the time of starting the polymerization reaction of the resin raw material, do not add the porous granular material to the reaction system, but put the porous granular material into the reaction system in the middle of the polymerization reaction to perform the reaction. You may do it. Furthermore, the porous granular material can be charged into the reaction system in a plurality of times during the period from the start to the end of the polymerization reaction of the porous granular material, and the reaction can be performed.

  The composite material particles prepared as described above, in which the thermosetting resin is completely cured, are heat-treated in a non-oxidizing atmosphere, and the thermosetting resin and porous particles in the particles are not carbonized. In the case of the organic material, the porous powder is carbonized to contain a carbonized component made of a carbide of a thermosetting resin and a carbonized component made of a carbide of the porous powder. The particles of the composite carbonized material according to the invention can be obtained. The non-oxidizing atmosphere may be an atmosphere in which the thermosetting resin is not oxidized, and can be set to an atmosphere using argon, helium, nitrogen gas, or the like as an inert gas. The heat treatment conditions are not particularly limited, but are preferably set to 400 to 3000 ° C. and about 1 to 100 hours. The carbonization yield varies greatly depending on the type of composite material. For example, the phenol resin is 45 to 60% by mass, the furan resin is 40 to 55% by mass, and the coconut shell is 10 to 25% by mass.

  Furthermore, the activated carbon which concerns on this invention can be obtained by activating the said composite carbonization material. The activation treatment can be performed by heating the composite carbonized material in an atmosphere of an oxidizing gas or a mixed gas of an oxidizing gas and an inert gas. For example, heating the composite carbonized material with water vapor. It can be activated by. The activation conditions are not particularly limited, but are preferably set to 500 to 1000 ° C. and about 1 to 10 hours. The activation treatment can be performed by a chemical activation method using molten potassium hydroxide or the like in addition to such a gas phase activation method.

  Here, when the composite material is heat-treated in a non-oxidizing atmosphere and carbonized as described above, the porous granular material made of the thermosetting resin or organic matter in the composite material is exposed to heat, causing thermal decomposition. It is volatilized as a decomposition product that has become a low-molecular-weight substance, and the traces become voids to form pores. In general, the pore diameter of the carbide of the porous granular material made of an organic substance having a large amount of volatile matter is larger than the pore diameter of the carbide of the thermosetting resin. Then, when the composite carbonized material is activated, the pore diameter of the carbide of the thermosetting resin such as phenol resin is generally 20 nm or less, and the pore diameter of the carbide of the porous granular material made of a wooden organic material is generally 20 to 1500 nm. The pores of the carbide of the thermosetting resin and the carbide of the porous granular material are greatly different. As described above, since the activated carbon according to the present invention is a composite of the carbonized component composed of the carbide of the organic powder and the carbonized component composed of the carbide of the resin, the pore diameter distribution is two. It has different zones, and a plurality of components having greatly different molecular weights can be adsorbed to each pore having different zones. Therefore, the composite activated carbon according to the present invention can be used as a hybrid activated carbon that simultaneously adsorbs a plurality of gas components having different molecular weights.

  And the conductive resin composition can be obtained by blending the granular composite carbonized material according to the present invention obtained as described above or the granular composite activated carbon into the resin as a conductive filler. . As the resin, thermoplastic resins such as polyphenylene sulfide resin, polyphenylene ether resin, liquid crystal polymer, polystyrene resin, ABS resin, polyacetal resin, polycarbonate resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyamide resin, polystyrene resin, Thermosetting resins such as phenol resins, unsaturated polyester resins, and epoxy resins can be used. Although the compounding quantity of the composite carbonized material and composite activated carbon mix | blended as an electroconductive filler can be set arbitrarily, a composite carbonized material is set to the range of about 0.1-2.0 with respect to the resin 1 by mass ratio. It is preferable to do this.

  By molding the conductive resin composition thus prepared by an arbitrary method such as injection molding or compression molding, it is possible to manufacture parts of electric / electronic devices having high conductivity.

  Moreover, said composite carbonized material and composite activated carbon can be used as a carbon material which forms the electrode of secondary batteries, such as a negative electrode of a lithium ion secondary battery. When using a composite carbonized material or a composite activated carbon as a carbon material to produce an electrode such as a negative electrode of a lithium ion secondary battery, for example, a composite carbonized material or a composite activated carbon is dispersed in a solvent together with a binder to form a slurry, This slurry can be applied to a metal foil such as a copper foil, dried and press-molded.

  Furthermore, a polarizable electrode is produced with this electrode, and an electric double layer capacitor for forming an electric double layer formed at the interface of the electrolytic solution can be formed. A secondary battery or an electric double layer capacitor having a high charge / discharge capacity is obtained by producing a secondary battery electrode or an electric double layer capacitor polarizable electrode using the composite carbonized material of the present invention, particularly composite activated carbon. It is something that can be done.

  Here, for the polarizable electrode of the electric double layer capacitor, activated carbon having a large specific surface area is used as an electrode material so that many ions can be adsorbed, and the composite carbonized material according to the present invention is carbonized by heat treatment. Although it has pores having the same effect as activated carbon, the specific surface area is not sufficiently large and is not satisfactory. Therefore, in the present invention, the composite carbonized material is activated as described above to increase the specific surface area and pore volume per unit mass of the composite carbonized material, and to improve the physical and chemical adsorption performance. It is preferable to use it to produce a polarizable electrode of an electric double layer capacitor.

  Next, the present invention will be specifically described with reference to examples.

Example 1
A reaction vessel equipped with a stirrer is charged with 123 parts by mass of phenol, 126 parts by mass of 37% by weight formalin, 14 parts by mass of hexamethylenetetramine, and 3000 parts by mass of water, and further pulverized to pass through a 350 μm sieve. 40 parts by mass of coconut shell powder having a carbonization yield of 25% by mass dried at 105 ° C. for 3 hours was charged. The mixture was boiled and refluxed for 60 minutes with stirring, and an addition condensation reaction was carried out for 2 hours. Next, after cooling until the internal temperature reached 50 ° C., the contents of the reaction vessel were filtered off with a Nutsche.

  The reaction product obtained by filtration was spread on a polyethylene sheet laid on a stainless steel vat, and this was placed in a dryer at 100 ° C. and dried by heating for 5 hours. The phenol resin was cured insoluble and infusible). The content of the coconut shell in this coconut shell / phenolic resin composite material was 19.6% by mass.

  Next, this coconut shell / phenolic resin composite material was fired by heating at 1200 ° C. for 3 hours under a nitrogen atmosphere at a temperature increase rate of 100 ° C./hour, and heat treatment at 1200 ° C. for 3 hours. Composite carbonized material particles were obtained. In the coconut shell / phenolic resin composite carbonized material thus obtained, the yield (ratio of the mass after heat calcination to the mass before heat calcination) is 49.1% by mass, and the coconut shell / phenolic resin composite carbonized material. The content of the coconut shell carbide in the interior was 10.0% by mass.

(Example 2)
The particles of the coconut shell / phenolic resin composite carbonized material were obtained in the same manner as in Example 1 except that the amount of coconut shell powder charged was changed to 360 parts by mass. The yield of the coconut shell / phenolic resin composite carbonized material thus obtained was 34.4% by mass, and the content of coconut shell carbide in the coconut shell / phenolic resin composite carbonized material was 50.0% by mass. there were.

(Example 3)
The particles of the coconut shell / phenolic resin composite carbonized material were obtained in the same manner as in Example 1 except that the amount of coconut shell powder charged was changed to 1440 parts by mass. The yield of the coconut shell / phenolic resin composite carbonized material thus obtained was 28.1% by mass, and the content of coconut shell carbide in the coconut shell / phenolic resin composite carbonized material was 79.9% by mass. there were.

Example 4
A reaction vessel equipped with a stirrer was charged with 137 parts by weight of furfuryl alcohol, 100 parts by weight of 37% by weight formalin, 3.2 parts by weight of 85% by weight phosphoric acid aqueous solution, and 3000 parts by weight of water. 360 parts by mass of the same coconut shell powder as 1 was charged. Thereafter, the reaction is made in the same manner as in Production Example 1 to prepare a coconut shell / furan resin composite material, and this coconut shell / furan resin composite material is further heat-treated in the same manner as in Example 1 to produce a coconut shell / furan resin composite carbonized material. Material particles were obtained. The yield of the coconut shell / furan resin composite carbonized material thus obtained was 28.5% by mass, and the content of coconut shell carbide in the coconut shell / furan resin composite carbonized material was 49.8% by mass. there were.

(Comparative Example 1)
A reaction vessel equipped with a stirrer was charged with 123 parts by weight of phenol, 126 parts by weight of 37% by weight formalin and 14 parts by weight of hexamethylenetetramine, and the temperature was raised to 65 ° C. over 60 minutes while stirring. The addition condensation reaction was carried out for 3 hours as it was. Next, after dehydrating to 70 ° C. under a reduced pressure of 133 hPa (100 Torr), 612 parts by mass of methanol was added and dissolved to obtain a methanol varnish of a phenol resin. The phenol resin concentration of this varnish was 20% by mass.

  Next, 400 parts by mass of the same coconut shell powder as in Example 1 was placed in a desiccator, and 910 parts by mass of phenolic resin methanol varnish was added and mixed well. Then, the pressure was reduced and the coconut shell was impregnated with phenolic resin. . Next, this was spread on a polyethylene sheet to volatilize methanol, and further cured by a dryer at 110 ° C. for 3 hours to cure the phenol resin.

  The coconut shell / phenolic resin composite material thus obtained was heat-treated and fired in the same manner as in Example 1 to obtain a coconut shell / phenolic resin composite carbonized material. The yield of the coconut shell / phenolic resin composite carbonized material thus obtained was 34.4% by mass, and the content of the coconut shell carbide in the coconut shell / phenolic resin composite carbonized material was 50.2% by mass. there were.

(Comparative Example 2)
The methanol varnish of the phenol resin obtained in Comparative Example 1 was cured without mixing the coconut shell powder, and then the phenol resin cured product was heat-treated in the same manner as in Example 1 to obtain a phenol resin carbonized material. The yield of the phenol resin carbonized material thus obtained was 54.9% by mass.

(Comparative Example 3)
The same coconut shell powder as in Example 1 was heat-treated in the same manner as in Example 1 to obtain a coconut shell carbonized material. The yield of the coconut shell carbonized material thus obtained was 24.9% by mass.

About the carbonized material obtained in said Examples 1-4 and Comparative Examples 1-3, the external appearance was observed visually and the loose filling bulk density was measured. The loosely packed bulk density was measured using an “ABD powder property measuring instrument” manufactured by Tsutsui Rika Kikai Co., Ltd., a 100 cm ³ sample container was placed on the measurement disk, and the sample was supplied from the upper hopper, When the sample container was full, the crested portion was scraped off with a spatula and the total amount of the sample in the sample container was measured. The loosely packed bulk density was calculated from the following equation.
Loosely filled bulk density (g / cm ³ )
= (Sample weight: g) / (Sample container volume: 100 cm ³ )

  Further, the appearance of the carbonized material of Example 2 and Comparative Example 3 was observed with an electron microscope (SEM) photograph. The carbonized material of Example 2 was shown in FIG. 1 (a), and the carbonized material of Comparative Example 3 was shown in FIG. 1 (b). Shown in As seen in the SEM photograph, it is confirmed that the carbonized material of Example 2 contains phenol resin charcoal on the surface of coconut shell charcoal and in the conduit.

(Examples 5-8 and Comparative Examples 4-6)
40 parts by mass of the carbonized material obtained in Examples 1 to 4 and Comparative Examples 1 to 3 and 60 parts by mass of a polyphenylene ether resin (“Iupiace AH8” manufactured by Mitsubishi Engineering Plastics) were taken and dry-blended, followed by a lab test. Using a mill, the mixture was uniformly melt-kneaded at 320 ° C. And after cooling and solidifying this, it grind | pulverized and obtained the conductive resin composition.

  Then, a test board having a length and width of 100 mm and a thickness of 2 mm was produced by injection molding the conductive resin composition, and the resistivity of the test board was measured according to JIS K 7194. The results are shown in Table 2.

  As seen in Table 2, it is confirmed that each example has a low resistivity and excellent conductivity.

(Examples 9-11 and Comparative Examples 7-9)
To 3 g of the carbonized material obtained in Examples 1 to 3 and Comparative Examples 1 to 3, 3 g of a binder prepared by dissolving 10% by mass of polyvinylidene fluoride in N-methylpyrrolidone was added and mixed to form a slurry. did. Then, this slurry was applied to a circular copper foil having a thickness of 20 μm and a diameter of 12 mm, vacuum-dried at 130 ° C. for 10 hours, and then press-molded under reduced pressure to produce an electrode.

The charge / discharge capacity of the electrode obtained as described above was measured. A two-electrode cell was used for charge / discharge capacity measurement. Metal lithium was used for the counter electrode, a carbon material was used for the working electrode, and a polypropylene porous membrane was used for the separator. As the electrolytic solution, an ethylene carbonate / diethylene carbonate solution (50/50% by mass) of 1 molar lithium perchlorate was used. Charging / discharging was performed by flowing a constant current of 25 mA / g between the positive electrode and the negative electrode, and the discharge time and charging time were determined by measuring the change with time of the potential difference between the two electrodes. Since the current density is constant, the charge / discharge capacity was determined by adding the discharge time or the charge time to the current density. Further, the charge / discharge capacity was similarly determined after 10 cycles of charge / discharge were repeated with this charge / discharge as one cycle. Furthermore, the cycle characteristics at that time were obtained from the following equation. The results are shown in Table 3.
Cycle characteristics (%) =
(10th cycle charge / discharge capacity / first cycle charge / discharge capacity) × 100

  As seen in Table 3, it is confirmed that each of the examples has a large charge / discharge capacity, and even after repeated charge / discharge, there is little decrease in charge / discharge capacity and can extend the battery life. .

(Examples 12-14 and Comparative Examples 10-12)
The carbonized materials obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were treated at 850 ° C. for 2 hours in a mixed gas atmosphere of a rotary kiln furnace circulated at a water flow rate of 5 ml / min and a nitrogen flow rate of 2 l / min. And activated carbon was obtained. The obtained activated carbon was measured for iodine adsorption performance and packing density according to JIS K 1474, and the specific surface area and pore volume were measured. The specific surface area and pore volume were measured by a low pressure method using nitrogen gas at a liquid nitrogen temperature using “Shimadzu Micromeritex Model 2200” manufactured by Shimadzu Corporation as a measuring device. Table 4 shows the measurement results.

(Examples 15 to 17 and Comparative Examples 13 to 15)
To 1 part by mass of the activated carbons of Examples 12 to 14 and Comparative Examples 10 to 12 obtained as described above, 1.5 parts by mass of sulfuric acid having a concentration of 30% by mass was impregnated and kneaded to obtain a paste. An electric double layer capacitor was manufactured by applying 0.9 g of this paste to each of two circular platinum electrodes having a diameter of 30 mm and pressing the electrodes together through a polypropylene separator.

  Then, after charging the electric double layer capacitor thus obtained at 0.9V for 1 hour, it is necessary to discharge the discharge current of 10 mA and reduce the voltage of the electric double layer capacitor to 0.54 to 0.45V. The measured time was measured, and the weight capacitance, which is the capacitance per unit time, and the capacitance capacitance, which is the capacitance per unit volume, were obtained. The results are shown in Table 5.

  As seen in Table 5, it is confirmed that each example has a large capacitance.

It is a microscope picture of the granular material of a carbonization material, (a) shows the 1000 time photograph of Example 2, (b) shows the 500 times photograph of the comparative example 3. FIG.

Claims (12)

  Heat treatment in a non-oxidizing atmosphere is performed on a composite material of a cured resin and porous particles obtained through a polymerization reaction in the presence of a reaction catalyst while mixing resin raw materials with porous particles. A composite carbonized material characterized by being carbonized.   The composite carbonized material according to claim 1, wherein the resin raw material is a phenol and an aldehyde, and the composite material is a composite material of a phenol resin and a porous granular material.   The composite carbonized material according to claim 1, wherein the resin raw material is furans and aldehydes, and the composite material is a composite material of furan resin and porous powder.   The composite carbonized material according to any one of claims 1 to 3, wherein the porous granular material is an uncarbonized organic substance.   The composite according to claim 4, wherein the porous granular material made of uncarbonized organic material has a carbide yield of 0.5% by mass or more when heated in a non-oxidizing atmosphere at 800 ° C. Carbonized material.   The porous granular material comprising an uncarbonized organic substance is selected from coconut husk, coffee beans, lignin, wood powder, cellulose, sawdust, rice husk, bamboo, plastic powder, and rubber powder. The composite carbonized material according to 4 or 5.   The composite carbonized material according to any one of claims 1 to 3, wherein the porous granular material is a carbide.   A composite material of cured resin and porous particles is prepared through a process of polymerizing in the presence of a reaction catalyst while mixing the resin raw material with porous particles, and this composite material is prepared in a non-oxidizing atmosphere. A method for producing a composite carbonized material, characterized by heat-treating and carbonizing.   A composite activated carbon, wherein the composite carbonized material according to any one of claims 1 to 7 is activated.   A conductive resin composition comprising at least one of the composite carbonized material according to any one of claims 1 to 7 and the composite activated carbon according to claim 9 as a conductive filler in a resin.   An electrode for a secondary battery, comprising at least one of the composite carbonized material according to any one of claims 1 to 7 and the composite activated carbon according to claim 9 as an electrode material. An electric double layer capacitor polarizable electrode comprising: the composite carbonized material according to any one of claims 1 to 7 and at least one of the composite activated carbon according to claim 9 as an electrode material. .

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