WO2003087262A1

WO2003087262A1 - Active polycyclic aromatic hydrocarbon material and method for production thereof

Info

Publication number: WO2003087262A1
Application number: PCT/JP2003/003294
Authority: WO
Inventors: Hisashi Satake; Shizukuni Yata; Hiroyuki Tajiri
Original assignee: Osaka Gas Company Limited
Priority date: 2002-04-17
Filing date: 2003-03-19
Publication date: 2003-10-23
Also published as: JPWO2003087262A1

Abstract

An active polycyclic aromatic hydrocarbon material, which is produced by subjecting a coal-based raw material having an oxygen concentration of 25 to 50 % to a heat treatment in an inert gas atmosphere and has the following characteristics: (a) a H/C ratio (a ratio the content of hydrogen atoms to that of carbon atoms) of 0.05 to 0.5, and (b) a specific surface area value according to the BET method of 1000 to 3000 m2/g; and a method for producing the hydrocarbon material. The hydrocarbon material can be produced by subjecting a raw material containing an inexpensive coal as a main component to a heat treatment, and also can provide an electrode exhibiting enhanced capability for ion adsorption per unit weight and/or unit volume.

Description

Description Active polycyclic aromatic hydrocarbon material and method for producing the same

The present invention relates to an active polycyclic aromatic hydrocarbon material having electrical conductivity. Background art

Polymer materials have excellent properties such as moldability, light weight, and mass productivity. In particular, in many industrial fields represented by the electronics industry, in addition to these characteristics, organic semiconductive or conductive organic polymer materials are required.

In particular, it has properties as n-type or p-type semiconductors, such as silicon and germanium, as well as organic polymer semiconductors whose electrical conductivity is in the semiconductor or conductor region, and their pn junctions There is a need for organic polymer semiconductors that can be applied to diodes, solar cells, and the like that utilize GaN. As organic polymer materials having properties as n-type or p-type semiconductors, boriaacetylene, polyphenylene, and the like are known.

For example, “Synthetic Metals” Chemical Supplement 87, 1980, pp. 15-28 states that acetylene is polymerized directly to obtain polyacetylene in the form of a film, which is then doped with an electron-donating doping agent or an electron-accepting material. There is disclosed a method of obtaining a P-type or n-type semiconductor in which electric conductivity is greatly increased by doping a doping agent. However, polyacetylene is very poor in practicality because it is easily oxidized by oxygen.

Also, polyphenylene, unlike polyacetylene, has relatively excellent oxidative stability. However, in polyphenylene, the phenylene skeleton forms a single bond on the line, and the conjugate system between carbon atoms is small, so it is thought that there is a limit to the electron conductivity achieved by doping with a doping agent. . Also, it is considered that there is a limit in controlling impurities by the dopant. Thus, an electrically conductive organic polymer material having the electrical conductivity of a semiconductor or conductor, excellent physical properties, and excellent oxidative stability has been developed (Japanese Patent Publication No. 6-43545). ). This material is a polycyclic aromatic hydrocarbon material (commonly referred to as a low-temperature-treated carbon material or a polyacene organic semiconductor), and is currently manufactured and widely applied as a semiconductor material. Polyacene-based organic semiconductors have excellent stability such as oxidation resistance, chemical resistance, and heat resistance. A wide range of conductivity can be obtained by selecting reaction conditions, and many conductive polymers (polyaniline, polypyrrole, etc.) This method has many advantages, such as the ability to do both P-type (negative ion) and n-type (cation) doping, which was difficult in).

Polyacene-based organic semiconductors have a higher-order structure with molecular-level gaps formed by the one-dimensional graphite cut ends developed into a three-dimensional network. For this reason, the ion adsorption capacity is stronger than activated carbon, and a large amount of dopant can be stored quickly. In addition, since the material does not change much in volume when the dopant is put in and taken out and is very stable, it is attracting attention as an electric double layer capacitor material. In addition, this material does not contain any heavy metals, so it is an environmentally friendly, safe and reliable material.

However, the above-mentioned known polyacene-based organic semiconductors have insufficient ion adsorption capacity per unit weight, and when used as an electrode material for electric double layer capacity, the ion adsorption capacity per unit volume of the electrode is not sufficient. There is a problem that it is enough. In addition, the use of phenolic resin as a raw material has the problem that the raw material costs are high.

Therefore, there is a need for an active polycyclic aromatic hydrocarbon material which has high ion adsorption capacity per unit weight of the electrode and ion adsorption capacity per Z or unit volume, and is easy to manufacture with a powerful and inexpensive raw material. . Disclosure of the invention

The present invention relates to an active polycyclic aromatic carbon having high ion adsorption capacity per unit weight of electrode and high ion adsorption capacity per unit volume of electrode obtained by heat-treating a raw material mainly composed of inexpensive coal. The purpose is to provide a hydrogen material and a method for producing the same. Furthermore, the present invention provides an electrode coating using the active polycyclic aromatic hydrocarbon material. It is also intended to provide a festival.

The present inventors have conducted intensive studies to solve the above problems, and as a result, by treating a coal-based raw material containing coal as a main component under specific conditions, an active polycyclic aromatic having specific physical properties has been obtained. The present inventors have found that a hydrocarbon-based material can be produced, and have conducted further research, thereby completing the present invention which can achieve the above object.

That is, the present invention provides the following active polycyclic aromatic hydrocarbon materials and the like.

1. An activated polycyclic aromatic hydrocarbon material having the following properties, obtained by heat-treating a coal-based raw material having an oxygen concentration of 25 to 50% in an inert gas atmosphere:

(a) The H / C ratio (content ratio of hydrogen atoms to carbon atoms) is 0.05 to 0.5,

(b) The specific surface area by the BET method is 1000 to 3000 mVg.

2. The active polycyclic aromatic hydrocarbon material according to 1 above, wherein (b) the specific surface area by BET method is 1500 to 3000 m ² / g.

3. The active polycyclic aromatic hydrocarbon material according to the above 1 or 2, wherein the coal-based raw material having an oxygen concentration of 25 to 50% is a coal-based raw material obtained by an oxygen crosslinking reaction of coal.

4. The activated polycyclic aromatic coal-based danishu material according to the above item 3, wherein the coal is lignite or lignite.

5. The active polycyclic aromatic hydrocarbon material according to any one of the above items 1 to 4, wherein the coal-based raw material is heat-treated together with a thermal reaction aid.

6. The active polycyclic aromatic hydrocarbon material according to 5 above, wherein the thermal reaction aid is at least one selected from the group consisting of zinc chloride, phosphoric acid, calcium chloride, sodium hydroxide, and K-oxidizing lime. .

7. The active polycyclic aromatic hydrocarbon material according to the above item 5, wherein the amount of the thermal reaction aid is 30 to 800 parts by weight based on 100 parts by weight of the coal-based raw material.

8. The activated polycyclic aromatic hydrocarbon material according to 1 above, having the following characteristics, obtained by heat-treating a coal-based raw material having an oxygen concentration of 25 to 50% in an inert gas atmosphere:

(b) Specific surface area by BET method is 1000-200 OmVg,

(c) Mesopore volume by the BJH method is 0.02 to 0.2 ml / g, (d) The total pore volume by the MP method is 0.3 to 1.0 ml / g.

9. The active polycyclic aromatic hydrocarbon material according to claim 8, wherein the coal-based raw material having an oxygen concentration of 25 to 50% is a coal-based raw material obtained by an oxygen crosslinking reaction of coal.

10. The active polycyclic aromatic hydrocarbon material according to the above item 8 or 9, wherein the coal is lignite or lignite.

11. The active polycyclic aromatic hydrocarbon material according to any one of the above items 8 to 10, wherein the coal-based raw material is heat-treated together with a thermal reaction aid.

12. The active polycyclic aromatic system according to the above 11, wherein the thermal reaction aid is at least one selected from the group consisting of zinc chloride, phosphoric acid, calcium chloride, sodium hydroxide, and water-soluble lime. Hydrocarbon materials.

13. The active polycyclic aromatic carbon material according to the above item 11, wherein the amount of the thermal reaction aid is 50 to 200 parts by weight based on 100 parts by weight of the coal-based raw material.

1 4. A method for producing an active polycyclic aromatic hydrocarbon material comprising the following steps:

(i) subjecting the coal to an oxygen crosslinking reaction to obtain a coal-based raw material having an oxygen concentration of 25 to 50%, and

(ii) a step of heat-treating a coal-based raw material having an oxygen concentration of 25 to 50% together with a thermal reaction aid in an inert gas atmosphere.

1 5. Above; An electrode comprising the active polycyclic aromatic hydrocarbon material according to any one of Items 1 to 13.

1 6. An electrode containing the active polycyclic aromatic hydrocarbon material according to any one of the above items 1 to 13, carbon black, and a binder.

17. The method is characterized in that after mixing the active polycyclic aromatic hydrocarbon material described in any one of the above items 1 to 13, the power pump rack, and the binder, the mixture is molded. Electrode manufacturing method. '

18. An electrode obtained by the method described in 17 above.

19. Capacitance containing the electrode described in 15 or 16 above.

20. A capacitor comprising the electrode, the current collector, the separator, and the electrolytic solution according to 15 or 16 above. Activated polycyclic aromatic carbon-based hydrogenated material of the present invention

The activated polycyclic aromatic hydrocarbon material of the present invention has the following properties. That is, the content ratio of hydrogen atoms to carbon atoms (hereinafter referred to as ΓΗ / C ratio) in the active polycyclic aromatic hydrocarbon material of the present invention is about 0.05 to 0.5, and is preferably Is about 0.1 to 0.3, more preferably about 0.15 to 0.3. If the HZC ratio is too high, the polycyclic aromatic conjugated structure is not sufficiently developed, so that a predetermined electrical conductivity cannot be obtained, so that sufficient ion adsorption capacity per unit weight cannot be exhibited. On the other hand, if the H / C ratio is too low, the carbonization proceeds too much to become a normal activated carbon, and a sufficient ion adsorption capacity per unit weight cannot be obtained. The H / C ratio is measured by an elemental analyzer.

One embodiment of the active polycyclic aromatic hydrocarbon material of the present invention (hereinafter referred to as “material A”) has a specific surface area value by the BET method under the condition that the H / C ratio is in the above range. It is about 1000-3000 m ² / g. The specific surface area is preferably about 1500 to 3000 mVg, more preferably about 1700 to 2800 m ² / g. If the specific surface area is too large, the bulk density tends to decrease and the amount of adsorbed ions per unit volume (specific capacity) tends to decrease, which is not preferable.

That is, the material A of the present invention is characterized in that the above-mentioned HZC ratio and the specific surface area determined by the BET method simultaneously satisfy specific numerical values. When an aromatic hydrocarbon material is used as an electrode, a sufficient ion adsorption amount can be obtained per unit weight of the electrode.

In another embodiment of the active polycyclic aromatic hydrocarbon material of the present invention (hereinafter referred to as “material B”), the specific surface area by the BET method under the condition that the H / C ratio is in the above range is described. However, it is about 1000 to 2000 m ² / g. Specific surface area by the BET method is preferably 1100 to 1800 m ² / g, more preferably about 1200~1600m ² / g approximately. If the specific surface area is too large, the bulk density tends to decrease and the amount of adsorbed ions per unit volume (specific capacity) tends to decrease, which is not preferable.

In addition, the material B of the present invention has a mesopore volume by the BJH method of about 0.02 to 0.2 ml / g, preferably about 0.02 to 0.1 ml / g. If the mesopore volume is too small, pores are not formed, and the ion adsorption capacity per unit weight is reduced. Although the ion adsorption capacity per weight is large, it is not preferable because the density decreases and the ion adsorption amount per unit volume decreases. The BJH method is a method proposed by Barrett, Joyner, and Harenda et al. For determining the distribution of mesopores (EP Barretts LG Joyner and PP Halenda, J, Am. Chem. Soc., 73, 373, (1951)).

Further, the material B of the present invention has a total pore volume by the MP method of about 0.3 to 1.0 ml / g, preferably about 0.4 to 0.8 ml / g. If the total pore volume is too low, the number of micropores serving as ion adsorption sites will decrease, and a sufficient ion adsorption capacity per unit volume will not be obtained. The MP method is defined as “t-plot method J (BC Lippens, JH de Boer, J. Catalys is, 4, 319 (1965))” and the micropore volume, micropore area, and micropore area. Mikhai (M. Mikhai 1), Brunauer, Bodor, and others (RS Mikhai 1, S. Brunauer, EE Bodor, J Colloid Interface Sc i., 26, 45 (1968)).

That is, in the material B of the present invention, the above-mentioned H / C ratio, the specific surface area by the BET method, the mesopore volume by the BJH method, and the total pore volume by the MP method simultaneously satisfy the specific values. When the activated polycyclic aromatic hydrocarbon material having this feature is used as an electrode, a sufficient ion adsorption amount per unit weight of the electrode can be obtained, and a sufficient amount per unit volume of the electrode can be obtained. It is also possible to obtain a suitable ion adsorption amount. Method for producing active polycyclic aromatic hydrocarbon material of the present invention

The active polycyclic aromatic hydrocarbon material (including the above-mentioned materials A and B) of the present invention can be produced by heat-treating a coal-based raw material under an inert gas atmosphere. Examples of coal-based raw materials include bituminous coal, lignite, lignite, peat coal, and the like. These may be used alone or as a mixture of two or more. In order for the active polycyclic aromatic hydrocarbon material of the present invention to have desired properties, it is preferable that the material contain a large amount of oxygen atoms and hydrogen atoms. In particular, as the coal-based raw material, a coal-based raw material having an oxygen concentration of about 25 to 50% is preferable. Here, the oxygen concentration refers to the weight percent (weight content) of oxygen atoms in the coal-based raw material measured by elemental analysis. In general, coal classification is based on coal dagger (eg, based on carbon content). For example, lignite and lignite have a carbon content of about 78% or less, bituminous coal has a carbon content of 78-90%, and anthracite has a carbon content of about 90% or more. The lower the degree of coalification, the higher the ratio of hydrogen and oxygen, especially the ratio of oxygen. Lignite and lignite have a high oxygen concentration of about 20% or more. ~ 20%, less than about 7% for anthracite. Therefore, lignite and lignite are preferred as coal-based raw materials.

As the coal-based raw material that can be used in the production method of the present invention, the above-described coal can be used, but a coal-based raw material in which the oxygen concentration is about 25 to 50% by performing an oxygen crosslinking reaction on coal in advance is used. Is preferred. In particular, lignite or lignite, which is a coal having a high oxygen concentration and a low degree of coalification, is preferably used as the coal used in the oxygen crosslinking reaction. The active polycyclic aromatic hydrocarbon material of the present invention is produced, for example, through the following process.

(1) Coal oxygen crosslinking reaction process

Examples of the method of the oxygen crosslinking reaction of coal include various methods such as a method of heating coal in air and a method of contacting coal with an acidic liquid such as nitric acid and sulfuric acid. The coal used is preferably in the form of a powder having a large surface area that is easily crosslinked with oxygen.

In the case of heating coal in the air, the heating temperature may be, for example, about 100 to 350 ° C, and preferably about 150 to 300 ° C. Normally, the pressure may be about normal pressure. The heating time may be, for example, about 1 to 30 hours. More specifically, for example, the temperature of coal powder is raised from room temperature to about 150 to 300 ° C over about 0.5 to 10 hours, and is maintained at the same temperature for about 1 to 20 hours, and then cooled to room temperature. Good.

The method of bringing coal into contact with an acidic liquid such as nitric acid or sulfuric acid may be performed using a known method.

The oxygen concentration of the coal-based raw material after the oxygen crosslinking treatment is preferably 25 to 50%, and more preferably 30 to 48%. If the oxygen concentration is less than 25%, it is difficult to obtain desired performance in the activated polycyclic aromatic hydrocarbon material of the present invention. (2) Adjustment of coal-based raw materials

The coal-based raw material after the above oxygen cross-linking reaction can be subjected to the heat treatment step (3) as it is, but it is difficult to obtain a large specific surface area. After that, it is preferable to perform the heat treatment step. Here, the thermal reaction aid has a function of increasing the specific surface area of the coal-based raw material by acting on the coal-based raw material after the oxygen crosslinking reaction to form pores on the surface of the coal-based raw material. Is what you have. Examples of the thermal reaction aid include inorganic salts such as zinc chloride, phosphoric acid, calcium chloride, sodium hydroxide, potassium hydroxide, and the like, and at least one selected from these may be selected. it can. Among them, it is preferable to use zinc chloride. The amount of the thermal reaction aid varies depending on the type of coal-based raw material, the type of inorganic salt, etc., but for both Material A and Material B, it is about 30 to 800 parts by weight based on the so-called oxygen-crosslinked coal. And preferably about 50 to 500 parts by weight. In particular, in the case of material B, the amount is about 50 to 200 parts by weight, preferably about 50 to 180 parts by weight, based on 100 parts by weight of the oxygen-crosslinked coal.

As a method for mixing the coal-based raw material and the thermal reaction aid, any method may be used as long as the two are uniformly mixed, and examples thereof include a method using a planetary mixer, a tandem and the like.

In addition, in order to facilitate the handling of the raw material composed of a mixture of the coal-based raw material and the thermal reaction aid obtained above (this mixture is referred to as a “raw material mixture”; the same applies hereinafter), the raw material mixture is formed into a film form. It may be formed into a predetermined shape such as a plate shape or a chip shape. When performing molding, a molding aid for improving moldability can be further mixed, if necessary. As the molding aid, any known molding aid can be used without particular limitation.

When the raw material mixture is press-formed as it is, for example, a molding aid having binding properties such as a cell opening, propyloxymethylcellulose (CMC), and methylcellulose (C) can be used. When the cell mouth is used as a molding aid, the amount of calorie added is usually about 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of coal which is the main component of the raw material mixture. It is about parts by weight.

When performing heat molding, for example, a phenolic resin (for example, resol, A thermosetting resin such as Nopolak) can also be used as a molding aid. When the thermosetting resin is used as a molding aid, the amount added is usually about 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of coal, which is the main component of the raw material mixture. It is about parts by weight. When a thermosetting resin is used as a molding aid, a temperature of about 50 to 250 (more preferably about 100 to 200 ° C) is used for about 1 to 120 minutes (more preferably 5 to 60 minutes). By heating, curing molding is possible.

(3) Heat treatment process

The active polycyclic aromatic hydrocarbon material of the present invention can be obtained by heat-treating the raw material mixture or the molded product obtained above.

The heat treatment of the raw material mixture or its molded product is performed in an inert gas atmosphere such as nitrogen or argon. Because heat treatment is performed at a high temperature, the molded product will burn if a combustible gas such as oxygen or a combustible gas is mixed. The pressure for the heat treatment is not particularly limited, but usually may be about normal pressure. The temperature of the heat treatment is appropriately determined according to the composition of the raw material mixture and other heat treatment conditions (heating rate, heat treatment time, etc.), but may be generally in the range of about 500 to 700 ° C, and 520 to 700 ° C. ° C is preferred. Particularly, in order to obtain an appropriate H / C ratio, it is more preferable that the peak temperature be 550 to 700 ° C. The heating rate is, for example, usually about 10 to 250 ° C / hour, preferably about 20 to 200 ° CZ hour.

(4) Cleaning and drying process

The thermal reaction product obtained above is washed with a detergent to remove inorganic salts contained in the thermal reaction product. The cleaning agent is not particularly limited as long as the inorganic salt can be removed, and examples thereof include 7f and dilute hydrochloric acid. If dilute hydrochloric acid is used, it is preferable to finally wash it further with water to remove hydrochloric acid.

Then, the washed material is dried to obtain the active polycyclic aromatic hydrocarbon material of the present invention. The drying method is not particularly limited, and a known drying method may be used. Electrode using activated polycyclic aromatic carbon bicarbonate material of the present invention

The hydrogenated active polycyclic aromatic hydrocarbon material of the present invention obtained as described above has a higher ion-adsorbing capacity per unit weight of an electrode than a known polyacene-based organic semiconductor, and is used as an electrode material in a capacitor or the like. Can be.

(1) Electrode

An electrode can be produced by using the activated polycyclic aromatic hydrocarbon material of the present invention as an electrode material.

For example, an electrode can be produced by pulverizing an active polycyclic aromatic hydrocarbon material, mixing the pulverized material, a carbon black and a binder, and then molding the mixture.

The method for pulverizing the active polycyclic aromatic hydrocarbon material is not particularly limited, and a known method may be used. For example, a pulverizing method using a pole mill, a jet mill, or the like can be used.

The average particle size of the carbon black used may be about 0.1 to 10 m. The average particle size is measured by dispersing a force pump rack uniformly in water and using a laser-based particle size distribution measurement method. The amount of the power pump rack used is, for example, about 0.5 to 30 parts by weight, preferably about 1 to 20 parts by weight, based on 100 parts by weight of the pulverized material of the activated polycyclic aromatic aromatic carbon material. .

Examples of the binder include polytetrafluoroethylene resin, styrene butadiene rubber (SBR), polyvinylidene fluoride (PVDF) and the like, and polytetrafluoroethylene resin is preferable. The binder is preferably in the form of a powder to facilitate moldability. The amount of the binder used may be, for example, about 1 to 30 parts by weight based on 100 parts by weight of the pulverized active polycyclic aromatic hydrocarbon material.

The method of mixing the pulverized active polycyclic aromatic hydrocarbon material, carbon black and the binder is not particularly limited, and a known mixing method may be used. For example, a method using a normal mixer, a kneader or the like may be used. No.

Examples of a method for molding the obtained mixture include press molding and extrusion molding. In particular, press molding is preferable. The thickness of the electrode can be appropriately selected according to the use of the electrode.

(2) Capacitor

A capacitor can be manufactured using the electrode obtained in the above (1).

For example, a capacitor can be manufactured by drying the electrode obtained in the above (1) to form a positive electrode and a negative electrode, then adding a separator and an electrolytic solution.

The shape of the electrode can be appropriately selected according to the purpose of use, but is preferably a sheet. The electrode may be dried as long as it can sufficiently remove water, and is usually 70 to 28 (about TC and dried for about 10 hours. The dried electrode is used as a positive electrode and a negative electrode.

Examples of the current collector include stainless steel mesh and aluminum, and among them, stainless steel mesh is preferable. The thickness of the current collector may be, for example, about 0.02 to 0.5 mm.

The structure of the separator is not particularly limited, but a single-layer or multi-layer separator can be used. The material of the separator is not particularly limited, but examples thereof include electrolytic capacitor paper, polyolefin such as polyethylene and polypropylene, polyamide, kraft paper, glass, and cellulosic materials. It is determined as appropriate according to the safety design. Among them, an electrolytic capacitor paper is preferable. Also, it is preferable that the separation is sufficiently dried.

As the electrolyte, for example, a known non-aqueous electrolyte containing an ammonium salt can be used. Specifically, ammonium salts such as triethylmethylammonium tetrafluoroporate (Et ₃ MeNBF ₄ ) and tetraethylammonium.tetrafluoroporate (Et ₄ NBF ₄ ) are mixed with propylene carbonate and ethylene carbonate. And dimethyl ether carbonate, dimethyl carbonate, methyl ethyl carbonate, dimethoxyethane, τ-butyrolactone, methyl acetate, methyl formate, or those dissolved in an organic solvent such as a mixed solvent of two or more thereof. Further, the concentration of the electrolytic solution is not particularly limited, but generally 0.5 mol / l to 2 mol / l is practical. Of course, it is preferable to use an electrolyte having a water content of 100 ppm or less.

Assemble the above electrodes, separator and electrolyte in a dry box, for example By doing so, you can get the capacity.

In the capacitor thus obtained, the ion adsorption amount per unit weight and the ion adsorption amount per unit volume (specific capacity) of the electrode using the material of the present invention are very good. For example, in the electrode using the material A, the ion adsorption amount per unit weight of the electrode is about 35 to 50 F / g, preferably about 40 to 50 F / g. In the electrode using material B, the ion adsorption amount per unit weight of the electrode is about 35 to 50 F / g, preferably about 40 to 50 F / g, and the ion adsorption amount per unit volume of the electrode is , About 25 to 50 FZcc, preferably about 26 to 50 F / cc. The ion adsorption amount per unit weight of the electrode and the ion adsorption amount per unit volume (specific capacity) were measured as described in Examples. Further, the active polycyclic aromatic hydrocarbon material of the present invention can be suitably used as an adsorbent for water treatment, an adsorbent for smoke exhaust, an adsorbent for deodorization, and the like. BEST MODE FOR CARRYING OUT THE INVENTION

Examples are shown below to further clarify features of the present invention. Example 1

First, oxygen crosslinking of lignite, the main raw material, was performed. That is, lignite (oxygen concentration 21.0%) powder was placed in a porcelain dish and heat-treated in air using a small cylindrical furnace. In the heat treatment, the brown coal powder was heated from room temperature to 250 ° C over 2 hours, kept at the same temperature for 7 hours, cooled to room temperature, and taken out of the cylindrical furnace. Oxygen concentration was determined by performing elemental analysis of the oxygen-crosslinked lignite (measurement device: PE2400 Series II, CHNS / 0, elemental analyzer manufactured by PerkinElmer) o The oxygen concentration was 34.5%. Was.

To the oxygen-crosslinked lignite, zinc chloride as a thermal reaction aid was added and mixed. The mixing ratio was 400 parts by weight of zinc chloride per 100 parts by weight of lignite subjected to oxygen crosslinking. An appropriate amount of water was added to these and mixed to obtain an aqueous slurry (solid content 85% by weight + moisture 15% by weight).

The aqueous slurry was placed in a graphite dish and heat-treated using a small cylindrical furnace. In the heat treatment, the temperature was raised to 600 ° C at a rate of 120 ° C / hour in a nitrogen atmosphere, held at the same temperature for 1 hour, allowed to cool naturally in the furnace, and then taken out of the furnace.

After the heat-treated product was washed with dilute hydrochloric acid, it was washed with distilled water until the pH value was about 7. The heat-treated product after the washing was dried to obtain an active polycyclic aromatic hydrocarbon material of the present invention.

Elemental analysis was performed on the obtained activated polycyclic aromatic hydrocarbon-based hydrogen material, and the HZC ratio was determined (measuring device: PE2400 series element analyzer manufactured by PerkinElmer I, CHNS / 0). Further, the isotherm was measured using nitrogen as an adsorbate (measurement device: "N0VA1200" manufactured by urea ionics Co., Ltd.), and the specific surface area was determined from the obtained isotherm by the BET method. The results of the above measurements and calculations are shown in Table 1 below.

Next, the active polycyclic aromatic hydrocarbon material was pulverized, and 10 parts by weight of carbon black and 8 parts by weight of polytetrafluoroethylene resin powder as a binder were mixed with 100 parts by weight of this powder. Then, an electrode having a thickness of 0.5 thigh was obtained by press molding.

The sheet electrode obtained above was pressed to 1.5 cm × 1.5 cm and dried at 150 for 1 hour. The obtained electrodes were used as a positive electrode and a negative electrode.A 0.2-thick stainless steel mesh was used as a current collector, a sufficiently dried electrolytic capacitor paper was used as a separator, and a concentration of 1.5 mol / l was used as an electrolytic solution. A capacitor was assembled in a dry box using a solution of triethylmethylammonium'tetrafluoroporate (Et ₃ MeNBF ₄ ) / propylene carbonate (PC).

The amount of ion adsorption per unit weight was determined using the obtained capacitor. The ion adsorption amount was measured as the electric capacity (F / g) of the capacity. In other words, the maximum charging current of the capacitor was regulated to 50 mA, and the capacitor was charged at 2.5 V for 1 hour, and then discharged at a constant current of 1 mA until the capacitor voltage became 0 V. The electric capacity (F) was obtained from the slope of the discharge curve, and the capacity per electrode weight (F / g) was obtained from the total weight of the positive electrode / negative electrode and the electric capacity, and this value was used as the ion adsorption amount. The results are shown in Table 1. Example 2

In the same manner as in Example 1, the lignite was subjected to oxygen crosslinking treatment. Processing conditions are brown in air The charcoal powder was heated from room temperature to 28 CTC over 2 hours, kept at the same temperature for 7 hours, cooled to room temperature, and taken out of the cylindrical furnace. Elemental analysis of the obtained oxygen-crosslinked lignite was performed to determine the oxygen concentration. The oxygen concentration was 33.2%.

A thermal reaction aid was added to the oxygen-crosslinked lignite, and the active polycyclic aromatic hydrocarbon material of the present invention was obtained in the same manner as in Example 1 thereafter.

Using the obtained active polycyclic aromatic hydrocarbon-based hydrogen material, an electrode was formed in the same manner as in Example 1, a capacitor was assembled, and charge and discharge were performed. Table 1 shows the obtained results together with various physical properties of the active polycyclic aromatic hydrocarbon material. Example 3

In the same manner as in Example 1, the lignite was subjected to oxygen crosslinking treatment. The processing conditions were as follows: the temperature was raised from room temperature to 230 ° C in air over 2 hours, kept at the same temperature for 10 hours, cooled to room temperature, and taken out of the cylindrical furnace. The oxygen concentration was 35.0%. Thereafter, in the same manner as in Example 1, an active polycyclic aromatic hydrocarbon material of the present invention was obtained.

Using the obtained active polycyclic aromatic hydrocarbon-based hydrogen material, an electrode was formed, a capacitor was assembled, and charge / discharge was performed in the same manner as in Example 1. Table 1 shows the obtained results together with various physical properties of the active polycyclic aromatic hydrocarbon material. Comparative Example 1

In the same manner as in Example 1, the lignite was subjected to oxygen crosslinking treatment. The processing conditions were as follows: the temperature was raised from room temperature to 250 ° C in air over 2 hours, kept at the same temperature for 1 hour, cooled to room temperature, and taken out of the cylindrical furnace. The oxygen concentration was 24.3%. Thereafter, an active polycyclic aromatic hydrocarbon material was obtained in the same manner as in Example 1.

Using the obtained active polycyclic aromatic hydrocarbon material, an electrode was formed, a capacitor was assembled, and charging and discharging were performed in the same manner as in Example 1. Table 1 shows the obtained results together with various physical properties of the active polycyclic aromatic hydrocarbon material. Comparative Example 2

Example 1 was carried out without subjecting lignite, the main raw material, to oxygen crosslinking treatment (oxygen concentration 20.1%). A thermal reaction treatment was performed in the same manner to obtain an active polycyclic aromatic hydrocarbon material. Using the obtained active polycyclic aromatic hydrocarbon material, an electrode was formed, a capacitor was assembled, and charging and discharging were performed in the same manner as in Example 1. Table 1 shows the obtained results together with various physical properties of the active polycyclic aromatic hydrocarbon material. Comparative Example 3

Without using lignite, heat treatment was carried out in the same manner as in Example 1 except that 100 parts by weight (solid content) of 7K-soluble phenol resin was mixed with 100 parts by weight of zinc chloride. Hydrogen was obtained. The specific surface area value by the BET method was 2060 mVg.

Using the obtained active polycyclic aromatic hydrocarbon, an electrode was formed in the same manner as in Example 1, a capacitor was assembled, and charge and discharge were performed. Table 1 shows the obtained results together with various physical properties of the active polycyclic aromatic hydrocarbon material.

table 1

From Table 1, it can be seen that the active polycyclic aromatic hydrocarbon material of the present invention has a high ion adsorption capacity per unit weight, and when this is used as a capacitor electrode, high capacity and low cost can be achieved. Example 4

The mixing ratio of zinc chloride to be added to the oxygen-crosslinked lignite The same treatment as in Example 1 was performed except that 100 parts by weight of zinc chloride was used.

Elemental analysis of the obtained active polycyclic aromatic hydrocarbon material was performed to determine the H / C ratio.

(Measurement device: Element analyzer "PE2400 series H, CHNS / 0" manufactured by Perkin Elmer). Further, the isotherm was measured using nitrogen as an adsorbate (measurement apparatus: "N0VA1200" manufactured by urea ionics Co., Ltd.), and the specific surface area was determined from the obtained isotherm by the BET method. The total pore volume was determined by the MP method from the total amount of nitrogen gas adsorbed near the relative pressure P / PQ 1 (P: P and equilibrium pressure, P „: saturated vapor pressure (77 k, N ₂ )).

The mesopore volume was calculated by the BJH method.

Table 2 below shows the results of the above measurements and calculations.

Then, the above active polycyclic aromatic hydrocarbon material is powder-framed, and 10 parts by weight of carbon black and 8 parts by weight of polytetrafluoroethylene resin powder as a binder are added to 100 parts by weight of the powder. After mixing, an electrode having a thickness of 0.51M was obtained by press molding.

The sheet electrode obtained above was cut into 1.5 cm × 1.5 cm, and dried at 150 ° C. for 2 hours. The obtained electrodes were used as a positive electrode and a negative electrode, a 0.2 mm thick stainless steel mesh was used as a current collector, a well-dried electrolytic capacitor paper was used as a separator, and the concentration of the electrolyte was 1.5 mol / l. The capillaries were assembled in a dry pox using a solution of 1 triethylmethylammonium * tetrafluoroporate (Et ₃ MeNBF ₄ ) / propylene monoponate (PC).

Next, the amount of ion adsorption per unit volume (specific capacity) was determined using the obtained capacitor. The specific capacity was measured as the electric capacity per unit volume of capacity (F / cc). In other words, the maximum charging current of the capacitor was regulated to 50 mA, the battery was charged at 2.5 V for 1 hour, and then discharged at a constant current of 1 mA until the capacitor voltage reached 0 V. The electric capacity (F) was obtained from the slope of the discharge curve, and the specific capacity per electrode volume (F / cc) was obtained from the total volume of the positive electrode / negative electrode and the electric capacity. The results are shown in Table 2. Example 5

In the same manner as in Example 4, the lignite was subjected to oxygen crosslinking treatment. Processing conditions are brown coal powder The temperature was raised from the temperature to 280 ° C over 2 hours, maintained at the same temperature for 5 hours, cooled to room temperature, and taken out of the cylindrical furnace. Elemental analysis of the obtained oxygen-crosslinked lignite was performed to determine the oxygen concentration. The oxygen concentration was 34.4%.

The activated polycyclic aromatic aromatic compound of the present invention was prepared in the same manner as in Example 4 except that a thermal reaction auxiliary was added to the oxygen-crosslinked lignite, and the mixing ratio was changed to 150 parts by weight of zinc chloride with respect to 100 parts by weight of the lignite. A series hydrocarbon material was obtained.

Using the obtained active polycyclic aromatic hydrocarbon-based hydrogen material, an electrode was formed, a capacitor was assembled, and charging and discharging were performed in the same manner as in Example 4. The results obtained are shown in Table 2 together with various physical properties of the active polycyclic aromatic hydrocarbon material. Comparative Example 4

As in Example 4, the lignite was subjected to oxygen crosslinking treatment. The processing conditions were as follows: the temperature was raised from room temperature to 250 over 2 hours, maintained at the same temperature for 7 hours, cooled to room temperature, and taken out of the cylindrical furnace. The oxygen concentration was 34.6%.

Next, an active polycyclic aromatic compound was prepared in the same manner as in Example 4 except that a thermal reaction aid was added to the oxygen-crosslinked lignite, and the mixing ratio was changed to 230 parts by weight of zinc chloride with respect to 100 parts by weight of pitch. A series hydrocarbon material was obtained.

Using the obtained active polycyclic aromatic hydrocarbon material, an electrode was prepared, a capacitor was assembled, and charge and discharge were performed in the same manner as in Example 4. The results obtained are shown in Table 2 together with various physical properties of the active polycyclic aromatic hydrocarbon material. Comparative Example 5

Lignite was used as it was without oxygen crosslinking treatment. The oxygen concentration was 20.1%. An activated polycyclic aromatic carbon-based hydrogenated material was prepared in the same manner as in Example ⁴ , except that a thermal reaction auxiliary was added to the brown coal and the mixing ratio was changed to 100 parts by weight of zinc chloride with respect to 100 parts by weight of pitch. Obtained.

Using the obtained active polycyclic aromatic hydrocarbon material, an electrode was prepared, a capacitor was assembled, and charge and discharge were performed in the same manner as in Example 4. The results obtained are shown in Table 2 together with various physical properties of the active polycyclic aromatic hydrocarbon material. Comparative Example 6

Heat-treated in the same manner as in Example 4 except that 100 parts by weight (solid content) of 7K-soluble phenol resin was mixed without using coal (brown coal) and 230 parts by weight of zinc chloride. An aromatic hydrocarbon was obtained. The specific surface area value by the BET method was 1890 m ² / g.

Using the obtained active polycyclic aromatic hydrocarbon, an electrode was formed in the same manner as in Example 4, a capacitor was assembled, and charge and discharge were performed. Table 2 shows the obtained results together with various physical properties of the active polycyclic aromatic hydrocarbon.

Table 2

As can be seen from Table 2, the active polycyclic aromatic hydrocarbon material of the present invention has a large specific capacity and a large amount of ion adsorption per unit weight, and when this is used as a capacity electrode, higher capacity and lower cost can be achieved. Can be achieved. The active polycyclic aromatic hydrocarbon material of the present invention can be produced by heat treatment at a relatively low temperature using inexpensive coal as a raw material, thereby reducing raw material costs, running costs, etc. in the production. can do. For this reason, the industrial value of the activated polycyclic aromatic hydrocarbon material of the present invention is very large.

In addition, the active polycyclic aromatic hydrocarbon material of the present invention has a high ion adsorption capacity per unit weight and a high Z or ion adsorption capacity per unit volume. It can be suitably used as an electrode material such as a paster, and can increase the capacity of the capacitor and reduce the manufacturing cost.

Claims

The scope of the claims

(a) H / C ratio (content ratio of chromium atoms to carbon atoms) is 0.05 to 0.5,

(b) The specific surface area by the BET method is 1000 to 3000 mVg.

2. The active polycyclic aromatic hydrocarbon material according to claim 1, wherein (b) the specific surface area determined by the BET method is from 1500 to 3000 m ² / g.

3. The activated polycyclic aromatic hydrocarbon material according to claim 1 or 2, wherein the coal-based raw material having an oxygen concentration of 25 to 50% is a coal-based raw material obtained by an oxygen crosslinking reaction of coal.

4. The activated polycyclic aromatic hydrocarbon material according to claim 3, wherein the coal is lignite or lignite.

5. The active polycyclic aromatic hydrocarbon material according to any one of claims 1 to 4, wherein the coal-based raw material is heat-treated together with a thermal reaction aid.

6. The active polycyclic aromatic system according to claim 5, wherein the thermal reaction auxiliary is at least one selected from the group consisting of zinc chloride, phosphoric acid, calcium chloride, sodium hydroxide and potassium hydroxide. Hydrocarbon materials.

7. The active polycyclic aromatic hydrocarbon material according to claim 5, wherein the amount of the thermal reaction aid is 30 to 800 parts by weight based on 100 parts by weight of the coal-based raw material.

8. The active polycyclic aromatic hydrocarbon material according to claim 1, which is obtained by heat-treating a coal-based raw material having an oxygen concentration of 25 to 50% in an inert gas atmosphere, having the following characteristics:

(b) The specific surface area value by the BET method is 1000 to 2000 m ² / g,

(c) Mesopore volume by the BJH method is 0.02 to 0.2 ml / g,

(d) The total pore volume by the MP method is 0.3 to 1 · Oml / g.

10. The activated polycyclic aromatic substance according to claim 8 or 9, wherein the coal is lignite or lignite. Group hydrocarbon materials.

11. The active polycyclic aromatic hydrocarbon material according to any one of claims 8 to L0, wherein the coal-based raw material is heat-treated together with a thermal reaction aid.

12. The method according to claim 1, wherein the thermal reaction aid is at least one selected from the group consisting of zinc chloride, phosphoric acid, calcium chloride, sodium hydroxide, and water-soluble lime.

2. The active polycyclic aromatic hydrocarbon material according to 1.

13. The active polycyclic aromatic hydrocarbon material according to claim 11, wherein the amount of the thermal reaction aid is 50 to 200 parts by weight based on 100 parts by weight of the coal-based raw material.

1 4. A method for producing an active polycyclic aromatic hydrocarbon material comprising the following steps: '(i) subjecting coal to an oxygen crosslinking reaction to obtain a coal-based raw material having an oxygen concentration of 25 to 50%, and

15. An electrode containing the active polycyclic aromatic hydrocarbon material according to any one of claims 1 to L3.

16. An electrode comprising the active polycyclic aromatic hydrocarbon material according to any one of claims 1 to 13, carbon black, and a binder.

1 7. An electrode characterized in that after mixing the active polycyclic aromatic hydrocarbon material according to any one of claims 1 to 13, carbon black, and a binder, the mixture is molded. Recipe.

18. An electrode obtained by the production method according to claim 17.

19. A capacity containing the electrode according to claim 15 or 16.

20. A capacitor containing the electrode, the current collector, the separator, and the electrolytic solution according to claim 15 or 16.