JP2000007315A - Solid active carbon, electric double layer capacitor using the same and production of solid active carbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a solid active carbon capable of protecting micropores of a porous active carbon from an organic resin which is a binder, maintaining the specific surface area at a high value, having good moldability capable of freely providing a flexible sheetlike molded product according to various molding methods, etc., and further a high specific surface area and a high mechanical strength, excellent in durability and applicable to various kinds of uses and to provide an electric double layer capacitor using the same and a method for producing the solid active carbon. SOLUTION: This solid active carbon comprises an active carbon powder and/or active carbon fibers impregnated with any one or more kinds of a phthalic acid-based or a phosphoric acid-based or a fatty acid-based ester compound and a carbide obtained by heat-treating polyvinyl alcohol(PVA) or a resin derived from the PVA and a phenol resin and has 700-2,500 m2g specific surface area and >=300 gf/mm2 mechanical strength. Dibutyl phthalate(DBP) which is a liquid at room temperature is more preferred as the ester compound and the resin derived from the PVA is more especially preferably polyvinyl butyral(PVB).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode material used for various large-capacity capacitors such as electric double-layer capacitors and lithium ion batteries, backup power supplies, vehicle power supplies, auxiliary power supplies, and the like. Solid activated carbon generally applicable widely as a porous activated carbon sintered body used as a gas adsorbent, a filter material for water purification, food purification, wastewater purification, an electric double layer capacitor using the same, and a method for producing the same More particularly, the present invention relates to a solid activated carbon capable of realizing a power storage system having a large capacitance and a large energy density, an electric double layer capacitor using the same as a polarizable electrode, and a method of manufacturing the same.

[0002]

2. Description of the Related Art In recent years, the application of activated carbon to various application fields focusing on its characteristics has been studied. In particular, activated carbon is taken up as a porous carbon material for electrode materials of small and large-capacity capacitors and various batteries. Various studies have been made.

[0003] Above all, a polarizable electrode mainly composed of carbonaceous material such as activated carbon is used as a conventional capacitor in which an electrolyte is contained between the polarizable electrodes and an electric double layer formed at an interface between the two is used. It is often used for electric double-layer capacitors that have several thousand times the capacitance per unit volume in comparison.Since such electric double-layer capacitors have the functions of both a capacitor and a battery, a small memory backup power supply and The demand has been rapidly increasing with the development of the electronics field, such as being applied to an auxiliary power supply such as a large-capacity motor mounted as a driving source of an automobile.

[0004] Initially, porous solid activated carbon that is generally widely used is used as the electrode material. Examples of such solid activated carbon include carbonaceous materials such as activated carbon and carbon black, and carbonaceous materials. An organic resin such as a fluoroethylene resin or a fluoropolymer is kneaded and formed into a sheet by known molding means such as a roll molding method or a compression molding method,
Activated carbon coated with an acrylic resin, a polycarbonate resin, or the like is kneaded with various carbons and a binder, and is formed into a sheet in the same manner as described above.

[0005] However, as the electrode material of the above-mentioned capacitor or battery, in order to satisfy the performance of particularly high capacitance and low internal resistance, and to satisfy the recent demand for miniaturization of electronic components, it is necessary to use a predetermined material. In addition to the characteristics of minimizing the volume with respect to the capacity and the characteristics of the porous structure taking into account the impregnating property of the electrolyte, it is less likely to cause cracks or breakage, etc. In addition, it has more excellent durability and mechanical properties for general use And so on.

In particular, the capacitance of an electric double layer capacitor is governed by the surface area of the polarizable electrode on which the electric double layer is formed, the capacitance per unit volume, the resistance of the electrode, and the like.
There is a close relationship with the size of the ions in the electrolyte forming the electric double layer, and it is considered that the specific surface area of the micropores determines the capacitance.

[0007] Therefore, in order to increase the capacitance per unit volume of the electrode, it has been required that the porous activated carbon has a large specific surface area without impairing the durability and mechanical strength.

Therefore, in order to satisfy the above requirements, activated carbon fine particles and carbon fibers are mixed and sintered under pressure, or a mixture of activated carbon powder and powdery phenol resin is injection-molded and heat-treated. Pulp fiber or the like is added to the activated carbon fiber to make a paper, a prepreg sheet containing activated carbon powder and cellulose fiber as main components is pressed and calcined, or a mixture of activated carbon powder and phenol resin is formed into a film on a substrate, Heat-treating in an oxidizing atmosphere or heat-curing a mixture of a spherical carbide obtained by carbonizing a curable spherical phenolic resin and a thermoreactive spherical phenolic resin, heat-treating in an inert atmosphere, and then activating. There have been proposed solid activated carbons produced by various production methods.

However, such a solid activated carbon is produced from a mixture of a porous activated carbon having a large specific surface area within a range that does not impair the durability and mechanical strength, and the organic resin, and a filling amount of the activated carbon. Is limited to a certain range from the relationship with the total pore volume, and moreover, an organic resin having good moldability is highly likely to block the fine pores of the activated carbon, and the specific surface area is further reduced in combination with the filling amount of the activated carbon. And
None of them was satisfactory from the viewpoint of minimizing the volume with respect to the capacitance.

[0010] On the other hand, when a high-viscosity organic resin that does not block the fine pores of the activated carbon is used, the moldability is poor and the mechanical strength after carbonizing heat treatment is low.

In order to solve this problem, an activated carbon electrode is manufactured by impregnating an activated carbon substrate with an organic solvent such as alkanes, alkenes, and alcohols composed of a carbon compound and then adding and mixing a binder composed of an organic resin. (See Japanese Patent Application Laid-Open No. 8-13879).

[0012]

However, as the binder, PVA which can react with hydroxyl groups in activated carbon by aging treatment in the air to form a network structure by a cross-linking reaction and whose strength can be increased with a small amount, and PVA and the like. When a resin derived from PVA is used as the activated carbon base material, the binder is not plasticized with an organic solvent such as the alkane or alkene, so that a granulated body is hard and a molded body which is easy to handle is obtained. Not only that, the desired shape could not be freely obtained.

[0013]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to protect the fine pores of a porous activated carbon from an organic resin used as a binder and maintain a high specific surface area of the activated carbon. And various types of materials having good moldability, a large specific surface area, a large mechanical strength, and excellent durability, which can freely obtain a flexible sheet-like molded body obtained by the roll molding method or the like. An object of the present invention is to provide a solid activated carbon applicable to an application, an electric double layer capacitor having a practical capacitance using the activated carbon as a polarizable electrode, and a method of manufacturing the same.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies on the above-mentioned problems, and as a result, have the effect of plasticizing an organic resin mixed as a binder with various types of activated carbon materials. By impregnating an acid-based or phosphoric acid-based, fatty acid-based ester compound as a microporous protective material for activated carbon, a carbonized heat treatment of a molded body using PVA or a resin derived from PVA and a phenolic resin as a binder is performed. By integrating, the specific surface area is 70
The present inventors have found that even in the range of 0 m ² / g or more and nearly 2500 m ² / g, solid activated carbon of various shapes having high mechanical strength, excellent durability and high capacitance can be obtained. Invented the invention.

That is, the solid activated carbon of the present invention is derived from activated carbon powder and / or activated carbon fiber impregnated with at least one of a phthalic acid-based or phosphoric acid-based or fatty acid-based ester compound, and PVA or PVA. It is characterized by having a specific surface area in the range of 700 m ² / g or more and 2500 m ² / g or less and a mechanical strength of 300 gf / mm ² or more. In particular, as the ester compound, DBP which is liquid at room temperature is more desirable, and the resin derived from PVA is preferably PVB.
Is more preferable.

Further, the use of the solid activated carbon as a polarizable electrode of an electric double layer capacitor is optimal.

On the other hand, the method for producing the solid activated carbon of the present invention is as follows: 100 parts by weight of activated carbon powder and / or activated carbon fiber are phthalic acid or phosphorus having a plasticizing effect of PVA or a resin derived from PVA. After impregnating 50 to 200 parts by weight of at least one of acid-based and fatty acid-based ester compounds, the activated carbon powder and / or activated carbon fiber 1
100 parts by weight of PVA or a resin derived from PVA is mixed at a ratio of 20 to 200 parts by weight, and 1 to 30 parts by weight of phenol is added to 100 parts by weight of the activated carbon powder and / or activated carbon fiber. A mixture prepared by adding and mixing a resin is molded.

Thereafter, the obtained molded body is placed in a range of 150 to 300
The aging treatment is performed at a temperature of ° C. to decompose and volatilize the impregnating liquid, thereby opening the fine pores of the activated carbon,
After the resin derived from A and the hydroxyl group in the molecule of the phenol resin cause a dehydration reaction to form a crosslinked structure, the activated carbon powder and / or activated carbon fiber and PVA or are subjected to carbonization heat treatment in a non-oxidizing atmosphere. It is characterized in that a resin derived from PVA and a carbide of a phenol resin are integrated by firing.

Above all, the ester compound is most preferably DBP which is liquid at room temperature, and the resin derived from PVA is most preferably PVB.

[0020]

The solid activated carbon of the present invention comprises activated carbon powder and / or activated carbon fiber impregnated with at least one of a phthalic acid-based or phosphoric acid-based or fatty acid-based ester compound, and PVA or a resin derived from PVA. , A phenolic resin obtained by heat treatment and having a specific surface area of 700 m ^2.
/ G or more and 2500 m ² / g or less, a part of the ester compound permeates into the fine pores of the activated carbon powder and / or the activated carbon fiber, and the remaining ester compound contains the activated carbon powder and / or Alternatively, the surface of the activated carbon fiber is covered.

Therefore, even after adding PVA or a resin derived from PVA and a phenol resin, the micropores are already closed by the ester compound.
The type of resin cannot enter the micropores and does not block the micropores.

The ester compound is PVA or P
In order to have the effect of plasticizing the resin derived from VA, the remaining ester compound covering the surface of the activated carbon powder and / or the activated carbon fiber plasticizes the resin, and the granulated material which is easily crushed and has plasticity Thus, a flexible sheet-shaped molded body can be easily obtained by the roll molding method or the like using the granulated body.

On the other hand, the molded body is kept at a high specific surface area by aging at a temperature of 150 to 300 ° C., whereby the ester compound penetrating into the fine pores is decomposed and the fine pores are opened. it can.

Further, the remaining ester compound coated on the surface of the activated carbon powder and / or the activated carbon fiber and plasticizing the resin is also decomposed at the same time as the aging, so that the plasticity of the resin is lost and the resin is lost. The strength of the resin itself is exhibited, and further, the hydroxyl groups present in the molecules of the resin and the phenol resin undergo a dehydrogenation reaction to form a crosslinked structure, whereby the strength is further improved.

As a result, it is possible to obtain multipurpose solid activated carbon of various shapes having a large capacitance and excellent mechanical strength and durability. When the solid activated carbon is used as a polarizable electrode of an electric double layer capacitor. It is possible to obtain a small-sized electric double layer capacitor having practical capacitance, low internal electric resistance of the electrode, simple structure, high efficiency, and excellent durability.

Further, the method for producing a solid activated carbon of the present invention comprises:
The activated carbon powder and / or the activated carbon fibers are impregnated with at least one of a phthalic acid-based or phosphoric acid-based or fatty acid-based ester compound that plasticizes PVA or a resin derived from PVA as a binder. At the same time as functioning as a hole protecting material, the resin is plasticized to swell and weaken the intermolecular bonding force, so that a molded article having a desired shape can be easily obtained at room temperature by the roll molding method or the press molding method. It becomes possible.

[0027]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The solid activated carbon of the present invention, an electric double layer capacitor using the same, and a method for producing the same will be described in detail below.

The solid activated carbon of the present invention comprises activated carbon powder and / or activated carbon fiber impregnated with at least one of phthalic acid-based, phosphoric acid-based, and fatty acid-based ester compounds;
It is composed of a resin derived from A or PVA and a carbide obtained by heat-treating a phenolic resin, and has a specific surface area of 700 m ² / g or more and 2500 m ² / g or less, and its mechanical strength. Is 300 gf / m
m ² or more.

In the present invention, the phthalic acid-based or phosphoric acid-based or fatty acid-based ester compound to be impregnated into the activated carbon powder and / or the activated carbon fiber is a compound formed by separating water from an acid and an alcohol.

[0030]

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## EQU1 ##

Specifically, the ester compound may be any as long as it has an effect of plasticizing PVA or a resin derived from PVA.
Dibutyl phthalate (DBP) or dioctyl phthalate (D
OP), tributyl phosphate (TBP), butyl sebacate (DBS), and the like. Among them, DBP, which is liquid at room temperature, is most preferable from the viewpoints of elongation and strength of the molded product during dry molding.

PVA or PVA as a binder
The derived resin is cross-linked by aging at a low temperature in advance, and any resin may be used as long as it remains and retains high strength even if subsequently subjected to a carbonizing heat treatment.
For example, in addition to PVA, polyvinyl acetal such as PVB and polyvinyl formal (PVFM), vinyl acetate, and the like can be mentioned.
PVB is most desirable from the viewpoint of the flexibility of the molded article.

The upper limit of the specific surface area of the obtained solid activated carbon is determined by the specific surface area of the activated carbon as a starting material. If the specific surface area is less than 700 m ² / g, the specific surface area occurs at the interface between the electrolyte and the electrode. Because the electric double layer decreases,
The capacitance is less than 30 F / g, which is not practical.

On the other hand, when the specific surface area exceeds 2500 m ² / g, the mechanical strength of the solid activated carbon is significantly reduced,
Not only is it difficult to handle, but the desired shape cannot be obtained freely, which is inappropriate.

Accordingly, the specific surface area of the solid activated carbon of the present invention is specified to be 700 m ² / g or more and 2500 m ² / g or less, and the specific surface area of the conventional solid activated carbon is 150 m ² / g.
If it exceeds 0 m ² / g, the strength tends to decrease,
In the present invention, since the strength can be improved by adding a phenol resin, the specific surface area is 800 to 2000 m ² from the viewpoint of having both the capacitance and the strength.
/ G, more preferably at least 300 gf / mm ^{2 in} order that the obtained solid activated carbon does not cause breakage such as chipping or cracking during the manufacturing process or during incorporation as an electrode of an electric double layer capacitor. A material having the above strength is required.

Such a solid activated carbon can maintain a sufficient capacitance and a sufficient mechanical strength, and is particularly suitable as a polarizable electrode of an electric double layer capacitor.

Further, the method for producing a solid activated carbon of the present invention comprises:
One or more phthalic acid-based, phosphoric acid-based, and fatty acid-based esters which are liquid at room temperature and have an effect of plasticizing activated carbon powder and / or activated carbon fibers and a resin derived from PVA or PVA are impregnated with PVA or PVA. After mixing the derived resin and further molding a molding material to which a phenolic resin is added by a well-known molding method in order to improve the strength, it is subjected to an aging treatment in the air and a carbonizing heat treatment in a non-oxidizing atmosphere. It consists of steps.

In the method for producing a solid activated carbon of the present invention, the activated carbon powder or activated carbon fiber used as a starting material is not particularly limited, and may be coconut shell, coal, or wood. Coconut shell systems are most desirable in terms of performance.

The specific surface area of the activated carbon powder or activated carbon fiber used as the starting material may be selected according to the desired capacitance. The obtained solid activated carbon is used as a polarizable electrode for an electric double layer capacitor. In this case, it is preferable that the activated carbon powder has a specific surface area of about 1500 m ² / g or more and about 3500 m ² / g, and the activated carbon fiber has a fiber diameter of 6 to 18 μm and a specific surface area of 1000 m ² / g or more.
Those having a weight of about 000 m ² / g or less are suitable, and they can be appropriately mixed and used.

The amount of one or more of the phthalic acid-based, phosphoric acid-based, and fatty acid-based ester compounds to be impregnated into the activated carbon powder and / or the activated carbon fiber is 100 parts by weight of the activated carbon powder and / or the activated carbon fiber. If the amount is less than 50 parts by weight, the pores in the activated carbon powder and / or the activated carbon fibers are impregnated to prevent the binder resin from closing the pores of at least 5 mm larger than the ionic diameter of the electrolyte. Since the amount is insufficient, the effect of protecting micropores does not work sufficiently, and the specific surface area of the obtained solid activated carbon decreases, which leads to a decrease in capacitance.

On the other hand, even if impregnated in an amount of 200 parts by weight or more, it is too much to close the fine pores of the activated carbon powder and / or activated carbon fiber. The releasability rapidly deteriorates, and in an extreme case, the ester compound may ooze out during molding and the molding itself may not be performed.

Accordingly, the amount of the ester compound to be impregnated is limited to 50 to 200 parts by weight based on 100 parts by weight of the activated carbon powder and / or the activated carbon fiber. Since it has the effect of plasticizing the resin derived from PVA, there is no need to add any other plasticizer, and a molded article that is flexible and easy to handle can be obtained without adversely affecting the moldability.

On the other hand, when the compounding amount of PVA or the resin derived from PVA is less than 20 parts by weight with respect to 100 parts by weight of activated carbon powder and / or activated carbon fiber, the strength of the obtained solid activated carbon is extremely high. If the amount is lower than 200 parts by weight, the molded article is greatly deformed during the aging treatment. Therefore, the amount is limited to 20 to 200 parts by weight.

When the blending amount of the phenolic resin is less than 1 part by weight with respect to 100 parts by weight of activated carbon powder and / or activated carbon fiber, activated carbon powder or activated carbon fiber having a specific surface area exceeding 2000 m ² / g was used. In this case, the strength of the obtained solid activated carbon is reduced to 300 gf / mm ² or less,
If the amount exceeds 30 parts by weight, the molded article is greatly deformed during the aging treatment, or the specific surface area of the obtained solid activated carbon is reduced, so the amount is limited to 1 to 30 parts by weight.

Next, using the raw material comprising the mixture,
Formed into a sheet by doctor blade method or calender roll method, etc. to form an activated carbon substrate, formed into a block shape by various press molding methods, or formed into a rod shape or cylindrical shape by extrusion molding method, or by combining them The aging treatment of the molded articles formed into various shapes decomposes the ester compound of the fine pore protective material to open the fine pores of the activated carbon, and also performs PVA or PVA.
The strength is improved by a crosslinking reaction between the resin and the phenol resin derived from the resin, and a carbide having a high specific surface area and high mechanical strength can be obtained.

Therefore, when the aging treatment temperature is 150
If the temperature is lower than 0 ° C., the decomposition of the impregnated microporous protective material is insufficient, so that not only the micropores of the activated carbon cannot be completely opened, but also the crosslinking reaction between the binder PVA or the resin derived from PVA and the phenol resin. Does not proceed, resulting in a decrease in strength. When the temperature exceeds 300 ° C., the molded article is deformed by a rapid crosslinking reaction, and at the same time, the binder starts to be decomposed, resulting in a decrease in strength and lack of practicality.

Therefore, the aging treatment temperature is 15
It is limited to a temperature range of 0 to 300 ° C., and from the viewpoint of the strength of the solid activated carbon and formation of micropores, a temperature range of 180 to 220 ° C. is more preferable.

Incidentally, after laminating a plurality of the sheet-shaped molded bodies, it is also possible to perform a heat treatment in a non-oxidizing atmosphere.
By laminating a plurality of sheet-like molded bodies and bonding them by thermocompression bonding or with an adhesive liquid or an adhesive, it becomes possible to offset the warping directions of each other and reduce the occurrence of warpage during heat treatment. .

The carbonization heat treatment temperature in the present invention is P
In order to sufficiently promote the carbonization of the resin and phenolic resin derived from VA or PVA, and to promote the sintering of the neck portion of the activated carbon powder or the activated carbon fiber to maintain sufficient strength, it is necessary to use a non-oxidizing atmosphere. , 600-1200 ° C., and more preferably 800-1000 ° C.

Therefore, if the carbonization heat treatment temperature is increased or the carbonization time is increased, the strength is improved,
Since the specific surface area is reduced, it is important to select carbonization heat treatment conditions so as to have an optimum pore distribution in consideration of the balance between strength and capacitance according to the application.

In the method for producing a solid activated carbon according to the present invention, in order to activate the carbide of PVA or a binder derived from PVA and a resin and a phenolic resin after the carbonization heat treatment, the activated carbon is again in a steam atmosphere or CO
₂ It is also desirable to perform the activation treatment by heat treatment in an atmosphere or in the air, since a higher capacitance can be obtained.

[0053]

EXAMPLES The solid activated carbon of the present invention, an electric double layer capacitor using the same, and a method for producing the same were evaluated as follows.

First, various impregnants were added to 100 parts by weight of coconut shell activated carbon powder having a BET value of 3000 m ² / g in Table 1.
And in the ratio shown in Table 2 to the activated carbon powder, and impregnated using a high-speed mixing stirrer.

Thereafter, an organic resin used as a binder was added at the ratios shown in Tables 1 and 2, and the mixture was stirred with a high-speed mixing stirrer, and the obtained powder was sieved with a 40-mesh sieve. Was added and mixed by a ball mill to prepare a raw material for molding. The details of the impregnating agent and the organic resin are as shown in Table 3.

Next, the obtained molding material is press-molded,
Alternatively, after obtaining a flat molded body by roll molding, the molded body is subjected to an aging treatment at a temperature shown in Tables 1 and 2 in the air to decompose and volatilize the impregnated ester to form fine pores of the activated carbon raw material. Pore and then carbonization heat treatment in vacuum at 900 ° C, PVA or P added as binder
A resin derived from VA and a phenol resin are carbonized to form a composite of activated carbon and carbon 70 mm long and 50 mm wide.
A sample material for evaluation having a thickness of 1 mm and a thickness of 1 mm was prepared.

Further, the sample material was subjected to an oxidizing heat treatment in the air to perform an activation treatment, and the added carbide of the binder was activated to prepare a solid activated carbon substrate for evaluation.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

Using the thus-obtained solid activated carbon substrate for evaluation, the specific surface area was determined from nitrogen adsorption by the BET method.

Next, a test piece having a thickness of 1 mm, a width of 4 mm, and a length of 40 mm was prepared by using the same material as the solid activated carbon substrate for evaluation. Using the test piece, the distance between supports was set to 30 mm, and the crosshead speed was set to 0.5 mm / min.

Further, the solid activated carbon substrate for evaluation was used as an electrode, charged in a 40% aqueous sulfuric acid solution at a voltage of 0.9 V for 10 minutes, and then subjected to a constant voltage discharge method of 3 mA / cm ^{2 for} a unit weight of the electrode. Per unit capacitance (F / g).

The equivalent series resistance of the electrode at 1 kHz was measured by assembling a capacitor for evaluation using two substrates having a thickness of 1 mm and a length and width of 10 mm.
In the present invention, the value was 5Ω or less.

On the other hand, as to the evaluation of the moldability, the crushed state of the granules and the releasability during the molding were visually observed through molding of the sample material for evaluation to judge the quality.

[0066]

[Table 4]

[0067]

[Table 5]

As is clear from Tables 4 and 5, in the sample No. 60 of the comparative example, the granulated product was not crushed, the formability was poor, the specific surface area of the solid activated carbon as well as the capacitance could not be measured. The bending strength of the target strength is also extremely low at 46 gf / mm ² .

Samples Nos. 1, 5, 22, 26, 46, and 59, which are out of the scope of the present invention, have poor moldability, such as not crushed granules and poor releasability, and have a specific surface area. Even if the mechanical strength or the physical properties could not be measured, or the physical properties could be measured, the specific surface area was less than 700 m ² / g, and sample numbers 6, 11, 18, 21, 27, 3
In 2, 39, 42, 47, and 50, the bending strength of the mechanical strength was as low as less than 300 gf / mm ^2, and in Sample Nos. 10, 17, 31, and 38, the aging treatment was performed, although the moldability was good. Thus, the solid activated carbon of the present invention lacks practicality, such as cracks and deformation.

On the other hand, the solid activated carbon for evaluation of the present invention has a specific surface area of 700 m ² / g or more and 25 m ² / g or more.
00 m ² / g or less, the bending strength of the mechanical strength is as high as 300 gf / mm ² or more, and the capacitance is 36
F / g is within the practical range, no adhesion to the molding die is observed, and the moldability is good, and it can be seen that the solid activated carbon satisfies various practical requirements.

It should be noted that the present invention is not limited to the above-described embodiment, and can be applied to any shape and form without departing from the gist of the present invention.

[0072]

As described above in detail, according to the solid activated carbon of the present invention, the electric double layer capacitor using the same, and the method of manufacturing the same, the compact can be easily handled and the manufacturing process of heat treatment is stable. In addition to a large specific surface area, a large capacitance can be obtained, and a multipurpose solid activated carbon applicable to various uses having high mechanical strength and excellent durability can be obtained.

Therefore, when the solid activated carbon of the present invention is used as a polarizable electrode, the surface area of the electrode in contact with the electrolyte increases, and the number of electric paths through which electric charges pass increases.
A simple structure having a practical capacitance exceeding 36 F / g can be used to obtain an efficient, excellent and small electric double-layer capacitor, and it has excellent mechanical strength and is durable for an auxiliary power supply. A multipurpose solid activated carbon suitable for various uses such as electrode materials for various batteries can be obtained.

Continued on the front page F term (reference) 4G032 AA04 AA16 AA52 BA04 BA05 GA09 4G046 HA03 HA10 HB05 HC03 HC05 HC12

Claims (7)

[Claims] An activated carbon powder and / or activated carbon fiber impregnated with at least one of a phthalic acid type, a phosphoric acid type and a fatty acid type ester compound, and polyvinyl alcohol (PV).
A) or a resin derived from polyvinyl alcohol (PVA) and a carbide obtained by heat-treating a phenol resin, and having a specific surface area of 700 m ² / g or more and 2500 m ² / g.
Or less, and having a mechanical strength of 300 gf / mm ² or more. 2. The solid activated carbon according to claim 1, wherein the ester compound is dibutyl phthalate (DBP) which is liquid at room temperature. 3. The solid activated carbon according to claim 1, wherein the resin derived from the polyvinyl alcohol (PVA) is polyvinyl butyral (PVB). 4. An electric double layer capacitor comprising the solid activated carbon according to claim 1 as a polarizable electrode. 5. A standard amount of 100 parts by weight of activated carbon powder and / or activated carbon fiber, and 50 to 200 parts by weight of at least one of phthalic acid, phosphoric acid and fatty acid ester compounds based on the standard amount. After the impregnation, 20 to 200 parts by weight of polyvinyl alcohol (PVA) or a resin derived from polyvinyl alcohol (PVA) is mixed with the reference amount, and the mixture is further mixed with the reference amount. After 1 to 30 parts by weight of a phenolic resin is added and mixed to prepare a molding material, it is molded into various shapes using the molding material, and the obtained molded body is subjected to an aging treatment at a temperature of 150 to 300 ° C. Activated carbon powder and / or activated carbon fiber and polyvinyl alcohol (PVA) or polyvinyl alcohol (PVA) Method for producing a solid activated carbon and firing integrating carbide resin and phenolic resin. 6. The method according to claim 5, wherein the ester compound is dibutyl phthalate (DBP) which is liquid at room temperature. 7. The method for producing a solid activated carbon according to claim 5, wherein the resin derived from the polyvinyl alcohol (PVA) is polyvinyl butyral (PVB).