JP2006319321A - Activated carbon and manufacturing method thereof - Google Patents

Abstract

An activated carbon that provides an electric double layer capacitor with improved capacitance per unit volume and a method for manufacturing the same are provided.
In an activated carbon for an electric double layer capacitor obtained by carbonizing an organic aerogel obtained by polymerizing a phenolic compound having at least one hydroxyl group in the molecule and an aldehyde compound in the presence of an aqueous solvent and a basic catalyst. Activated carbon, wherein the pore volume of the activated carbon is 1.5 cc / g or less, and
In the method for producing activated carbon in which a phenolic compound having at least one hydroxyl group in the molecule and an aldehyde compound are polymerized in the presence of an aqueous solvent and a basic catalyst, and the resulting organic aerogel is carbonized, A method for producing activated carbon, wherein the phenolic compound is polymerized at 0.25 to 1000 mol of phenolic compound at 0.5 to 5 parts by weight of phenolic compound per 1 part by weight of the aqueous solvent.
[Selection figure] None

Description

  The present invention relates to activated carbon suitable for an electric double layer capacitor excellent in capacitance per unit volume and a method for producing the same.

Currently, there is a demand for electric energy storage devices that can store a lot of electric energy in the fields of late-night power storage, and in the field of rechargeable transportation equipment such as electric vehicles and hybrid vehicles, as well as mobile personal computers, mobile phones, In the field of portable electronic terminals such as audio equipment, there is a demand for an electrical energy storage device that stores a large amount of electrical energy per unit volume so that it can operate for a long time even in a small volume.
An electric double layer capacitor is composed of an electrode, a separator, and an electrolytic solution. The electrolyte dissolved in the electrolytic solution is adsorbed by the electrode, and electric energy is applied to the interface (electric double layer) formed between the electrolyte and the electrode. It is a storage device and is expected as an electrical energy storage device in the above field. The stored energy is represented by 1/2 · C · V ² (where C is a capacitance (F), V is a potential), and in order to store a lot of energy, an electrical energy storage device is used. In order to store a large amount of electric energy in a compact manner, it is required to improve the capacitance per unit volume.
As an electrode of the electric double layer capacitor, activated carbon is widely used. Specifically, it is activated carbon mainly composed of micropores (pore diameter of 20 mm or less) obtained by carbonizing and activating raw materials such as coconut shells. In order to improve the electrostatic capacity per unit volume, an electric double layer capacitor using a new activated carbon has been demanded.
In recent years, resorcin and formaldehyde are polymerized in the presence of a basic catalyst and an aqueous solvent to obtain an organic aerogel having uniform mesopores (pore diameter of 20 mm or more), and then washed with an organic solvent to remove the aqueous solvent. It has been proposed that mesopore-based activated carbon obtained by substitution with an organic solvent, drying and subsequent carbonization is used as an electrode of an electric double layer capacitor having a large capacitance per unit weight.
Specifically, for example, in Patent Document 1, the molar ratio (R / C) of resorcinol (R) to the basic catalyst (C) is about 200 to 410 times, and resorcinol (R) and an aqueous solvent ( W) and activated carbon of organic aerogel obtained by polymerization at a weight ratio (R / W) of about 0.027 to 0.067 times are disclosed. Patent Document 2 discloses that R / C is 2000 or more. , Activated carbon of organic aerogel obtained by polymerization at R / W of about 0.39 to 0.56 times.

US Pat. No. 4,873,218 (Table 1) JP-T-2002-511899 (Claim 1, Examples 1 to 4)

When the present inventors examined the electric double layer capacitor using such activated carbon, it became clear that the electrostatic capacity per unit volume was not fully obtained.
The object of the present invention is to improve the electrostatic capacity per unit volume of activated carbon obtained by carbonizing an organic aerogel obtained by polymerizing a phenolic compound and an aldehyde compound in the presence of a basic catalyst. It is to provide an activated carbon that provides a multilayer capacitor and a method for manufacturing the same.

The present invention relates to an activated carbon obtained by carbonizing an organic aerogel obtained by polymerizing a phenolic compound having at least one hydroxyl group in the molecule and an aldehyde compound in the presence of an aqueous solvent and a basic catalyst. Obtained by polymerizing activated carbon having a volume of 1.5 cc / g or less, and a phenolic compound having at least one hydroxyl group in the molecule and an aldehyde compound in the presence of an aqueous solvent and a basic catalyst. In the method for producing activated carbon for an electric double layer capacitor for carbonizing organic airgel, 0.25 to 1000 mol of phenolic compound per 1 mol of basic catalyst and 0.5 to 5 wt. Of phenolic compound per 1 part by weight of aqueous solvent It is a manufacturing method of activated carbon characterized by superposing | polymerizing in a part.

  The activated carbon of the present invention has a further improved capacitance per unit volume among activated carbons obtained by carbonizing an organic airgel obtained by polymerizing a phenolic compound and an aldehyde compound in the presence of a basic catalyst. Activated carbon that gives an electric double layer capacitor.

Hereinafter, the present invention will be described in detail.
The activated carbon of the present invention is an activated carbon obtained by carbonizing an organic aerogel obtained by polymerizing a phenolic compound having at least one hydroxyl group in the molecule and an aldehyde compound in the presence of an aqueous solvent and a basic catalyst. The pore volume is 1.5 cc / g or less, preferably 0.1 to 1.5 cc / g, particularly preferably 0.3 to 1.0 cc / g, and most preferably 0.3 to 0.6 cc / g. It is activated carbon characterized by being. It is preferable that the pore volume of the activated carbon is in the range of 0.1 to 1.5 cc / g because the capacitance per unit volume tends to be improved.
The activated carbon of the present invention is used, for example, as an electrode for a dry cell, a sensor for a piezoelectric element, a carrier for supporting a catalyst, a chromatographic material, an adsorbent, an electrode of an electric double layer capacitor, etc. Since it is excellent in electrostatic capacity, it is suitable for an electrode of an electric double layer capacitor.

  Examples of the method for producing activated carbon of the present invention include a method of polymerizing a phenolic compound and an aldehyde compound in the presence of a basic catalyst and an aqueous solvent to obtain an organic airgel, and carbonizing the organic airgel. Below, the manufacturing method is demonstrated.

式中、Ｒ^1０は置換基が結合していてもよい炭素数１〜１２程度のアルキル基を表す。Ｒ^1０が複数の場合には、Ｒ^1０が互いに異なっていてもよい。ｎは０〜３の整数を表し、ｍは２〜５の整数を表す。ただし、ｎ及びｍの和は５以下である。 The phenolic compound used for the production of the organic airgel is a phenolic compound having at least one hydroxyl group in the molecule, and specifically, a compound represented by the formula (3) is exemplified.

In the formula, R ¹⁰ represents an alkyl group having about 1 to 12 carbon atoms to which a substituent may be bonded. When R ¹⁰ is plural may be R ¹⁰ are different from each other. n represents an integer of 0 to 3, and m represents an integer of 2 to 5. However, the sum of n and m is 5 or less.

Examples of the substituent which may be bonded to the alkyl group include a halogen atom, hydroxy group, cyano group, alkoxy group, carbamoyl group, carboxy group, alkoxycarbonyl group, alkylcarbonyloxy group, sulfo group and sulfamoyl group. Can be mentioned.
R ¹⁰ may be linear, branched or cyclic.

R ¹⁰ is, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-octyl group, nonyl group, pt An alkyl group such as a butyl group;
2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl An alkyl group to which a hydroxy group such as a group is bonded;
An alkyl group to which cyano is bonded, such as a cyanomethyl group, a 2-cyanoethyl group, and a 3-cyanopropyl group;
Alkyl groups to which alkoxy such as methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 2-hydroxy-3-methoxypropyl group is bonded;
Halogenated alkyl groups such as chloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl group, 3-chloropropyl group, 3-bromopropyl group, 4-chlorobutyl group, 4-bromobutyl group;

Carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 1,2-dicarboxyethyl group, carbamoylmethyl group, 2-carbamoylethyl group, 3-carbamoylpropyl group, 4-carbamoyl group Butyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 3-methoxycarbonylpropyl group, 3-ethoxycarbonylpropyl group, 4-methoxycarbonylbutyl group, 4- Ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, 3-ethylcarbo Examples thereof include a nyloxypropyl group, a 4-methylcarbonyloxybutyl group, and a 4-ethylcarbonyloxybutyl group.

R ¹⁰ usually has about 1 to 12 carbon atoms.
R ¹⁰ is preferably a hydrogen atom or an unsubstituted alkyl group, and more preferably a hydrogen atom, a methyl group, an ethyl group, or an n-octyl group.
In Formula (1), as n, 3 or 4 is preferable and 4 is more preferable.
As m, 1 or 2 is preferable and 1 is more preferable.

Specific examples of the compound represented by the formula (3) include o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, and 2,6-xylenol. 3,4-xylenol, 3,5-xylenol, o-ethylphenol, i-propylphenol, butylphenol, pt-butylphenol, p-octylphenol, p-nonylphenol, 2-chlorophenol, 4-methoxyphenol, 2 , 4-dichlorophenol, 3,5-dichlorophenol, 4-chloro-3-methylphenol, catechol, 3-methylcatechol, 4-t-butylcatechol, resorcinol, 2-methylresorcinol, 4-ethylresorcinol, 4- Chlororesorcinol, 5-methylresorcin Lumpur, 2,5-dimethyl resorcinol, 5-methoxy-resorcinol, 5-pentylene Relais sol maytansinol, phloroglucinol, may be mentioned pyrogallol.
The phenolic compounds may be used alone or in combination of two or more.
As the phenolic compound, it is particularly preferable to use resorcinol or phloroglucinol.

Examples of the aldehyde compound used for the production of the organic airgel include formaldehyde, paraformaldehyde, acetaldehyde, butyraldehyde, salicylaldehyde, benzaldehyde and the like. Of these, formaldehyde is preferably used.
The usage-amount of an aldehyde compound is about 1-3 mol normally with respect to 1 mol of phenolic compounds, Preferably it is about 1.2-2.5 mol.

Examples of basic catalysts used in the production of organic airgel include sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, barium carbonate, sodium phosphate, lithium phosphate, and potassium phosphate. Etc. Of these, sodium carbonate is preferably used.
The ratio of the amount used of the basic catalyst and the phenolic compound is such that the phenolic compound is 0.25 to 1000 mol, preferably 0.5 to 500 mol, more preferably, per mol of the basic catalyst. Is in the range of 10 to 500 moles.
It is preferable that the phenolic compound is in the range of 0.25 to 1000 mol with respect to the basic catalyst because the capacitance tends to be improved.

The aqueous solvent used for the production of the organic airgel means water, an organic solvent that can be mixed with water at an arbitrary ratio, and a mixture of the organic solvent and water. Specific examples of the organic solvent include alcohol solvents such as methanol, ethanol and i-propyl alcohol, and ether solvents such as tetrahydrofuran. These solvents may be used alone or in combination of two or more.
As the aqueous solvent, water, an alcohol solvent having 3 or less carbon atoms, and a mixture of water and an alcohol solvent having 3 or less carbon atoms are preferably used, and water is more preferably used.

The amount ratio of the aqueous solvent to the phenolic compound is usually 0.5 to 5 parts by weight, preferably 1 to 2 parts by weight, based on 1 part by weight of the aqueous solvent.
The amount ratio of the aqueous solvent to the phenolic compound is preferably 0.5 to 5 parts by weight because the electrostatic capacity per unit volume tends to be improved.
In the production method of the present invention, the use amount of the aqueous solvent means the use amount of the aqueous solvent at the time of polymerization, so the aqueous solvent contained in the phenolic compound or the aldehyde compound is also included in the use amount. For example, in the case of a 37% formalin aqueous solution, 63% water is calculated as an aqueous solvent.

As a method for producing an organic airgel, for example, a phenolic compound, an aldehyde compound, a basic catalyst, and an aqueous solvent are mixed together and usually stirred at 0 to 100 ° C, preferably 30 to 90 ° C to form a wet gel. A method of drying after obtaining; After obtaining a wet gel by mixing an aldehyde compound with a mixture comprising a phenolic compound, a basic catalyst and an aqueous solvent, usually at 0 to 100 ° C., preferably 30 to 90 ° C. A method of drying; a phenolic compound is usually mixed in a mixture comprising an aldehyde compound, a basic catalyst and an aqueous solvent at 0 to 100 ° C., preferably 30 to 90 ° C. to obtain a wet gel, and then dried. Method: A basic catalyst is usually added to a mixture comprising a phenolic compound, an aldehyde compound and an aqueous solvent, usually at 0 to 100 ° C., preferably 30 to 90 ° C. After obtaining the mixed with wet gel by, a method for drying.
Among them, a method of obtaining a wet gel by mixing an aldehyde compound with a mixture comprising a phenolic compound, a basic catalyst and an aqueous solvent is preferable.

Examples of the drying of the wet gel include a method of ventilating at room temperature to about 100 ° C. or drying under reduced pressure. In addition, when the solvent in the wet gel is water, after substitution with a hydrophilic organic solvent, a method of ventilating at room temperature to about 100 ° C. or drying under reduced pressure can be used.
Examples of the hydrophilic organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and t-butyl alcohol; aliphatic nitriles such as acetonitrile; aliphatic ketones such as acetone; dimethyl sulfoxide, and the like. Aliphatic sulfoxides; and aliphatic carboxylic acids such as acetic acid.
As the hydrophilic organic solvent, t-butyl alcohol, dimethyl sulfoxide, and acetic acid are preferably used, and t-butyl alcohol is particularly preferable because it can be easily replaced with water.
Moreover, it may replace with the method of ventilating at room temperature-about 100 degreeC, or drying under reduced pressure, and may perform freeze-drying. The temperature in lyophilization is usually in the range of −70 to 20 ° C., preferably in the range of −30 to 10 ° C. In addition, lyophilization is usually performed under vacuum.
Further, as described in JP-A-9-328308, carbon dioxide or the like may be used for drying under supercritical conditions.
As a method for drying the wet gel, lyophilization is preferable because there is little variation in pore volume due to drying.

The activated carbon used in the present invention can be obtained by carbonizing and activating an organic airgel obtained by drying. As a specific method for producing the activated carbon, (I) In a gas atmosphere inert to carbon such as nitrogen, argon, helium, hydrogen, etc., usually in the range of 200 to 1500 ° C., preferably in the range of 600 to 1100 ° C. In general, after firing (carbonization) for about 1 minute to 24 hours, in the presence of an oxidizing gas such as H ₂ O, CO ₂ , or O ₂ , the temperature is usually in the range of 200 to 1500 ° C., preferably 600 to 1100. A method of firing (activation) for about 1 minute to 10 hours in the range of ° C; (II) in the presence of an oxidizing gas, usually in the range of 200 to 1500 ° C, preferably in the range of 600 to 1100 ° C. Usually, a method of firing (carbonization and activation) for about 1 minute to 24 hours; (III) Compound (1) is usually 400 ° C. or less, preferably 200 to 300 ° C. in the presence of an oxidizing gas such as air. Usually 1 minute to 24 hours After firing (carbonization), it is usually fired (carbonized) in a gas atmosphere inert to carbon, usually in the range of 200 to 1500 ° C, preferably in the range of 600 to 1100 ° C for about 1 minute to 24 hours. Further, a method of firing (activation) usually in the range of 200 to 1500 ° C., preferably in the range of 600 to 1100 ° C., usually for about 1 minute to 10 hours in the presence of an oxidizing gas; (IV) Compound ( After firing (carbonizing) 1) in the presence of an oxidizing gas such as air, usually at 400 ° C. or lower, preferably 200-300 ° C., usually for about 1 minute to 24 hours, H ₂ O or CO ₂ In the presence, in the range of 200 to 1500 ° C., preferably in the range of 600 to 1100 ° C., usually firing (activation) for about 1 minute to 10 hours; (V) Compound (1) under vacuum, Usually in the range of 200-1500 ° C In the range of preferably 600 to 1100 ° C., usually after firing (carbonization) for about 1 minute to 24 hours, in the presence of an oxidizing gas, usually in the range of 200 to 1500 ° C., preferably 600 to A method of firing (activation) usually in the range of 1100 ° C. for about 1 minute to 10 hours; (VI) When firing (carbonization and activation) in the oxidizing gas atmosphere of (II) above, zinc chloride, Examples include a method of mixing phosphoric acid, potassium sulfide, potassium hydroxide and the like.
Among these, the methods (I) to (V) are preferable because they do not contain a metal. As the oxidizing gas, H ₂ O and CO ₂ are preferable.
A firing temperature of 200 ° C. or higher is preferable because the pore volume tends to improve, and a temperature of 1100 ° C. or lower is preferable because the yield of activated carbon tends to improve. Further, if the firing time is 1 minute or more, the pore volume tends to improve, and if it is 24 hours or less, the yield of activated carbon tends to improve.

  The activated carbon used in the present invention preferably has a pore volume of 1.5 cc / g or less, more preferably 0.1 to 1.5 cc / g, still more preferably 0.3 to 1.0 cc / g, Particularly preferred is 0.3 to 0.6 cc / g. It is preferable that the pore volume of the activated carbon is 1.5 cc / g or less because the electrostatic capacity per unit volume tends to be improved.

As a method of using the activated carbon thus obtained as an electrode for an electric double layer capacitor, for example, a method of using as it is in a carbonized state, a method of using a crushed activated carbon, granulating a crushed activated carbon, Examples thereof include a method of forming into various shapes such as granules, fibers, felts, fines or sheets. The particle diameter of the activated carbon particles used in the molding method is usually pulverized to an average particle diameter of 50 μm or less, preferably 30 μm or less, particularly preferably 10 μm or less. By finely pulverizing the activated carbon, the bulk density of the electrode can be improved and the internal resistance can be reduced.
As the pulverization method, for example, impact pulverization pulverizer, centrifugal pulverizer, ball mill (tube mill, compound mill, conical ball mill, rod mill), vibration mill, colloid mill, friction disk mill, jet mill, etc. Is preferably used.
As a pulverization method, a ball mill is generally used. However, when a ball mill is used, it is preferable that the balls and the pulverization container are made of nonmetal such as alumina, zirconia, agate, etc. in order to avoid mixing of metal powder. .

The electrode of the present invention is an electrode characterized by containing the activated carbon. Usually, the electrode further contains a binder, a conductive agent and the like so as to be easily formed as an electrode.
As a method for producing an electrode, a mixture containing activated carbon, a binder, a conductive agent and the like is usually formed on a current collector. Specifically, for example, a method in which a mixed slurry obtained by adding a solvent to activated carbon, a binder, a conductive agent, etc. is applied to or dipped in a current collector by a doctor blade method or the like, and dried, for example, activated carbon, a binder, a conductive agent. A method in which a sheet obtained by kneading, shaping and drying by adding a solvent to the current collector is bonded to the current collector surface via a conductive adhesive, followed by pressing and heat treatment drying, for example, activated carbon, binder, conductive And a method of forming a mixture of an agent and a liquid lubricant on a current collector, removing the liquid lubricant, and then stretching the obtained sheet-like molded product in a uniaxial or multiaxial direction. It is done.
When making an electrode into a sheet form, the thickness is about 50-1000 micrometers.

Examples of current collector materials include metals such as nickel, aluminum, titanium, copper, gold, silver, platinum, aluminum alloys, and stainless steel, such as carbon materials, activated carbon fibers, nickel, aluminum, zinc, copper, tin, What is formed by plasma spraying or arc spraying of lead or an alloy thereof, for example, a conductive film in which a conductive agent is dispersed in a resin such as rubber, styrene-ethylene-butylene-styrene copolymer (SEBS), etc. Can be mentioned. Particularly preferred is aluminum which is lightweight, excellent in electrical conductivity and electrochemically stable.
The shape of the current collector is, for example, a foil, a flat plate, a mesh, a net, a lath, a punching or an embossed shape, or a combination thereof (for example, a mesh flat plate). Is mentioned.
Concavities and convexities may be formed on the current collector surface by etching.

Examples of the conductive agent include graphite, carbon black, acetylene black, ketjen black, conductive carbon such as activated carbon different from the present invention; graphite-based conductive agents such as natural graphite, thermally expanded graphite, scale-like graphite, and expanded graphite; Carbon fibers such as vapor grown carbon fibers; metal fine particles or metal fibers such as aluminum, nickel, copper, silver, gold, platinum; conductive metal oxides such as ruthenium oxide or titanium oxide; polyaniline, polypyrrole, polythiophene, polyacetylene, Examples thereof include conductive polymers such as polyacene.
Carbon black, acetylene black, and ketjen black are particularly preferable in that the conductivity is effectively improved in a small amount.
The compounding amount of the conductive agent in the electrode is usually about 5 to 50 parts by weight, preferably about 10 to 30 parts by weight with respect to 100 parts by weight of the activated carbon of the present invention.

  Examples of the binder include a polymer of a fluorine compound. Examples of the fluorine compound include a fluorinated alkyl (having 1 to 18 carbon atoms) (meth) acrylate, a perfluoroalkyl (meth) acrylate [for example, perfluoro Dodecyl (meth) acrylate, perfluoro n-octyl (meth) acrylate, perfluoro n-butyl (meth) acrylate], perfluoroalkyl-substituted alkyl (meth) acrylate [for example, perfluorohexylethyl (meth) acrylate, perfluorooctyl Ethyl (meth) acrylate], perfluorooxyalkyl (meth) acrylate [for example, perfluorododecyloxyethyl (meth) acrylate and perfluorodecyloxyethyl (meth) acrylate], Kill (carbon number 1-18) crotonate, fluorinated alkyl (carbon number 1-18) malate and fumarate, fluorinated alkyl (carbon number 1-18) itaconate, fluorinated alkyl-substituted olefin (carbon number about 2-10, fluorine 1 to 17 atoms), for example, perfluorohexylethylene, about 2 to 10 carbon atoms, and a fluorine atom bonded to a double bond carbon having about 1 to 20 fluorine atoms, tetrafluoroethylene, tri Examples include fluoroethylene, vinylidene fluoride, hexafluoropropylene, and the like.

Other examples of the binder include an addition polymer of a monomer containing an ethylenic double bond not containing a fluorine atom. Examples of such a monomer include (cyclo) alkyl (having 1 to 3 carbon atoms). 22) (Meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (Meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, etc.]; aromatic ring-containing (meth) acrylate [benzyl (meth) acrylate, phenylethyl (meth) acrylate, etc.]; alkylene glycol or dialkylene glycol (alkylene) 2 to 2 carbon atoms ) Mono (meth) acrylate [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate]; (poly) glycerin (degree of polymerization 1 to 4) mono (meth) acrylate Polyfunctional (meth) acrylate [(poly) ethylene glycol (degree of polymerization 1 to 100) di (meth) acrylate, (poly) propylene glycol (degree of polymerization 1 to 100) di (meth) acrylate, 2,2-bis ( 4-hydroxyethylphenyl) propane di (meth) acrylate, trimethylolpropane tri (meth) acrylate and the like]; (meth) acrylic acid ester monomers; (meth) acrylamide, (meth) acrylamide derivatives [N-methylol (Meth) acrylamide, Diase (Meth) acrylamide monomers such as acrylamide]; cyano group-containing monomers such as (meth) acrylonitrile, 2-cyanoethyl (meth) acrylate, 2-cyanoethylacrylamide; styrene and styrene having 7 to 18 carbon atoms Styrene monomers such as derivatives [α-methylstyrene, vinyltoluene, p-hydroxystyrene, divinylbenzene, etc.]; Diene monomers such as alkadienes having 4 to 12 carbon atoms [butadiene, isoprene, chloroprene, etc.]; Carboxylic acid (2 to 12 carbon atoms) vinyl ester [vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, etc.], carboxylic acid (2 to 12 carbon atoms) (meth) allyl ester [acetic acid (meth) allyl, propion Acid (meth) allyl, octanoic acid (meth) allyl, etc. Alkenyl ester monomers such as glycidyl (meth) acrylate, (meth) allyl glycidyl ether and other epoxy group-containing monomers; C2-C12 monoolefins [ethylene, propylene, 1-butene, 1-octene And mono-olefins such as 1-dodecene]; chlorine, bromine or iodine atom-containing monomers, for example, halogen atom-containing monomers other than fluorine such as vinyl chloride and vinylidene chloride; (meth) such as acrylic acid and methacrylic acid Acrylic acid; conjugated double bond-containing monomers such as butadiene and isoprene.
Further, the addition polymer may be a copolymer composed of a plurality of types of monomers such as an ethylene / vinyl acetate copolymer, a styrene / butadiene copolymer, an ethylene / propylene copolymer, and the like. Moreover, the carboxylic acid vinyl ester polymer may be partially or completely saponified, such as polyvinyl alcohol.
The conjugate may be a copolymer of a fluorine compound and a monomer containing an ethylenic double bond not containing a fluorine atom.

Other examples of the binder include, for example, polysaccharides such as starch, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylhydroxyethylcellulose, nitrocellulose, and derivatives thereof; phenol resin; melamine resin; polyurethane Resin; Urea resin: Polyimide resin; Polyamideimide resin; Petroleum pitch; Coal pitch and the like.
As the binder, a polymer of a fluorine compound is preferable, and polytetrafluoroethylene which is a polymer of tetrafluoroethylene is particularly preferable.

A plurality of types of binders may be used as the binder.
As a compounding quantity of the binder in an electrode, it is about 0.5-30 weight part normally with respect to 100 weight part of activated carbon, Preferably it is about 2-30 weight part.
Examples of the solvent used for the binder include alcohols such as IPA (isopropyl alcohol), ethanol, and methanol, ethers, and ketones. When the binder is thickened, a plasticizer may be used to facilitate application to the current collector.

  The conductive adhesive is usually a mixture of the conductive agent and the binder, and among them, the mixture of carbon black and polyvinyl alcohol does not require the use of an organic solvent, is easy to prepare, and is further storable. It is also preferable because of its superiority.

  The electrolyte used in the electric double layer capacitor of the present invention is a salt that dissolves in the electrolytic solution, and is usually a salt containing an organic quaternary ammonium cation having 4 to 12 carbon atoms. Among them, a salt composed of an anion and an organic quaternary ammonium cation is preferably used.

Examples of the electrolyte include BO ₃ ³⁻ , F ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , ClO ₄ ⁻ , AlF ₄ ⁻ , AlCl ₄ ⁻ , TaF ₆ ⁻ , NbF ₆ ⁻ , A combination of an inorganic anion such as SiF ₆ ²⁻ , CN ⁻ , F (HF) _n ⁻ (wherein n represents a numerical value of 1 or more and 4 or less) and an organic cation described later, an organic anion and an organic cation described later And a combination of an organic anion and an inorganic cation such as lithium ion, sodium ion, potassium ion or hydrogen ion.

The organic cation is a cationic organic compound, and examples thereof include an organic quaternary ammonium cation and an organic quaternary phosphonium cation.
An organic quaternary ammonium cation consists of an alkyl group (1-20 carbon atoms), a cycloalkyl group (6-20 carbon atoms), an aryl group (6-20 carbon atoms), and an aralkyl group (7-20 carbon atoms). A quaternary ammonium cation in which a hydrocarbon group selected from the group is substituted with a nitrogen atom.
A hydroxyl group, amino group, nitro group, cyano group, carboxyl group, ether group, aldehyde group, or the like may be bonded to the substituted hydrocarbon group.

式中、Ｒ及びＲ’は、それぞれ独立に、炭素数１〜６程度のアルキル基を表わす。炭素数１〜６程度のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基などが挙げられる。中でも、メチル基及びエチル基であることが、単位体積あたりの静電容量が増加する傾向があることから好ましい。
また、Ｒ^１〜Ｒ^３は、それぞれ独立に、水素原子又は炭素数１〜６程度のアルキル基を表わす。炭素数１〜６程度のアルキル基は、前記と同じものが挙げられる。Ｒ^１〜Ｒ^３は、互いに異なった基であってもよい。
有機４級アンモニウムカチオンのその他の具体例としては、以下の化合物が挙げられる。 Specific examples of the organic quaternary ammonium cation include an ammonium cation represented by the formula (1).

In the formula, R and R ′ each independently represents an alkyl group having about 1 to 6 carbon atoms. Examples of the alkyl group having about 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Among these, a methyl group and an ethyl group are preferable because the capacitance per unit volume tends to increase.
R ^{1 to} R ³ each independently represents a hydrogen atom or an alkyl group having about 1 to 6 carbon atoms. Examples of the alkyl group having about 1 to 6 carbon atoms are the same as those described above. R ^{1 to} R ³ may be groups different from each other.
Other specific examples of the organic quaternary ammonium cation include the following compounds.

(Tetraalkylammonium cation)
Tetramethylammonium, ethyltrimethylammonium, triethylmethylammonium, tetraethylammonium, tetran-propylammonium, tetran-butylammonium, diethyldimethylammonium, methyltri-n-propylammonium, tri-n-butylmethylammonium, ethyltri-n- Butylammonium, tri-n-octylmethylammonium, ethyltri-n-octylammonium, diethylmethyl-i-propylammonium, diethylmethyl-n-propylammonium, ethyldimethyl-i-propylammonium, ethyldimethyl-n-propylammonium, Diethylmethylmethoxyethylammonium, dimethylethylmethoxyethylammonium, benzyltrimethylammonium Umm, (CF3CH2) (CH3) 3N +, (CF3CH2) 2 (CH3) 2N +, etc.

（式中、Ｑは窒素原子又はリン原子を表し、ｎ、ｍはそれぞれ独立に、４〜６の整数を表す。） (Ethylene diammonium cation)
N, N, N, N ′, N ′, N′-hexamethylethylenediammonium, N, N′-diethyl-N, N, N ′, N′-tetramethylethylenediammonium, etc. Bicyclo type ammonium cation)

(In the formula, Q represents a nitrogen atom or a phosphorus atom, and n and m each independently represents an integer of 4 to 6.)

(Guanidinium cation with imidazolinium skeleton)
2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolinium, 2- Dimethylamino-1-methyl-3,4-diethylimidazolinium, 2-diethylamino-1-methyl-3,4-diethylimidazolinium, 2-diethylamino-1,3,4-tetraethylimidazolinium, 2- Dimethylamino-1,3-dimethylimidazolinium, 2-diethylamino-1,3-dimethylimidazolinium, 2-dimethylamino-1-ethyl-3-methylimidazolinium, 2-diethylamino-1,3-diethyl Imidazolium, 1,5,6,7-tetrahydro-1,2-dimethyl-12H-0 imide 1,2a] imidazolinium, 1,5-dihydro-1,2-dimethyl-2H-imide [1,2a] imidazolinium, 1,5,6,7-tetrahydro-1,2-dimethyl-2H- Pyrimido [1,2a] imidazolinium, 1,5-dihydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolinium, 2-dimethylamino-4-cyano-1,3-dimethylimidazoli , 2-dimethylamino-3-cyanomethyl-1-methylimidazolinium, 2-dimethylamino-4-acetyl-1,3-dimethylimidazolinium, 2-dimethylamino-3-acetylmethyl-1-methylimidazolium Linium, 2-dimethylamino-4-methylcarbooxymethyl-1,3-dimethylimidazolinium, 2-dimethylamino-3-methylcarb Oxymethyl-1-methylimidazolinium, 2-dimethylamino-4-methoxy-1,3-dimethylimidazolinium, 2-dimethylamino-3-methoxymethyl-1-methylimidazolinium, 2-dimethylamino- 4-formyl-1,3-dimethylimidazolinium, 2-dimethylamino-3-formylmethyl-1-methylimidazolinium, 2-dimethylamino-3-hydroxyethyl-1-methylimidazolinium, 2-dimethyl Amino-4-hydroxymethyl-1,3-dimethylimidazolinium and the like.

(Guanidinium cation with imidazolium skeleton)
2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-dimethylamino- 1-methyl-3,4-diethylimidazolium, 2-diethylamino-1-methyl-3,4-diethylimidazolium, 2-diethylamino-1,3,4-tetraethylimidazolium, 2-dimethylamino-1,3 -Dimethylimidazolium, 2-diethylamino-1,3-dimethylimidazolium, 2-dimethylamino-1-ethyl-3-methylimidazolium, 2-diethylamino-1,3-diethylimidazolium, 1,5,6, 7-Tetrahydro-1,2-dimethyl-2H-imide [1,2a] imidazolium 1,5-dihydro-1,2-dimethyl-2H-imide [1,2a] imidazolium, 1,5,6,7-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolium 1,5-dihydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolium, 2-dimethylamino-4-cyano-1,3-dimethylimidazolium, 2-dimethylamino-3-cyanomethyl- 1-methylimidazolium, 2-dimethylamino-4-acetyl-1,3-dimethylimidazolinium, 2-dimethylamino-3-acetylmethyl-1-methylimidazolium, 2-dimethylamino-4-methylcarbooxy Methyl-1,3-dimethylimidazolium, 2-dimethylamino-3-methylcarbooxymethyl-1-methylimidazolium 2-dimethylamino-4-methoxy-1,3-dimethylimidazolium, 2-dimethylamino-3-methoxymethyl-1-methylimidazolium, 2-dimethylamino-4-formyl-1,3-dimethylimidazolium, 2-dimethylamino-3-formylmethyl-1-methylimidazolium, 2-dimethylamino-3-hydroxyethyl-1-methylimidazolium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolium, etc. .

(Guanidinium cation with tetrahydropyrimidinium skeleton)
2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-1-methyl-3,4-diethyl-1,4,5,6 -Tetrahydropyrimidinium, 2-diethylamino-1-methyl-3,4-diethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3,4-tetraethyl-1,4,5 , 6-tetrahydropyrimidinium, 2-dimethylamino-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl 1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-diethyl-1 , 4,5,6-tetrahydropyrimidinium, 1,3,4,6,7,8-hexahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,3,4,6- Tetrahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,3,4,6,7,8-hexahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 1, 3,4,6-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2-dimethylamino-4-cyano-1,3-dimethyl-1,4,5,6-tetrahydro Limidinium, 2-dimethylamino-3-cyanomethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-acetyl-1,3-dimethyl-1,4,5,6 -Tetrahydropyrimidinium, 2-dimethylamino-3-acetylmethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-methylcarbooxymethyl-1,3-dimethyl -1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-methylcarbooxymethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4- Methoxy-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-methoxymethyl-1-methyl- 1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-formyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-formylmethyl -1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-hydroxyethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino- 4-hydroxymethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium and the like.

(Guanidinium cation with dihydropyrimidinium skeleton)
2-dimethylamino-1,3,4-trimethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4 (6) -dihydropyrimidinium, 2 -Diethylamino-1,3-dimethyl-4-ethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-1-methyl-3,4-diethyl-1,4 (6) -dihydropyrimidi 2-diethylamino-1-methyl-3,4-diethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3,4-tetraethyl-1,4 (6) -dihydropyrimidi 2-dimethylamino-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2 Dimethylamino-1-ethyl-3-methyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3-diethyl-1,4 (6) -dihydropyrimidinium, 1,6,7 , 8-tetrahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,6-dihydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,6,7,8 -Tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 1,6-dihydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2-dimethylamino-4-cyano- 1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-cyanomethyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2 Dimethylamino-4-acetyl-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-acetylmethyl-1-methyl-1,4 (6) -dihydropyrimidinium 2-dimethylamino-4-methylcarbooxymethyl-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-methylcarbooxymethyl-1-methyl-1,4 (6) -Dihydropyrimidinium, 2-dimethylamino-4-methoxy-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-3-methoxymethyl-1-methyl- 1,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-formyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethyl Tilamino-3-formylmethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-hydroxyethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium 2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-1,4 (6) -dihydropyrimidinium and the like.

(Pyrrolidinium cation)
N, N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, Nn-propyl-N-methylpyrrolidinium, Nn-butyl-N-methylpyrrolidinium, N, N- Diethylpyrrolidinium, spiro (1,1 ')-bipyrrolidinium and the like.
(Piperidinium cation)
N, N-dimethylpiperidinium, N-ethyl-N-methylpiperidinium, N, N-diethylpiperidinium, Nn-propyl-N-methylpiperidinium, Nn-butyl-N- Methylpiperidinium, N-ethyl-Nn-butylpiperidinium, and the like.
(Hexamethyleneiminium cation)
N, N-dimethylhexamethyleneiminium, N-ethyl-N-methylhexamethyliminium, N, N-diethylhexamethyleneiminium, etc.
(Morpholinium cation)
N, N-dimethylmorpholinium, N-ethyl-N-methylmorpholinium, N-butyl-N-methylmorpholinium, N-ethyl-N-butylmorpholinium and the like.
(Piperazinium cation)
N, N, N ′, N′-tetramethylpiperazinium, N-ethyl-N, N ′, N′-trimethylpiperazinium, N, N′-diethyl-N, N′-dimethylpiperazinium, N, N, N′-triethyl-N′-methylpiperazinium, N, N, N ′, N′-tetraethylpiperazinium and the like.

(Tetrahydropyrimidinium cation)
1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1,3,4-trimethyl-1, 4,5,6-tetrahydropyrimidinium, 1,3,5-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1-ethyl-2,3-dimethyl-1,4,5,6- Tetrahydropyrimidinium, 1-ethyl-3,4-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1-ethyl-3,5-dimethyl-1,4,5,6-tetrahydropyrimidinium 1-ethyl-3,6-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-ethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-ethyl -1,3-dimethyl- , 4,5,6-tetrahydropyrimidinium, 5-ethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetramethyl-1,4 5,6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 8-methyl-1,8-diazabicyclo [5.4.0]- 7-undecenium, 5-methyl-1,5-diazabicyclo [4.3.0] -5-nonenium, 8-ethyl-1,8-diazabicyclo [5.4.0] -7-undecenium, 5-ethyl- 1,5-diazabicyclo [4.3.0] -5-nonenium, 5-methyl-1,5-diazabicyclo [5.4.0] -5-undecenium, 5-ethyl-1,5-diazabicyclo [5. 4.0] -5-un Cenium, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1-ethyl-2,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1-ethyl-2,3,5-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1-ethyl-2,3,6-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-ethyl-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-ethyl-1,3,5-trimethyl-1,4,5,6-tetrahydropyrimidinium, 4-ethyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 4-ethyl-1,3,5-tri Methyl-1,4,5,6-tetrahydropyrimidinium, 4-ethyl-1,3,6-trimethyl-1,4,5,6-tetrahydropyrimidinium, 5-ethyl-1,2,3- Trimethyl-1,4,5,6-tetrahydropyrimidinium, 5-ethyl-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2-diethyl-3,4- Dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2-diethyl-3,5-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2-diethyl-3,6- Dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,3-diethyl-2,4-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,3-diethyl-2,5- Dimethyl-1,4,5,6-te Lahydropyrimidinium, 1,4-diethyl-2,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,4-diethyl-3,5-dimethyl-1,4,5,6 -Tetrahydropyrimidinium, 1,4-diethyl-3,6-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,5-diethyl-2,3-dimethyl-1,4,5,6 -Tetrahydropyrimidinium, 1,5-diethyl-3,4-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,5-diethyl-3,6-dimethyl-1,4,5,6 -Tetrahydropyrimidinium, 2,4-diethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2,5-diethyl-1,3-dimethyl-1,4,5,6 -Tetrahydropyrimidinium, , 5-diethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4,6-diethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4,5-pentamethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4,6-pentamethyl-1,4,5,6-tetrahydropyrimidinium, , 2,3,4,5,6-hexamethyl-1,4,5,6-tetrahydropyrimidinium, 4-cyano-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium 3-cyanomethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-cyanomethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-acetyl -1,2,3-tri Methyl-1,4,5,6-tetrahydropyrimidinium, 3-acetylmethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-methylcarbooxymethyl-1,2, 3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-methylcarbooxymethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-methoxy-1,2 , 3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-methoxymethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-formyl-1,2, 3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-formylmethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 3-hydroxy Til-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-hydroxymethyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-hydroxy Ethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium and the like.

(Dihydropyrimidinium cation)
1,3-dimethyl-1,4- or -1,6-dihydropyrimidinium, [these are expressed as 1,3-dimethyl-1,4 (6) -dihydropyrimidinium, Use. 1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4 (6) -dihydropyrimidinium, 1,2,3 5-tetramethyl-1,4 (6) -dihydropyrimidinium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,9 (10) -undecadienium, 5-methyl- 1,5-diazabicyclo [4,3,0] -5,7 (8) -nonadienium, 4-cyano-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3-cyanomethyl- 1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 2-cyanomethyl-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 4-acetyl-1,2,3- Trimethyl-1,4 (6) -dihydropyrimidinium, 3 Acetylmethyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-methylcarbooxymethyl-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3- Methylcarbooxymethyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-methoxy-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3-methoxy Methyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-formyl-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3-formylmethyl-1 , 2-Dimethyl-1,4 (6) -dihydropyrimidinium, 3-hydroxyethyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-hydroxymethyl-1,2,3 Trimethyl-1,4 (6) -dihydropyrimidinium, 2-hydroxyethyl-1,3-dimethyl-1,4 (6) -hydropyrimidinium, and hydrogen at the 2-position of the dihydropyrimidinium cation A cation in which an atom is substituted with a fluorine atom.

1,3,4,6,7,8-Hexahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium

(Pyridinium cation)
N-methylpyridinium, N-ethylpyridinium, Nn-propylpyridinium, Nn-butylpyridinium, N-methyl-4-methylpyridinium, N-ethyl-4-methylpyridinium, Nn-propyl-4- Methylpyridinium, Nn-butyl-4-methylpyridinium, N-methyl-3-methylpyridinium, N-ethyl-3-methylpyridinium, Nn-propyl-3-methylpyridinium, Nn-butyl-3 -Methylpyridinium, N-methyl-2-methylpyridinium, N-ethyl-2-methylpyridinium, Nn-propyl-2-methylpyridinium, Nn-butyl-2-methylpyridinium, N-methyl-2, 4-dimethylpyridinium, N-ethyl-2,4-dimethylpyridinium, Nn-propi -2,4-dimethylpyridinium, Nn-butyl-2,4-dimethylpyridinium, N-methyl-3,5-dimethylpyridinium, N-ethyl-3,5-dimethylpyridinium, Nn-propyl-3 , 5-dimethylpyridinium, Nn-butyl-3,5-dimethylpyridinium, N-methyl-4-dimethylaminopyridinium, N-ethyl-4-dimethylaminopyridinium, Nn-propyl-4-dimethylaminopyridinium N-n-butyl-4-dimethylaminopyridinium and the like.

(Picolinium cation)
N-methylpicolinium, N-ethylpicolinium, etc. (imidazolinium cation)
1,2,3-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethyl-2,4- Diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1-methyl-2,3,4-triethylimidazolinium, 1,2,3,4-tetraethylimidazolinium, 1, 3-dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium, 1,2,3-triethylimidazolinium, 1,1-dimethyl-2-heptylimidazolinium, 1, 1-dimethyl-2- (2′-heptyl) imidazolinium, 1,1-dimethyl-2- (3′-heptyl) imidazolinium, 1,1-dimethyl-2- (4′-hept L) imidazolinium, 1,1-dimethyl-2-dodecylimidazolinium, 1,1-dimethylimidazolinium, 1,1,2-trimethylimidazolinium, 1,1,2,4-tetramethylimidazole Linium, 1,1,2,5-tetramethylimidazolinium, 1,1,2,4,5-pentamethylimidazolinium, 1,2,3-trimethylimidazolinium, 1,3,4 Trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, 1,2,3,4-tetraethylimidazolinium, 1,2,3,5-pentamethylimidazolinium, 1,3- Dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazolinium, 1-ethyl-3,4-dimethylimidazolinium, 1-ethyl-3,5-di Tyrimidazolinium, 4-ethyl-1,3-dimethylimidazolinium, 1,2-diethyl-3-methylimidazolinium, 1,4-diethyl-3-methylimidazolinium, 1,5-diethyl- 3-methylimidazolinium, 1,3-diethyl-2-methylimidazolinium, 1,3-diethyl-4-methylimidazolinium, 1,2,3-triethylimidazolinium, 1-ethyl-2, 3,4-trimethylimidazolinium, 1-ethyl-2,3,5-trimethylimidazolinium, 1-ethyl-3,4,5-trimethylimidazolinium, 2-ethyl-1,3,4-trimethyl Imidazolinium, 4-ethyl-1,2,3-trimethylimidazolinium, 1,2-diethyl-3,4-dimethylimidazolinium, 1,3-diethyl -2,4-dimethylimidazolinium, 1,4-diethyl-2,3-dimethylimidazolinium, 2,4-diethyl-1,3-dimethylimidazolinium, 4,5-diethyl-1,3- Dimethylimidazolinium, 3,4-diethyl-1,2-dimethylimidazolinium, 1,2,3-triethyl-4-methylimidazolinium, 1,2,4-triethyl-3-methylimidazolinium, 1,2,5-triethyl-3-methylimidazolinium, 1,3,4-triethyl-2-methylimidazolinium, 1,3,4-triethyl-5-methylimidazolinium, 1,4,5 -Triethyl-3-methylimidazolinium, 2,3,4-triethyl-1-methylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium, 3-si Nomethyl-1,2-dimethylimidazolinium, 2-cyanomethyl-1,3-dimethylimidazolinium, 4-acetyl-1,2,3-trimethylimidazolinium, 3-acetylmethyl-1,2-dimethylimidazole Linium, 4-methylcarbooxymethyl-1,2,3-trimethylimidazolinium, 3-methylcarbooxymethyl-1,2-dimethylimidazolinium, 4-methoxy-1,2,3-trimethylimidazoli Ni, 3-methoxymethyl-1,2-dimethylimidazolinium, 4-formyl-1,2,3-trimethylimidazolinium, 3-formylmethyl-1,2-dimethylimidazolinium, 3-hydroxyethyl- 1,2-dimethylimidazolinium, 4-hydroxymethyl-1,2,3-trimethylimidazoli Um, such as 2-hydroxyethyl, 3-dimethyl imidazolinium, and compounds the 2-position of the hydrogen atoms substituted with fluorine atoms of the imidazolinium-based cation.

(Quinolinium cation)
N-methylquinolinium, N-ethylquinolinium, etc.
(Bipyridinium cation)
Ion such as N-methyl-2,2′-bipyridinium, N-ethyl-2,2′-bipyridinium and the like are represented. )
Examples of the imidazolium cation include 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1,3-diethylimidazolium, 1,2,3-trimethylimidazolium, 1,3,4- Trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1-ethyl-3,4-dimethylimidazolium, 1-ethyl-3,5-dimethylimidazolium, 2-ethyl-1,3-dimethylimidazole 4-ethyl-1,3-dimethylimidazolium, 1,2-diethyl-3-methylimidazolium, 1,4-diethyl-3-methylimidazolium, 1,5-diethyl-3-methylimidazolium, 1,3-diethyl-2-methylimidazolium, 1,3-diethyl-4-methylimidazolium, 1,2, -Triethylimidazolium, 1,3,4-triethylimidazolium, 1,2,3,4-tetramethylimidazolium, 1-ethyl-2,3,4-trimethylimidazolium, 1-ethyl-2,3,3 5-trimethylimidazolium, 1-ethyl-3,4,5-trimethylimidazolium, 2-ethyl-1,3,4-trimethylimidazolium, 4-ethyl-1,2,3-trimethylimidazolium, 1, 2-diethyl-3,4-dimethylimidazolium, 1,3-diethyl-2,4-dimethylimidazolium, 1,4-diethyl-2,3-dimethylimidazolium, 2,4-diethyl-1,3- Dimethylimidazolium, 4,5-diethyl-1,3-dimethylimidazolium, 1,2,3-triethyl-4-methylimidazolium, 1, , 4-triethyl-3-methylimidazolium, 1,2,5-triethyl-3-methylimidazolium, 1,3,4-triethyl-2-methylimidazolium, 1,3,4-triethyl-5-methyl Examples include imidazolium, 1,4,5-triethyl-3-methylimidazolium, 1,2,3,4,5-pentamethylimidazolium and the like.

(Other ammonium cations)
N-methylthiazolium, N-ethylthiazolium, N-methyloxazolium, N-ethyloxazolium, N-methyl-4-methylthiazolium, N-ethyl-4-methylthiazolium, N-ethyl-isothiazolium, 1,4-dimethyl-1,2,4-triazolium, 1,4-diethyl-1,2,4-triazolium, 1-methyl-4-ethyl-1,2,4-triazolium, 1 -Ethyl-4-methyl-1,2,4-triazolium, 1,2-dimethylpyrazolium, 1,2-diethylpyrazolium, 1-methyl-2-ethylpyrazolium, N-methylpyrazinium, N-ethylpyrazinium, N-methylpyridazinium, N-ethylpyridazinium, etc. are mentioned.

An organic quaternary phosphonium cation which is one of organic cations is an alkyl group (having 1 to 20 carbon atoms), a cycloalkyl group (having 6 to 20 carbon atoms), an aryl group (having 6 to 20 carbon atoms) and an aralkyl group ( A quaternary phosphonium cation in which a hydrocarbon group selected from the group consisting of 7 to 20 carbon atoms is substituted with a phosphorus atom.
A hydroxyl group, amino group, nitro group, cyano group, carboxyl group, ether group, aldehyde group, or the like may be bonded to the substituted hydrocarbon group.
The following compounds are illustrated as main organic quaternary ammonium cations and organic quaternary phosphonium cations.

(Tetraalkylphosphonium cation)
Tetramethylphosphonium, ethyltrimethylphosphonium, triethylmethylphosphonium, tetraethylphosphonium, diethyldimethylphosphonium, trimethyl-n-propylphosphonium, trimethylisopropylphosphonium, ethyldimethyl-n-propylphosphonium, ethyldimethylisopropylphosphonium, diethylmethyl-n-propylphosphonium , Diethylmethylisopropylphosphonium, dimethyldi-n-propylphosphonium, dimethyl-n-propylisopropylphosphonium, dimethyldiisopropylphosphonium, triethyl-n-propylphosphonium, n-butyltrimethylphosphonium, isobutyltrimethylphosphonium, t-butyltrimethylphosphonium, triethylisopropyl Ho Phonium, ethylmethyldi-n-propylphosphonium, ethylmethyl-n-propylisopropylphosphonium, ethylmethyldiisopropylphosphonium, n-butylethyldimethylphosphonium, isobutylethyldimethylphosphonium, t-butylethyldimethylphosphonium, diethyldi-n-propylphosphonium, diethyl N-propylisopropylphosphonium, diethyldiisopropylisopropylphosphonium, methyltri-n-propylphosphonium, methyldi-n-propylisopropylphosphonium, methyl-n-propyldiisopropylphosphonium, n-butyltriethylphosphonium, isobutyltriethylphosphonium, t-butyltriethylphosphonium Di-n-butyldimethylphosphonium, Isobutyldimethylphosphonium, di-t-butyldimethylphosphonium, n-butylisobutyldimethylphosphonium, n-butyl-t-butyldimethylphosphonium, isobutyl-t-butyldimethylphosphonium, tri-n-octylmethylphosphonium, ethyltri-n-octyl Phosphonium etc.

The organic anion is an anion containing a hydrocarbon group which may have a substituent, for example, N (SO ₂ R _f ) ²⁻ , C (SO ₂ R _f ) ³⁻ , R _f COO ⁻ , And an anion selected from the group consisting of R _f SO ³⁻ (R _f represents a C 1-12 perfluoroalkyl group), and organic acids (carboxylic acid, organic sulfonic acid, organic phosphoric acid) shown below ) Or an anion obtained by removing an active hydrogen atom from phenol.

(carboxylic acid)
-C2-C15 divalent to tetravalent polycarboxylic acid: aliphatic polycarboxylic acid [saturated polycarboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid , Sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, pentylmalonic acid, hexylmalon Acid, dimethylmalonic acid, diethylmalonic acid, methylpropylmalonic acid, methylbutylmalonic acid, ethylpropylmalonic acid, dipropylmalonic acid, methylsuccinic acid, ethylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid Acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-methyl-3-ethyl Glutaric acid, 3,3-diethylglutaric acid, methylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, 3,3-dimethylglutaric acid, 3-methyladipic acid and the like) 1,2-dicarboxylic acid, 4-methyl-cyclobutene-1,2-dicarboxylic acid, cyclopentene-1,2-dicarboxylic acid, 5-methyl-cyclopentene-1,2-dicarboxylic acid, bicyclo [2,2,1] Hept-2-ene-2,3-dicarboxylic acid, 1-methyl-bicyclo [2,2,1] hept-2-ene-2,3-dicarboxylic acid, 6-methyl-bicyclo [2,2,1] Hept-2-ene-2,3-dicarboxylic acid, bicyclo [2,2,1] hepta-2,5-diene-2,3-dicarboxylic acid, 1-methyl-bicyclo [2,2,1] he 2-2,5-diene-2,3-dicarboxylic acid, 6-methyl-bicyclo [2,2,1] hepta-2,5-diene-2,3-dicarboxylic acid, furan-2,3-dicarboxylic acid 5-methyl-furan-2,3-dicarboxylic acid, 4-methyl-furan-2,3-dicarboxylic acid, 4,5-dihydroxy-furan-2,3-dicarboxylic acid, 4,5-dihydroxy-4- Methyl-furan-2,3-dicarboxylic acid, 4,5-dihydroxy-5-methyl-furan-2,3-dicarboxylic acid, 2,5-dihydroxy-furan-3,4-dicarboxylic acid, 2,5-dihydroxy 2-methyl-furan-3,4-dicarboxylic acid, etc. Preferred among these are cyclobutene-1,2-dicarboxylic acid, 4-methyl-cyclobutene-1,2-dicarboxylic acid, cyclopentene-1 , 2-dicarboxylic acid, 5-methyl-cyclopentene-1,2-dicarboxylic acid, bicyclo [2,2,1] hept-2-ene-2,3-dicarboxylic acid, bicyclo [2,2,1] hepta 2,5-diene-2,3-dicarboxylic acid, furan-2,3-dicarboxylic acid, 5-methyl-furan-2,3-dicarboxylic acid, 4-methyl-furan-2,3-dicarboxylic acid, 5- Methyl-2,3-furan-dicarboxylic acid, 4,5-dihydroxy-furan-2,3-dicarboxylic acid, 2,5-dihydroxy-furan-3,4-dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, Citraconic acid, 1,2-cyclobutadiene-1,2-dicarboxylic acid, 4-methyl-1,2-cyclobutadiene-1,2-dicarboxylic acid, 1,2-cyclopentadiene-1,2-dicarboxylic acid 5-methyl-1,2-cyclopentadiene-1,2-dicarboxylic acid, 1,2-cyclohexadiene-1,2-dicarboxylic acid, 6-methyl-1,2-cyclohexadiene-1,2-dicarboxylic acid, 5-methyl-1,2-cyclohexadiene-1,2-dicarboxylic acid, furan-3,4-dicarboxylic acid, 2-methyl-furan-3,4-dicarboxylic acid and the like. Among these, preferred are 1,2-cyclobutadiene-1,2-dicarboxylic acid, 4-methyl-1,2-cyclobutadiene-1,2-dicarboxylic acid, 1,2-cyclopentadiene-1,2- Dicarboxylic acid, 5-methyl-1,2-cyclopentadiene-1,2-dicarboxylic acid, furan-3,4-dicarboxylic acid, 2-methyl-3,4-furan-dicarboxylic acid, etc.)], aromatic polycarboxylic acid Acids [phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.], S-containing polycarboxylic acids [thiodibropionic acid, etc.];

C2-C20 oxycarboxylic acid: aliphatic oxycarboxylic acid [glycolic acid, lactic acid, tartaric acid, castor oil fatty acid, etc.]; aromatic oxycarboxylic acid [salicylic acid, mandelic acid, 4-hydroxybenzoic acid, 1-hydroxy- 2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid and the like];
C1-C30 monocarboxylic acid: aliphatic monocarboxylic acid [saturated monocarboxylic acid (formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, lauric acid Acid, myristic acid, stearic acid, behenic acid, undencanic acid, etc.), unsaturated monocarboxylic acid (acrylic acid, methacrylic acid, crotonic acid, oleic acid, squaric acid, 4,5-dihydroxy-4-cyclopentene-1,3 -Dione, 2,3-dihydroxy-2-cyclohexene-1,4-dione, etc.)]; aromatic monocarboxylic acid [benzoic acid, cinnamic acid, naphthoic acid, toluic acid, ethylbenzoic acid, propylbenzoic acid, isopropyl Benzoic acid, butyl benzoic acid, isobutyl benzoic acid, secondary butyl benzoic acid, tertiary butyl benzoic acid, hydroxy Benzoic acid, ethoxybenzoic acid, propoxybenzoic acid, isopropoxybenzoic acid, butoxybenzoic acid, isobutoxybenzoic acid, second butoxybenzoic acid, tertiary butoxybenzoic acid, aminobenzoic acid, N-methylaminobenzoic acid, N- Ethylaminobenzoic acid, N-propylaminobenzoic acid, N-isopropylaminobenzoic acid, N-butylaminobenzoic acid, N-isobutylaminobenzoic acid, N-secondarybutylaminobenzoic acid, N-tertiarybutylaminobenzoic acid N, N-dimethylaminobenzoic acid, N, N-diethylaminobenzoic acid, nitrobenzoic acid, fluorobenzoic acid, etc.]

(Phenol)
-Monohydric phenols (including phenols and naphthols): phenols, alkyl (C1-C15) phenols (cresol, xylenol, ethylphenol, n- or isopropylphenol, isododecylphenol, etc.), methoxyphenols ( Eugenol, guaiacol, etc.), α-naphthol, β-naphthol, cyclohexylphenol, etc .;
Polyhydric phenol: catechol, resorcin, pyrogallol, phloroglucin, bisphenol A, bisphenol F, bisphenol S, etc.

(Phosphate ester having 1 to 2 alkyl groups having 1 to 15 carbon atoms in the molecule)
Mono and dimethyl phosphate, mono and diisopropyl phosphate, mono and dibutyl phosphate, mono and di- (2-ethylhexyl) phosphate, mono and diisodecyl phosphate, and the like.

(Organic sulfonic acid)
Alkyl (C1-C15) benzenesulfonic acid (p-toluenesulfonic acid, nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, etc.), sulfosalicylic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.
(Organic acid having triazole or tetrazole skeleton)
1-H-1,2,4-triazole, 1,2,3-triazole, 1,2,3-benzotriazole, carboxybenzotriazole, 3-mercapto-1,2,4-triazole, 1,2,3 -Triazole-4,5-dicarboxylic acid, 3-mercapto-5-methyl-1,2,4-triazole, 1,2,3,4-tetrazole, etc.

(Boron-containing organic acid)
Borodioxalic acid, borodiglycolic acid, borodi (2-hydroxyisobutyric acid), alkaneboric acid, arylboric acid, methaneboric acid, ethaneboric acid, phenylboric acid, etc.

Anion represented by the following formula [(R _f ) _k BF _4-k ] ⁻
(In the formula, k represents an integer of 1 to 4. R _f represents the same meaning as described above.)

Trifluoromethyl trifluoroborate, bis (trifluoromethyl) difluoroborate, tris (trifluoromethyl) fluoroborate, tetrakis (trifluoromethyl) borate, pentafluoroethyl trifluoroborate, bis (pentafluoroethyl) difluoroborate, tris (Pentafluoroethyl) fluoroborate, tetrakis (pentafluoroethyl) borate and the like.

（式中、Ｒ’は、水酸基、アミノ基、ニトロ基、シアノ基、クロル基、フルオロ基、ホルミル基もしくはエーテル結合を有する基を有していてもよい炭素数１〜１０の炭化水素基または水素原子かフッ素原子である。Ｒ’は、互いに同一でも異なっていてもよい。Ｒ’の相互がアルキレン基として結合して環を形成してもよい。） Anion represented by the following formula

(In the formula, R ′ represents a hydroxyl group, an amino group, a nitro group, a cyano group, a chloro group, a fluoro group, a formyl group, or a hydrocarbon group having 1 to 10 carbon atoms which may have a group having an ether bond, or (It is a hydrogen atom or a fluorine atom. R ′ may be the same or different from each other. R ′ may be bonded together as an alkylene group to form a ring.)

（式中、Ｒ”はＲ’と同じ意味を表す。Ｒ”は、互いに同一でも異なっていてもよい。Ｒ”の相互が炭化水素基として結合して環を形成してもよい。） Anion represented by the following formula

(In the formula, R ″ represents the same meaning as R ′. R ″ may be the same as or different from each other. R ″ may be bonded to each other as a hydrocarbon group to form a ring.)

（式中、Ｒ^１及びＲ^２は炭素数１〜４でフッ素を含有する１価の有機基である。Ｒ^１及びＲ^２は互いに同一でも異なっていてもよい。Ｒ^３は炭素数２〜８でフッ素を含有する２価の有機基である。） Anion represented by the following formula

(In the formula, R ¹ and R ² are monovalent organic groups having 1 to 4 carbon atoms and containing fluorine. R ¹ and R ² may be the same as or different from each other. R ³ is 2 to 2 carbon atoms. 8 is a divalent organic group containing fluorine.)

As the anion of the electrolyte, an inorganic anion is preferable, and BF ₄ ⁻ , AsF ₆ ⁻ and SbF ₆ ⁻ are particularly preferable, and among them, BF ₄ ⁻ is preferable because the capacitance tends to be improved.

As the solvent for the electrolytic solution for dissolving the electrolyte, a polar solvent is usually used. Specific examples include linear carbonates such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, diphenyl carbonate, and methyl phenyl carbonate;
Carbonates such as cyclic carbonates such as ethylene carbonate, propylene carbonate, 2,3-dimethylethylene carbonate, butylene carbonate, vinylene carbonate, 2-vinylethylene carbonate;
Carboxylic acid esters such as methyl formate, methyl acetate, methyl propionate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl benzoate, ethyl benzoate, γ-butyrolactone, γ-valerolactone, δ-valerolactone;
Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,6-dimethyltetrahydrofuran, tetrahydropyran, etc. Ethers;

Nitriles such as acetonitrile, propionitrile, methoxypropionitrile, glutaronitrile, adiponitrile, 2-methylglutaronitrile;
Amides such as N-methylformamide, N-ethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone;
Sulfones such as dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, sulfolane, 3-methyl sulfolane, 2,4-dimethyl sulfolane;
Sulfoxides such as dimethyl sulfoxide, methyl ethyl sulfoxide and diethyl sulfoxide; Sulfate esters such as dimethyl sulfate, diethyl sulfate, ethylene sulfate and propylene sulfate;
Sulfites such as dimethyl sulfite, diethyl sulfite, ethylene sulfite and propylene sulfite; phosphate esters such as trimethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate and triethyl phosphate;
Examples include 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 3-methyl-2-oxazolidinone, and nitromethane.
The solvent for dissolving the electrolyte may be a mixture of different solvents.

  As the solvent for dissolving the electrolyte, carbonic acid esters, carboxylic acid esters, nitriles, amides, and sulfones are preferably used, and carbonic acid esters and carboxylic acid esters are more preferably used.

The concentration of the electrolyte in the electrolytic solution is usually 0.5 to 5.0 mol (electrolyte) / L (electrolytic solution), preferably about 0.7 to 3.0 mol (electrolyte) / L (electrolytic solution). is there. When the electrolyte is dissolved by 0.5 mol / L or more, it is preferable because the capacitance tends to increase, and when it is 5.0 mol / L or less, the viscosity of the electrolytic solution tends to be low.
The water content contained in the electrolytic solution is usually 200 ppm or less, preferably 50 ppm or less, and more preferably 20 ppm or less. By suppressing the water content, it is possible to avoid the influence on the electrode due to the electrolysis of water, in particular, the decrease in the withstand voltage.

The electrode of the present invention is used for an electrode of, for example, a dry battery, a redox capacitor, a hybrid capacitor, and an electric double layer capacitor.
Here, the redox capacitor can be used for an electrode as described in Chapter 3 (p141-) of “The Front Line of Large-Capacity Electric Double-Layer Capacitors (Supervision Hideo Tamura, Issuer NTS)”. It is a device characterized by containing a substance and storing electricity by oxidation-reduction reaction. A separator similar to that used in an electric double layer capacitor described later is sandwiched between the two electrodes, and the electrolyte solution is filled. In the present invention, the electrolytic solution means a mixture of an electrolyte and a solvent.
Examples of the active material used for the redox capacitor include transition metal oxides such as ruthenium, transition metal hydroxides, and conductive polymers. The electrode contains 1 to 60% by weight of the activated carbon of the present invention alone or a mixture of the activated carbon of the present invention and the conductive agent exemplified above, and 2 to 30% by weight of the binder exemplified above.
As an electrolytic solution for a redox capacitor, when a transition metal oxide such as ruthenium or a transition metal hydroxide is used as an active material, a sulfuric acid aqueous solution is exemplified by the conditions described in JP-A-2002-359155. It is done. Moreover, when using an organic acid as an electrolyte and using an electrolytic solution dissolved in an organic solvent, for example, the conditions described in JP-A No. 2002-267860 are exemplified. When a conductive polymer is used as an active material, an electrolyte that dissolves in an organic solvent and dissociates may be used. Examples thereof include lithium salts such as LiBF ₄ , LiPF ₆ , and LiClO _4. It is done. In particular, it is desirable to use LiPF ₆ because it has a high degree of ionization and good solubility. These electrolytes may be used alone, or two or more of these electrolytes may be used in combination. The concentration of the electrolyte in the electrolytic solution is preferably 0.5 to 1.5 mol / L because the ionic conductivity is good. When the concentration of the electrolyte is 0.5 mol / L or more, the electrostatic capacity tends to be improved, and when it is 1.5 mol / L or less, the viscosity of the electrolytic solution is lowered and the ionic conductivity is improved. It is preferable because of its tendency.
As the solvent contained in the redox capacitor electrolyte, an organic polar solvent exemplified by an electric double layer capacitor described later is preferably used. Among these, it is desirable to use an aprotic organic solvent, and for example, a mixed solvent composed of one or more of cyclic carbonate, chain carbonate, cyclic ester and the like can be used. Examples of cyclic carbonates include ethylene carbonate, propylene carbonate, etc., examples of chain carbonates include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, etc., examples of cyclic esters include γ-butyrolactone, γ-valerolactone, etc. Respectively. Any one of these can be used alone, or two or more can be mixed and used. The electrolyte has a high dielectric constant to promote the dissociation of the electrolyte, a low viscosity so as not to hinder the movement of ions, and a high electrochemical oxidation-reduction resistance. Is required. Therefore, carbonic acid esters are particularly suitable as the solvent. For example, it is desirable to use a mixture of ethylene carbonate or the like as the high dielectric constant solvent and diethyl carbonate or the like as the low viscosity solvent.

A hybrid capacitor is characterized in that during charging, lithium ions are inserted between carbon layers such as graphite in the negative electrode, and in the positive electrode, an anion of the electrolyte is attracted to the electrode surface to form an electric double layer, thereby storing electricity. It is a device. An electrode similar to the negative electrode of the lithium ion secondary battery is used for the negative electrode, the electrode of the present invention described above is used for the positive electrode, and a separator similar to the electric double layer capacitor described later is interposed between the positive electrode and the negative electrode. It is configured to be sandwiched and filled with the electrolytic solution. Specifically, the negative electrode can be used as described in Chapter 1, Section 3 (p25 to 25) of “Next-generation lithium secondary battery (supervised by Hideo Tamura, NTS)”. .
As an electrolyte for a hybrid capacitor, a combination of an inorganic anion and a lithium cation is usually used, and in particular, at least one inorganic anion selected from the group consisting of BF ₄ ⁻ , PF ₆ ⁻ , and ClO ₄ ^— and a lithium cation. The combination of is preferable.
As the organic polar solvent contained in the electrolytic solution of the hybrid capacitor, a solvent mainly containing at least one selected from the group consisting of carbonates and lactones is usually used. Specific examples include cyclic carbonates such as propylene carbonate, ethylene carbonate and butylene carbonate, chain carbonates such as dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate, and solvents such as γ-butyrolactone, preferably ethylene carbonate. And a mixed solvent of γ-butyrolactone, a mixed solvent of γ-butyrolactone and one or more chain carbonates, and the like.
As the additive, the additive exemplified in the section of the electric double layer capacitor may be used.

The electrode of the present invention is suitable for an electrode of an electric double layer capacitor because of its excellent capacitance. Hereinafter, the electric double layer capacitor will be described in detail.
The electric double layer capacitor of the present invention is a capacitor including the electrode. Specifically, for example, there is an independent separator between the positive electrode and the negative electrode that are the electrodes, and the separator For example, a capacitor in which an electrolyte solution is filled between the electrode and the electrode, for example, a capacitor in which a solid electrolyte (gel electrolyte) is filled between the positive electrode and the negative electrode, which are the electrodes, can be used.
By charging, the positive electrode is positively charged, the negative electrolyte forms an electric double layer at the positive electrode interface, and at the same time, the negative electrode is negatively charged, and the positive electrolyte forms an electric double layer at the negative electrode interface. Electric energy is stored by Even if charging is stopped, the electric double layer is maintained, but when discharged, the electric double layer is canceled and electric energy is released.
The electric double layer capacitor may be a single cell including a positive electrode and a negative electrode, or may be a capacitor in which a plurality of cells are combined.

The solid electrolyte is obtained by dispersing an electrolyte described later in a resin, and an organic polar solvent described later may be further dispersed. Specifically, the gel electrolyte described in p79 of “The forefront of large-capacity electric double layer capacitors (supervised by Hideo Tamura, publisher NTS)”, Japanese Patent Application Laid-Open No. 2004-172346 and its cited documents, Examples thereof include solid electrolytes described in Japanese Unexamined Patent Application Publication No. 2004-303567 and references cited therein, Japanese Patent Application Laid-Open No. 2003-68580 and reference materials thereof, Japanese Patent Application Laid-Open No. 2003-257240, and the like.
The electric double layer capacitor of the present invention is preferably an electric double layer capacitor in which a separator is independently provided between the positive electrode and the negative electrode, which are the electrodes, and an electrolyte is filled between the separator and the electrode. The electric double layer capacitor will be described in detail below.

Examples of the shape of the electric double layer capacitor include a coin type, a wound type, a laminated type, and a bellows type.
As an example of coin-type manufacturing, as shown in FIG. 1, a current collector (12), an electrode (13), a separator (14), an electrode (13) and a current collector are placed in a metal container (11) such as stainless steel. Examples include a method of sequentially laminating the electric bodies (12), filling them with an electrolytic solution, and sealing with a metal lid (15) and a gasket (16).
As an example of winding type production, as shown in FIG. 2, a mixed slurry containing the activated carbon is applied to a current collector (22) and dried, and a laminated sheet of the current collector (22) and electrode (23). The two sheets are wound through a separator (24) and housed in a cylindrical metal container (21) such as aluminum or stainless steel together with an electrode sealing plate (25).
The current collector is provided with a lead in advance, and electricity is charged and discharged with the lead (26) of one laminated sheet as a positive electrode and the lead (26) of the other laminated sheet as a negative electrode.
As shown in FIG. 3, after laminating sheets of current collectors (32) and electrodes (33) and separators (34) alternately, as shown in FIG. 3, a metal container (31) such as aluminum or stainless steel is used. , Filled with electrolyte, and the current collector is alternately connected to the lead (35) and sealed; as shown in FIG. 4, the laminated sheet of the current collector (42) and the electrode (43) and the separator Examples include a method of alternately pressing (44), sealing the outer layer with a rubber material or the like, filling the electrolytic solution, and then sealing. Also. As a bipolar structure including the gasket (46) as appropriate, a structure in which the working voltage can be arbitrarily set may be used.
As shown in FIG. 5, the embodiment of the present invention includes a sheet-shaped electrode (53), a separator (54), an electrode (53), a current collector (52), and a pressure plate (51). An electric double layer capacitor was formed by laminating an insulating material (55), filling an electrolyte between the separator (54) and the electrode (53), sealing the outer layer with a fluororesin, and pressing with a bolt. The bolt is insulated from the current collector (52).
The bellows type is a method in which two sheets of electrodes and current collectors are laminated while being folded in a bellows shape via a separator, and then prepared in the same manner as the laminated type.

The separator used in the electric double layer capacitor separates the positive electrode and the negative electrode and plays a role of holding the electrolytic solution, and has a large ion permeability, a predetermined mechanical strength, and an insulating film is used. .
Examples of the separator include paper made of viscose rayon and natural cellulose, electrolytic paper, craft paper, manila paper, mixed paper obtained by making fibers such as cellulose and polyester, polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, glass Fiber, porous polyethylene, porous polypropylene, porous polyester, aramid fiber, polybutylene terephthalate nonwoven fabric, para-type wholly aromatic polyamide, vinylidene fluoride, tetrafluoroethylene, copolymer of vinylidene fluoride and hexafluoropropylene , Non-woven fabrics such as fluorine-containing resins such as fluoro rubber, or porous membranes.
The separator may be a molded product made of ceramic powder particles such as silica and the binder. The molded product is usually formed integrally with the positive electrode and the negative electrode. Moreover, about the separator using polyethylene, a polypropylene, etc., in order to improve hydrophilicity, you may mix surfactant and a silica particle. Further, the separator may contain an organic solvent such as acetone and a plasticizer such as dibutyl phthalate (DBP).

As the separator, a proton conductive polymer may be used.
As the separator, among others, electrolytic paper, viscose rayon or natural cellulose paper, kraft paper, manila paper, mixed paper obtained by making cellulose or polyester fiber, polyethylene non-woven fabric, polypropylene non-woven fabric, polyester non-woven fabric, manila hemp sheet, A glass fiber sheet or the like is preferable.
The pore diameter of the separator is usually about 0.01 to 10 μm. The thickness of the separator is usually about 1 to 300 μm, preferably about 5 to 30 μm.
The separator may be a laminate of separators having different porosity.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to an Example.

Example 1
In a reaction vessel, 33.0 g of resorcinol, 48.7 g of 37% by weight formalin, 0.16 g of sodium carbonate and 22 g of distilled water were mixed, and kept at 50 ° C. for 24 hours to obtain an organic aerogel wetted with water. At this time, the amount of the phenolic compound used per 1 mol of the base catalyst is 200 mol, and the amount of the phenolic compound used per 1 part by weight of water (the sum of water contained in formalin and distilled water) is 0.63 wt. Was part.
T-Butyl alcohol was added to the obtained gel for washing, and water in the gel was replaced with t-butyl alcohol. The gel substituted with t-butyl alcohol was freeze-dried at −30 ° C. for 24 hours under vacuum and then calcined at 800 ° C. in an argon atmosphere to obtain activated carbon. The obtained activated carbon had a pore volume of 0.47 cc / g.
The obtained activated carbon was pulverized and powdered (a mixture of 80 parts by weight, 10 parts by weight of carbon black, and 10 parts by weight of polytetrafluoroethylene was kneaded and then formed into a sheet shape. Between the two sheets, paper was put as a separator, and then a bipolar electric double layer capacitor filled with a propylene carbonate solution of 3 mol / L EMI ⁺ BF ₄ ^- salt as an electrolyte was prepared.
The capacitance per unit volume of the activated carbon was 21.3 F / cc and the capacitance per unit weight was 20.2 F / g by constant current charge / discharge measurement using the capacitor (100 mA / g). The results are shown in Table 1.

(Examples 2 to 8)
In Example 1, the amount of the phenolic compound used per 1 mol of sodium carbonate is the value shown in Table 2, and the use of the phenolic compound per part by weight of water (the sum of water and distilled water contained in formalin). The amount shown in Table 1 was used, the firing temperature was adjusted to the value shown in Table 1, tetraethylammonium BF ₄ salt was used as the electrolyte, and the electrolyte was adjusted to 1 mol / L, and 30 mA / g It carried out based on Example 1 except having performed constant current charge / discharge measurement. The results are shown in Table 1.

＊１：炭酸ナトリウム１モルあたりのフェノール性化合物の使用量
＊２：水（ホルマリンに含まれる水及び蒸留水の総和）１重量部あたりのフェノール性化合物の使用量

* 1: Amount of phenolic compound used per mole of sodium carbonate * 2: Amount of phenolic compound used per part by weight of water (sum of water contained in formalin and distilled water)

(Comparative Example 1)
In Example 1, the amount of phenolic compound used per part by weight of water (the total amount of water contained in formalin and distilled water) is the value shown in Table 1, and the firing temperature is the value shown in Table 1. This was carried out in accordance with Example 1 except that tetraethylammonium BF ₄ salt was used as the electrolyte, the electrolyte was adjusted to 1 mol / L, and a constant current charge / discharge measurement of 30 mA / g was performed. The results are shown in Table 1.

The activated carbon of the present invention can be used, for example, as an electrode for a dry cell, a sensor for a piezoelectric element, a carrier for supporting a catalyst, a chromatographic material, an adsorbent, an electrode for an electric double layer capacitor, and the like. Since it has an excellent per-capacitance, it is suitably used for an electrode of an electric double layer capacitor.
Since the electric double layer capacitor of the present invention is excellent in capacitance per unit volume, it can be used for adsorption and storage of energy sources. In particular, because of its excellent characteristics, it can be suitably used for adsorption and storage of energy sources in the field of portable electronic terminals and the field of transport equipment having a charging function.

An example of a coin-type electric double layer (schematic diagram) An example (schematic diagram) of a wound electric double layer Example of stacked electric double layer (schematic diagram) An example (schematic diagram) of a stacked electric double layer different from FIG. Example (schematic diagram) of laminated electric double layer used in Examples and Comparative Examples of the present invention

Explanation of symbols

11: Metal container 12: Current collector 13: Electrode 14: Separator 15: Metal lid 16: Gasket 21: Metal container 22: Current collector 23: Electrode 24: Separator 25: Electrode sealing plate 26: Lead 31: Metal container 32: Current collector 33: Electrode 34: Separator 35: Lead 36: Terminal 37: Safety valve 41: Pressure plate and terminal 42: Current collector 43; Electrode 44: Separator 46: Gasket 51: Pressure plate 52: Current collector Electric body 53; Electrode 54: Separator 55: Insulating material

Claims (6)

  In an activated carbon for an electric double layer capacitor obtained by carbonizing an organic aerogel obtained by polymerizing a phenolic compound having at least one hydroxyl group in the molecule and an aldehyde compound in the presence of an aqueous solvent and a basic catalyst, Activated carbon having a pore volume of 1.5 cc / g or less.   The activated carbon according to claim 1, wherein the phenol compound is resorcinol.   An electrode comprising the activated carbon according to claim 1.   An electric double layer capacitor comprising the electrode according to claim 3, a separator, an electrolyte, and a solvent.   In the method for producing activated carbon in which a phenolic compound having at least one hydroxyl group in the molecule and an aldehyde compound are polymerized in the presence of an aqueous solvent and a basic catalyst, and the resulting organic aerogel is carbonized, A method for producing activated carbon, wherein the phenolic compound is polymerized at 0.25 to 1000 mol of phenolic compound at 0.5 to 5 parts by weight of phenolic compound per 1 part by weight of aqueous solvent.   Carbonization is implemented at the calcination temperature of 650-850 degreeC, The manufacturing method of Claim 5 characterized by the above-mentioned.

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