JP2007043091A - Electrode and electric double layer capacitor - Google Patents

Abstract

（式中、Ｒは炭素数１〜１２の炭化水素基を表し、該炭化水素基には、水酸基、アルキル基、アルコキシル基、アリール基、アリールオキシ基、スルホニル基、ハロゲン原子、ニトロ基、チオアルキル基、シアノ基、カルボキシル基、アミノ基又はアミド基が結合していてもよい。Ｒ’は水素原子又はメチル基を表す。ｎは４、６又は８を表す。）
【選択図】なしProvided is an electrode suitable for an electric double layer capacitor having an improved capacitance among carbides obtained from a polymer of resorcinols and an aldehyde compound.
An electrode comprising activated carbon obtained by carbonizing and activating a compound represented by formula (1).

(In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and the hydrocarbon group includes a hydroxyl group, an alkyl group, an alkoxyl group, an aryl group, an aryloxy group, a sulfonyl group, a halogen atom, a nitro group, and a thioalkyl group. A group, a cyano group, a carboxyl group, an amino group or an amide group may be bonded, R ′ represents a hydrogen atom or a methyl group, and n represents 4, 6 or 8.)
[Selection figure] None

Description

  The present invention relates to an electric double layer capacitor and an electrode suitable for the capacitor.

Currently, there are demands for electrical energy storage devices that can store a lot of electrical energy in the fields of late-night power storage and auxiliary power supplies for power outages, and in the field of rechargeable transportation equipment such as electric vehicles and hybrid vehicles. In the field of portable electronic terminals such as mobile personal computers, mobile phones, and portable audio devices, there is a demand for electrical energy storage devices that store large amounts of electrical energy per unit volume so that they can operate for a long time even in small volumes. .
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 expected as a device to store. 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 electric 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 an electric double layer capacitor, activated carbon is widely used. Specifically, activated carbon having micropores (pore diameter of 20 mm or less) mainly obtained by carbonizing and activating a raw material such as coconut shell is used. Used. In order to improve the capacitance, an electric double layer capacitor using a new activated carbon as an electrode has been demanded.
In recent years, mesopore-based activated carbon obtained by polymerizing resorcinol and formaldehyde in the presence of a basic catalyst to obtain an organic aerogel having uniform mesopores (pore diameter of 20 mm or more), followed by carbonization and activation has been obtained. Although it is proposed in Patent Document 1 that it can be used as an electrode of an electric double layer capacitor having a large capacitance per unit volume, the inventors have investigated using such activated carbon, and the capacitance is sufficiently high. I couldn't say anything.
Moreover, although it is reported in the nonpatent literature 1 that the cyclic | annular tetramer which is 1 type of the polymer of a resorcinol and an aldehyde compound can be carbonized, it does not disclose about the electrostatic capacitance of this carbide.

U.S. Pat. No. 4,873,218 Kazuhisa Murata, Takashi Masuda, Hisashi Ueda, Chemistry Express, Vol.5, No.8, pp.606-608 (1990).

When the present inventors examined, it became clear that the electric double layer capacitor which consists of an electrode containing the carbide | carbonized_material obtained from the cyclic tetramer of a resorcinol and an aldehyde compound does not show sufficient electrostatic capacitance.
An object of the present invention is to provide an electrode suitable for an electric double layer capacitor having an improved capacitance among electrodes having a carbide obtained from a polymer of resorcinols and an aldehyde compound.

（式中、Ｒは炭素数１〜１２の炭化水素基を表し、該炭化水素基は、水酸基、アルキル基、アルコキシル基、アリール基、アリールオキシ基、スルホニル基、ハロゲン原子、ニトロ基、チオアルキル基、シアノ基、カルボキシル基、アミノ基又はアミド基を有していてもよい。Ｒ’は水素原子又はメチル基を表す。ｎは４、６又は８を表す。） The present inventors have found that an electrode including activated carbon obtained by firing and activating a cyclic polymer of resorcinols and an aldehyde compound gives remarkably excellent capacitance to an electric double layer capacitor, and has completed the present invention. I let you.
That is, this invention is an electrode characterized by containing activated carbon which carbonizes and activates the compound represented by Formula (1).

(In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and the hydrocarbon group is a hydroxyl group, an alkyl group, an alkoxyl group, an aryl group, an aryloxy group, a sulfonyl group, a halogen atom, a nitro group, or a thioalkyl group. , A cyano group, a carboxyl group, an amino group or an amide group, R ′ represents a hydrogen atom or a methyl group, and n represents 4, 6 or 8.)

  In the electric double layer capacitor including the electrode of the present invention, both the capacitance per unit volume and the capacitance per unit weight are remarkably improved. Further, the capacitor has a low resistance value at the time of discharge, heat generation is suppressed, and the capacitance hardly decreases even when rapid charge / discharge is repeated. Furthermore, even if the battery is sufficiently charged and stored at a high temperature of about 70 ° C., the capacitance hardly decreases during discharge.

Hereinafter, the present invention will be described in detail.
The activated carbon used in the present invention is activated carbon obtained by carbonizing and activating the compound represented by the formula (1).
In the formula (1), R represents a hydrocarbon group having 1 to 12 carbon atoms, and the hydrocarbon group includes a hydroxyl group, an alkyl group, an alkoxyl group, an aryl group, an aryloxy group, a sulfonyl group, a halogen atom, a nitro group, It may have a thioalkyl group, a cyano group, a carboxyl group, an amino group or an amide group.
Examples of R include alkyl groups such as methyl group, ethyl group, and butyl group, cycloalkyl groups such as cyclohexyl group, and aromatic groups such as phenyl group and naphthyl group. Examples of the hydrocarbon group having the substituent include an aromatic group to which an alkyl group such as a 2-tolyl group, a 3-tolyl group, and a 4-tolyl group is bonded, such as a 2-hydroxybenzyl group, 3- An aromatic group to which a hydroxyl group such as a hydroxybenzyl group or a 4-hydroxybenzyl group is bonded may be mentioned. Among these, from the viewpoint of yield during carbonization, an aromatic group to which the substituent may be bonded is preferable, and an aromatic group to which a hydroxyl group or an alkyl group may be bonded is particularly preferable.

R ′ in the formula (1) represents a hydrogen atom or a methyl group. Among them, a hydrogen atom is preferable because production is easy.
N in the formula (1) is 4, 6, or 8, but n is preferably 4 from the viewpoint of ease of production.
The hydroxyl group bonded to the benzene ring of formula (1) together with R ′ is usually bonded to the ortho and para positions of —CH (R) —.
Although compound (1) has a stereoisomer, it may be a stereoisomer of any one or a mixture of stereoisomers. If the compound (1) is produced using an acid catalyst as described later, a mixture of stereoisomers is usually obtained.

If the specific example of a compound (1) is shown, the compound of a following formula will be mentioned. Here, R is exemplified by the groups shown on the right.

As a production method of the compound (1), for example, as described in P. Timmerman et al., Tetrahedron, 52, (1996) p2663-2704, resorcinol which may have a methyl group in the presence of an aqueous solvent (hereinafter referred to as “resorcinol”) And resorcinols) and an aldehyde may be subjected to dehydration condensation polymerization using an acid catalyst.
Examples of resorcinols used in the production of compound (1) include resorcinol, 2-methylresorcinol, 5-methylresorcinol and the like, and resorcinol is preferable from the viewpoint of availability.

Examples of the aldehyde used for the production of the compound (1) include fats such as acetaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde, n-dodecylaldehyde, 3-phenylpropionaldehyde, and 5-hydroxypentanal. Group aldehydes such as benzaldehyde, 1-naphthaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 4-t-butylbenzaldehyde, 4 -Phenylbenzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-chlorobenzaldehyde, 3- Lorobenzaldehyde, 4-chlorobenzaldehyde, 2-bromobenzaldehyde, 3-bromobenzaldehyde, 4-bromobenzaldehyde, 2-fluorobenzaldehyde, 3-fluorobenzaldehyde, 4-fluorobenzaldehyde, 2-methylthiobenzaldehyde, 3-methylthiobenzaldehyde, 4- Examples include aromatic aldehydes such as methylthiobenzaldehyde, 2-carboxybenzaldehyde, 3-carboxybenzaldehyde, 4-carboxybenzaldehyde, 3-nitrobenzaldehyde, 4-aminobenzaldehyde, 4-acetylaminobenzaldehyde, 4-cyanobenzaldehyde, and the like.
The amount of aldehyde used is usually about 1 to 3 moles, preferably about 1.2 to 2.5 moles per mole of resorcinols.

  As an acid catalyst used for manufacture of a compound (1), hydrochloric acid, a sulfuric acid, phosphoric acid, nitric acid, an acetic acid etc. are mentioned, for example, Among these, hydrochloric acid and a sulfuric acid are preferable. The usage-amount of an acid catalyst is about 0.001-3 mol normally with respect to 1 mol of resorcinols.

The aqueous solvent used for the production of the compound (1) is a mixed solvent of water and an organic solvent that can be mixed at an arbitrary ratio or water, and specifically, alcohols such as methanol, ethanol, i-propyl alcohol and the like. And ether solvents such as tetrahydrofuran and tetrahydrofuran. When using these solvents, they can be used alone or in admixture of two or more.
As the aqueous solvent, an alcohol solvent having 3 or less carbon atoms or a mixed solvent of water and an alcohol having 3 or less carbon atoms is preferable, and an alcohol solvent having 3 or less carbon atoms is particularly preferable.
The ratio of the amount used of the aqueous solvent and resorcinol is usually 0.5 to 5 parts by weight, preferably 1 to 2 parts by weight per part by weight of the aqueous solvent.

As a manufacturing method of a compound (1), resorcinols, an aldehyde, an acid catalyst, and an aqueous solvent are mixed in a lump, and it stirs normally at 0-100 degreeC, Preferably it is 30-90 degreeC, and a compound (1) The aldehyde is usually mixed in a mixture comprising resorcinols, acid catalyst and aqueous solvent at 0 to 100 ° C., preferably 30 to 90 ° C. to precipitate the compound (1) and filter. Another method; a method in which resorcinols are usually mixed in a mixture comprising an aldehyde, an acid catalyst and an aqueous solvent at 0 to 100 ° C., preferably 30 to 90 ° C., and the compound (1) is precipitated and filtered; An acid catalyst is usually mixed in a mixture composed of resorcinols, aldehyde and an aqueous solvent at 0 to 100 ° C., preferably 30 to 90 ° C., and the compound (1) is precipitated and separated by filtration. The method and the like.
In these production methods, a poor solvent such as water may be added before the compound (1) is filtered off.

  The filtered compound (1) is usually dried at room temperature to about 100 ° C. by a method such as ventilation drying or drying under reduced pressure. Further, the compound (1) separated by filtration may be dried after being substituted with a hydrophilic organic solvent. Here, 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 Aliphatic sulfoxides such as; aliphatic carboxylic acids such as acetic acid.

The activated carbon used in the present invention can be obtained by carbonizing and activating the compound (1) obtained by drying. As a specific method for producing the activated carbon of the present invention, for example, (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 600 to 1100. After firing (carbonization) for about 1 minute to 24 hours in the range of ° C., usually in the presence of an oxidizing gas such as H ₂ O, CO ₂ , O ₂ , usually in the range of 200 to 1500 ° C., preferably Is a method of firing (activation) in the range of 600 to 1100 ° C. for about 1 minute to 10 hours; (II) in the presence of oxidizing gas, usually in the range of 200 to 1500 ° C., preferably in the range of 600 to 1100 ° C. In general, a method of firing (carbonization and activation) for about 1 minute to 24 hours; (III) Compound (1) in the presence of an oxidizing gas such as air, at 400 ° C. or less, preferably at 200 to 300 ° C. 1 to 24 hours (Carbonization) and then firing (carbonization) usually in the range of 200 to 1500 ° C., preferably in the range of 600 to 1100 ° C., usually for about 1 minute to 24 hours in an inert gas atmosphere. In the presence of an oxidizing gas, 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; (IV) Compound (1) Is usually calcined (carbonized) at 400 ° C. or lower, preferably 200 to 300 ° C. for about 1 minute to 24 hours, and then in the presence of H ₂ O or CO ₂ . In general, 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; (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 In the range of 1100 ° C., there is usually a method of firing (activation) for about 1 minute to 10 hours.
According to said method, since a metal does not mix, it is preferable. As the oxidizing gas, H ₂ O and CO ₂ are preferable.
A firing temperature of 200 ° C. or higher is preferred because the pore volume tends to improve, and a firing temperature of 1500 ° C. or lower is preferred 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 total pore volume of the activated carbon used in the present invention is usually less than 0.95 ml / g, preferably 0.5 ml / g or more and 0.93 ml / g or less. If the total pore volume is less than 0.95 ml / g, it is preferable because the electrostatic capacity per unit volume is improved.
In order to provide such a total pore volume, the firing time and the firing temperature may be set as appropriate.
Here, the total pore volume is calculated from the amount of nitrogen adsorbed in the vicinity of a relative pressure of 0.95 on the nitrogen adsorption isotherm at the liquid nitrogen temperature using AUTOSORB manufactured by Yuasa Ionics.

The activated carbon used in the present invention is usually pulverized to an average particle size 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.
Here, the average particle size means a volume average particle size measured using a laser diffraction particle size distribution analyzer SALD2000J (registered trademark, manufactured by Shimadzu Corporation) after dispersing activated carbon in a neutral detergent-containing aqueous solution.
Examples of the pulverization method include an impact friction pulverizer, a centrifugal pulverizer, a ball mill (tube mill, compound mill, conical ball mill, rod mill), vibration mill, colloid mill, friction disk mill, jet mill, etc. A pulverizer 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 non-metal such as alumina and agate in order to avoid mixing metal powder.

  As described above, activated carbon having a total pore area of less than 0.95 ml / g and an alkali metal content and an alkaline earth metal content of 100 ppm or less is not polarized by the metal content and gives many electric double layers. Therefore, it is suitably used as an electrode.

The electrode of the present invention is an electrode containing the activated carbon, and the electrode further usually 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 surface of the current collector 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 preferred in that the conductivity is effectively improved with 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, and examples of the fluorine compound include a fluorinated alkyl (having 1 to 18 carbon atoms) (meth) acrylate, 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 About 1 to 17 atoms), for example, perfluorohexylethylene, about 2 to 10 carbon atoms, and fluorinated olefins, tetrafluoroethylenes, tricarbons having fluorine atoms bonded to double bond carbons having about 1 to 20 fluorine atoms. 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 (C1-C1). 22) (Meth) acrylate [for example, 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 [for example, benzyl (meth) acrylate, phenylethyl (meth) acrylate, etc.]; alkylene glycol or di Alkylene glycol (alkyle Mono (meth) acrylate having 2 to 4 carbon atoms [for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate]; (poly) glycerin (degree of polymerization) 1-4) mono (meth) acrylate; polyfunctional (meth) acrylate [for example, (poly) ethylene glycol (degree of polymerization 1 to 100) di (meth) acrylate, (poly) propylene glycol (degree of polymerization 1 to 100) di (Meth) acrylate monomers such as (meth) acrylate, 2,2-bis (4-hydroxyethylphenyl) propane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc.]; (meth) acrylamide , (Meth) acrylamide derivatives [eg N-mes (Meth) acrylamide monomers such as roll (meth) acrylamide, diacetone acrylamide, etc .; cyano group-containing monomers such as (meth) acrylonitrile, 2-cyanoethyl (meth) acrylate, 2-cyanoethylacrylamide; styrene and Styrenic monomers such as styrene derivatives having 7 to 18 carbon atoms [for example, α-methylstyrene, vinyltoluene, p-hydroxystyrene, divinylbenzene and the like]; alkadienes having 4 to 12 carbon atoms [for example, butadiene, isoprene, Diene monomers such as chloroprene]; carboxylic acid (carbon number 2 to 12) vinyl ester [for example, vinyl acetate, vinyl propionate, vinyl butyrate and vinyl octoate], carboxylic acid (2 to 12 carbon atoms) (Meth) allyl ester [for example, acetic acid ( ) Alkenyl ester monomers such as allyl, propionic acid (meth) allyl and octanoic acid (meth) allyl]; epoxy group-containing monomers such as glycidyl (meth) acrylate and (meth) allyl glycidyl ether; carbon Monoolefins of 2 to 12 monoolefins [for example, ethylene, propylene, 1-butene, 1-octene and 1-dodecene and the like]; chlorine, bromine or iodine atom-containing monomers, vinyl chloride, vinylidene chloride, etc. Halogen atom-containing monomers other than fluorine; (meth) acrylic acid such as acrylic acid and methacrylic acid; conjugated double bond-containing monomers such as butadiene and isoprene.
Further, as the addition polymer, for example, a copolymer composed of plural kinds of monomers such as an ethylene / vinyl acetate copolymer, a styrene / butadiene copolymer, and an ethylene / propylene copolymer may be used. 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, among them, 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 electrode of the present invention is used for, for example, an electrode of a dry battery, a redox capacitor, a hybrid capacitor, an electric double layer capacitor, etc. Among them, it is suitable for an electrode of an electric double layer capacitor because of its excellent electrostatic capacity.
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 that contains a substance and stores 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 the cyclic carbonate include ethylene carbonate and propylene carbonate. Examples of the chain carbonate include dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate. Examples of the cyclic ester include γ-butyrolactone and γ-valerolactone. 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 a device that stores electricity when lithium ions are inserted between carbon layers such as graphite at the negative electrode during charging, and an anion of an electrolyte is attracted to the electrode surface at the positive electrode to form an electric double layer. . 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 electrolyte for hybrid capacitor, usually, inorganic combination of anion and lithium cation are used, inter ^{_{alia, BF 4 -, PF 6 -}} , ClO 4 - and at least one inorganic anion and a lithium cation selected from the group consisting of 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, which are the electrodes, 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 a resin in which an electrolyte described later is dispersed 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 related literature, 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. Therefore, 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 current collector (52), a sheet-shaped electrode (53), a separator (54), an electrode (53), and a collector between pressure plates (51). The electric double layer capacitor was formed by laminating the electric body (52), filling the electrolyte between the separator (54) and the electrode (53), sealing the outer layer with a fluororesin, and pressing with a bolt. Both bolts are insulated from the two current collectors.
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 electrolyte solution, and has a large ion permeability, a predetermined mechanical strength, and an insulating film is used. .
Examples of the separator include, for example, paper making such as viscose rayon or natural cellulose, mixed paper obtained by making fibers such as cellulose and polyester, electrolytic paper, kraft paper, manila paper, polyethylene non-woven fabric, polypropylene non-woven fabric, polyester non-woven 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. Furthermore, 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.

Electrolytes used for electric double layer capacitors are roughly classified into inorganic electrolytes and organic electrolytes. Examples of inorganic electrolytes include acids such as sulfuric acid, hydrochloric acid, perchloric acid, sodium hydroxide, potassium hydroxide, Examples include bases such as lithium hydroxide and tetraalkylammonium hydroxide, and salts such as sodium chloride and sodium sulfate. Among inorganic electrolytes, an aqueous sulfuric acid solution is preferable because of its excellent stability and low corrosiveness to the materials constituting the electric double layer capacitor.
The concentration of the inorganic electrolyte is usually about 0.2 to 5 mol (electrolyte) / L (electrolytic solution), and preferably about 1 to 2 mol (electrolyte) / L (electrolytic solution). When the concentration is 0.2 to 5 mol / L, ion conductivity in the electrolytic solution can be ensured.
The inorganic electrolyte is usually mixed with water and used as an electrolytic solution.

Examples of the organic 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; Combinations with organic cations, and combinations with organic anions and inorganic cations such as lithium ions, sodium ions, potassium ions, hydrogen ions, and the like can be mentioned.

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, and an organic quaternary phosphonium cation is a quaternary phosphonium cation in which the same hydrocarbon group as described above is substituted with a phosphorus atom. is there.
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.

(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、Ｘ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, X 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 Imidazolinium, 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-formyl Methyl-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- Such as diethylpyrrolidinium.
(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, etc.

(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 Cations with atoms substituted with fluorine atoms.

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.

(Imidazolium cation)
1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-n-propyl-3-methylimidazolium, 1-n-butyl-3-methylimidazolium, 1,3-diethylimidazolium, 1,2,3-trimethylimidazolium, 1,2,3,4-tetramethylimidazolium, 1,3,4-trimethylimidazolium, 1,3,4-trimethyl-2-ethylimidazolium, 1,3 -Dimethyl-2,4-diethylimidazolium, 1,2-dimethyl-3,4-diethylimidazolium, 1-methyl-2,3,4-triethylimidazolium, 1,2,3,4-tetraethylimidazolium 1,3-dimethyl-2-ethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1-n-propyl-2,3- Methylimidazolium, 1-n-butyl-2,3-dimethylimidazolium, 1,2,3-triethylimidazolium, 1,1-dimethyl-2-heptylimidazolium, 1,1-dimethyl-2- (2 '-Heptyl) imidazolium, 1,1-dimethyl-2- (3'-heptyl) imidazolium, 1,1-dimethyl-2- (4'-heptyl) imidazolium, 1,1-dimethyl-2-dodecyl Imidazolium, 1,1-dimethylimidazolium, 1,1,2-trimethylimidazolium, 1,1,2,4-tetramethylimidazolium, 1,1,2,5-tetramethylimidazolium, 1,1 2,4,5-pentamethylimidazolium, 1-ethyl-3,4-dimethylimidazolium, 1-ethyl-3,5-dimethylimidazolium, 2-ethyl 1,3-dimethylimidazolium, 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, 1,2,3-triethylimidazolium, 1,3,4-triethylimidazolium 1-ethyl-2,3,4-trimethylimidazolium, 1-ethyl-2,3,5-trimethylimidazolium, 1-ethyl-3,4,5-trimethylimidazolium, 2-ethyl-1, 3,4-trimethylimidazolium, 4-ethyl-1,2,3-trimethylimidazolium, 1,2-diethyl-3,4-dimethylimidazole Zolium, 1,3-diethyl-2,4-dimethylimidazolium, 1,4-diethyl-2,3-dimethylimidazolium, 1,4-diethyl-2,5-dimethylimidazolium, 2,4-diethyl- 1,3-dimethylimidazolium, 4,5-diethyl-1,3-dimethylimidazolium, 3,4-diethyl-1,2-dimethylimidazolium, 2,3,4-triethyl-1-methyl-imidazolium 1,2,3-triethyl-4-methylimidazolium, 1,2,4-triethyl-3-methylimidazolium, 1,2,5-triethyl-3-methylimidazolium, 1,3,4-triethyl 2-methylimidazolium, 1,3,4-triethyl-5-methylimidazolium, 1,4,5-triethyl-3-methylimidazolium, , 3,4-tetraethylimidazolium, 1,2,3,4,5-pentamethylimidazolium, 1-phenyl-3-methylimidazolium, 1-phenyl-3-ethylimidazolium, 1-benzyl-3- Methylimidazolium, 1-benzyl-3-ethylimidazolium, 1-phenyl-2,3-dimethylimidazolium, 1-phenyl-2,3-diethylimidazolium, 1-phenyl-2-methyl-3-ethyl Imidazolium, 1-phenyl-2-ethyl-3-methylimidazolium, 1-benzyl-2,3-dimethylimidazolium, 1-benzyl-2,3-diethylimidazolium, 1-benzyl-2-methyl-3 -Ethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 1,3-diethyl-2-phenyl Dazolium, 1-methyl-2-phenyl-3-ethylmethylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 1,3-diethyl-2-benzylimidazolium, 1,3-dimethyl-2-ethoxy Methylimidazolium, 1,3-diethyl-2-ethoxymethylimidazolium, 1-methyl-2-ethoxymethyl-3-ethylimidazolium, 1-ethoxymethyl-2,3-dimethylimidazolium, 1-ethoxymethyl- 2,3-diethylimidazolium, 1-ethoxymethyl-2-methyl-3-ethylimidazolium, 1,3-dimethyl-2-methoxymethylimidazolium, 1,3-diethyl-2-methoxymethylimidazolium, 1 -Methyl-2-methoxymethyl-3-ethylimidazolium, 1-methoxymethyl-2 , 3-dimethylimidazolium, 1-methoxymethyl-2,3-diethylimidazolium, 1-methoxymethyl-2-methyl-3-ethylimidazolium, 1,3-dimethyl-2-methoxyethylimidazolium, 1, 3-diethyl-2-methoxyethylimidazolium, 1-methyl-2-methoxyethyl-3-ethylimidazolium, 1-methoxyethyl-2,3-dimethylimidazolium, 1-methoxymethyl-2,3-diethylimidazolium 1-methoxyethyl-2-methyl-3-ethylimidazolium, 1,3-dimethylbenzimidazolium, 1,3-diethylbenzimidazolium, 1-methyl-3-ethylbenzimidazolium, 1,2,3 -Trimethylbenzimidazolium, 1,2-dimethyl-3-ethylbenzimi Zorium, 2-cyanomethyl-1,3-dimethyl-imidazolium, 4-acetyl-1,2,3-trimethylimidazolium, 3-acetylmethyl-1,2-dimethylimidazolium, 4-methylcarbooxymethyl-1 , 2,3-trimethylimidazolium, 3-methylcarbooxymethyl-1,2-dimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 3-methoxymethyl-1,2-dimethylimidazolium 4-formyl-1,2,3-trimethylimidazolium, 3-formylmethyl-1,2-dimethylimidazolium, 3-hydroxyethyl-1,2-dimethylimidazolium, 4-hydroxymethyl-1,2, 3-trimethylimidazolium, 2-hydroxyethyl-1,3-dimethylimidazole Um, and the 2-position of the hydrogen atoms of the imidazolium cation such as cations substituted with fluorine atoms.

(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. )

(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.

(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.

で表される１−エチル−３−メチルイミダゾリウム（ＥＭＩ^＋）であると、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。 As the organic cation, an organic quaternary ammonium cation is preferable, and among them, an imidazolium cation is preferable.

1-ethyl-3-methylimidazolium (EMI ⁺ ) represented by the formula is preferred because the capacitance per unit volume tends to increase.

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, etc.), unsaturated polycarboxylic acid (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, 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, uraryl 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, resorcinol, 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

(Wherein, ^{R 1} and ^{R 2} .R ¹ and ^{R 2} may .R ³ be the same as or different from each other a monovalent organic group containing fluorine in 1 to 4 carbon atoms is 2 to carbon atoms 8 is a divalent organic group containing fluorine.)

As the anion, 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.

  Examples of the solvent used in the electrolytic solution containing the electrolyte include water and / or an organic polar solvent. As the electrolytic solution containing an inorganic electrolyte, a solvent mainly containing water is usually used, and the hydrophilic organic solvent exemplified above may be used together with water. As the electrolytic solution containing an organic electrolyte, a solvent containing an organic polar solvent as a main component is used, and the content of water contained in the electrolytic solution containing an organic polar solvent is usually 200 ppm or less, preferably 50 ppm or less. More preferably, it is 20 ppm or less. By suppressing the water content in the electrolytic solution containing the organic polar solvent, it is possible to suppress the influence on the electrode due to the electrolysis of water, in particular, the decrease in withstand voltage.

Here, the following are illustrated as a specific example of an organic polar solvent.
(ether)
Monoether (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monophenyl ether, tetrahydrofuran, 3-methyltetrahydrofuran, etc.), diether (ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol) Dimethyl ether, diethylene glycol diethyl ether, diethyl ether, methyl isopropyl ether, etc.), triethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, cyclic ether [carbon number 2-4 (tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, , 4-dioxane, 2-methyl-1,3-dioxolane, etc.); 4-butyl-dioxolane, etc. Crown ethers] of 5 to 18 carbon atoms.
(Fluorinated dioxolane)
2,2-di (trifluoromethyl) -1,3-dioxolane, 2,2-di (trifluoromethyl) -4,5-difluoro-1,3-dioxolane, 2,2-di (trifluoromethyl) -4,4,5,5-tetrafluoro-1,3-dioxolane, 2,2-dimethyl-4,4,5,5-tetrafluoro-1,3-dioxolane or 2,2-dimethyl-4,5 -Difluoro-1,3-dioxolane

(Amide)
Formamides (N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, etc.), acetamides (N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N , N-diethylacetamide), propionamides (N, N-dimethylpropionamide, etc.), hexamethylphosphorylamide, etc. Oxazolidinones; N-methyl-2-oxazolidinone, 3,5-dimethyl-2-oxazolidinone, and the like. In addition, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone and the like.
(Nitrile)
A fluorine-containing propionitrile in which one or more hydrogen atoms of acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, acrylonitrile, propionitrile are substituted with fluorine atoms, and the like.

(Carboxylic acid ester)
Maleic anhydride and its derivatives, such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, methyl butyrate, methyl valerate, ethyl propionate, dimethyl malonate, diethyl malonate,
(Lactone)
γ-butyrolactone, 3-methyl-γ-butyrolactone, 2-methyl-γ-butyrolactone, α-acetyl-γ-butyrolactone, β-butyrolactone, γ-valerolactone, 3-methyl-γ-valerolactone, δ-valerolactone Such.

(Carbonate)
Ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, diethyl carbonate, 4-allyloxymethyl-1,3-dioxolan-2-one, 4- (1 '-Propenyloxymethyl) -1,3-dioxolan-2-one, 4-allyloxymethyl-5-vinyl-1,3-dioxolan-2-one, 4- (1'-propenyloxymethyl) -5 Vinyl-1,3-dioxolan-2-one, 4-acryloyloxymethyl-1,3-dioxolan-2-one, 4-methacryloyloxymethyl-1,3-dioxolan-2-one, 4-methacryloyloxymethyl- 5-vinyl-1 3-dioxolan-2-one, 4-methoxycarbonyloxymethyl-1,3-dioxolan-2-one, 4-allyloxycarbonyloxymethyl-1,3-dioxolan-2-one, 4- (1′-propenyloxycarbonyl) Oxymethyl) -1,3-dioxolane-2-one, 4-vinylethylene carbonate, 4,5-divinylethylene carbonate, 4,4,5,5-tetramethyl-1,3-dioxolan-2-one, 4, 4,5,5-tetraethyl-1,3-dioxolan-2-one, vinylene carbonate, 4-methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, 5,5-dimethyl-1,3-dioxane-2-one And 5,5-diethyl-1,3-dioxane-2-one, dipropyl carbonate, methyl butyl carbonate, ethyl butyl carbonate, ethyl propyl carbonate, butyl B pills carbonate, and compounds obtained by substituting a fluorine atom of one or more hydrogen atoms of the above compounds and the like.

(Sulphoxide)
Dimethyl sulfoxide, sulfolane, 3-methyl sulfolane, 2,4-dimethyl sulfolane, and fluorine-containing sulfolane in which one or more hydrogen atoms of sulfolane are substituted with fluorine atoms.
1,3-propane sultone, 1,4-butane sultone, and compounds in which one or more hydrogen atoms are substituted with fluorine atoms (sulfone)
Dimethylsulfone, diethylsulfone, di-n-propylsulfone, diisopropylsulfone, di-n-butylsulfone, di-sec-butylsulfone, di-tert-butylsulfone and the like.

(Nitro compounds)
Nitromethane, nitroethane, etc. (other heterocyclic compounds)
N-methyl-2-oxazolidinone, 3,5-dimethyl-2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidinone and the like.

(Monohydric alcohol)
C1-C6 monohydric alcohol (methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, diacetone alcohol, furfuryl alcohol, etc.), C7 or more monohydric alcohol (benzyl alcohol, octyl alcohol, etc.)
(Polyhydric alcohol)
C1-C6 dihydric alcohol (ethylene glycol, propylene glycol, diethylene glycol, hexylene glycol, etc.), C7 or more dihydric alcohol (octylene glycol, etc.), trivalent alcohol (glycerin, etc.), hexavalent Alcohol (eg hexitol).

(hydrocarbon)
Aromatic solvents (toluene, xylene, ethylfluorobenzene, fluorobenzene in which 1 to 6 hydrogen atoms of benzene are substituted with fluorine atoms), paraffinic solvents (normal paraffin, isoparaffin, etc.), etc.

(Silicon compound)
Oxazolidinone compounds such as 3-trimethylsilyl-2-oxazolidinone, 3-trimethylsilyl-4-trifluoromethyl-2-oxazolidinone, 3-triethylsilyl-2-oxazolidinone having a silicon atom in the molecule, N-trimethylsilylimidazole, N-trimethylsilyl- Imidazole compounds such as 4-methyl-imidazole and N-triethylsilylimidazole, phosphate compounds such as tris (trimethylsilyl) phosphate, tris (triethylsilyl) phosphate, trimethylsilyldimethylphosphate, trimethylsilyldiallyl phosphate, 4-trimethylsilyl-1,3-dioxolane 2-one, 4-trimethylsilyl-5-vinyl-1,3-dioxolan-2-one, 4-trimethylsilylme Cyclic carbonate compounds such as til-1,3-dioxolan-2-one, phenyl compounds such as phenyltrimethylsilane, phenyltriethylsilane, phenyltrimethoxysilane, phenylthiotrimethylsilane, phenylthiotriethylsilane, methyl-N-trimethylsilylcarbamate Carbamate compounds such as methyl-N, N-bistrimethylsilylcarbamate, ethyl-N-trimethylsilylcarbamate, methyl-N-triethylsilylcarbamate, vinyl-N-trimethylsilylcarbamate, methyltrimethylsilylcarbonate, allyltrimethylsilylcarbonate, ethyltrimethylsilylcarbonate, etc. Carbonate compounds, methoxytrimethylsilane, hexamethyldisiloxane, pentamethyldisiloxa , Methoxy trimethylsilane, trimethylchlorosilane, butyldiphenylchlorosilane, trifluoromethyltrimethylsilane, acetyl trimethyl silane, 3-trimethylsilyl cyclopentene, allyltrimethylsilane, vinyltrimethylsilane, such as hexamethyldisilazane.

The organic polar solvent for dissolving the electrolyte may be a mixture of two or more different solvents.
The organic polar solvent contained in the electrolytic solution is a solvent mainly comprising at least one selected from the group consisting of carbonates, lactones and sulfoxides, preferably propylene carbonate, ethylene carbonate, butylene. A solvent mainly composed of at least one selected from the group consisting of carbonate, sulfolane, 3-methylsulfolane, acetonitrile, dimethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, ethylene glycol and diethyl carbonate, particularly preferably It is a solvent mainly comprising at least one selected from the group consisting of ethylene carbonate, propylene carbonate, γ-butyrolactone, and sulfolane. Here, “main component” means that the compound occupies 50% by weight or more, preferably 70% by weight or more of the solvent. The higher the content of the organic polar solvent, the longer the capacitor. Durability and operating voltage can be improved.

Various additives can be added to the electrolytic solution as necessary. Specifically, phosphoric acid esters (trimethyl phosphate, triethyl phosphate, triallyl phosphate, etc.), phosphonic acids, etc. for suppressing gas generation and improving withstand voltage, and the following formulas for high capacity and high output. And fluorine-containing organosilicon compounds.
CF ₃ CH ₂ CH ₂ Si (CH ₃ ) _{3
(CH 3) 3 Si-O} -Si (CH 3) (CF 3 CH 2 CH 2) -Si (CH 3)

  The addition amount of the phosphate ester is usually about 10% by weight or less of the electrolyte from the viewpoint of the electric conductivity of the electrolyte and the solubility in the electrolyte solution, and the addition amount of the fluorine-containing organosilicon compound is as follows. It is about 0.1 to 5% by weight.

  Benzoic acids that are one of organic polar solvents [benzoic acid alkyl esters such as methyl benzoate, ethyl benzoate, propyl benzoate, benzoic acid, etc.] may be used as additives for preventing metal elution from the current collector. . When benzoic acid is used as an additive, it is usually about 0.001 to 10.0% by weight of the electrolyte, preferably 0.005 to 5% by weight, more preferably 0.1 to 1% by weight. .

  The concentration of the organic electrolyte in the electrolytic solution containing the organic electrolyte is usually 0.5 to 5.0 mol (electrolyte) / L (electrolytic solution), preferably 0.7 to 3.0 mol (electrolyte) / L ( Concentration of electrolyte solution). 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 tends to decrease.

The electric double layer capacitor is usually charged by applying a current of about 5 mA / g to 10 A / g, preferably about 10 mA / g to 5 A / g. Application of 5 mA / g or more is preferable because the charging rate tends to be improved, and 10 A / g or less is preferable because the decrease in capacitance tends to be suppressed.
Further, the electric double layer capacitor of the present invention has little decrease in capacitance even when rapid charge / discharge of 1 A / g or more is repeated.

According to the present invention, the electric double layer capacitor of the present invention has an electric capacity excellent in electrostatic capacity, wherein the electrostatic capacity per unit volume of activated carbon is usually 15 F / ml or more, preferably 18 F / ml or more. It is a double layer capacitor. Further, the electrostatic capacity per unit weight of the activated carbon also has excellent electrical characteristics, usually 19 F / g or more, preferably 24 F / g or more.
The activated carbon has a capacitance of 80 parts by weight of activated carbon and 10 parts by weight of polytetrafluoroethylene (solid content), kneaded and then placed in a 13 mm diameter container and pressed at 162 kgf / cm ² to form. Then, the density (g / cc) of the molded product was obtained, and subsequently, the molded product was charged to 2.8 V at a constant current of 300 mA / g with the Toyo System Co., Ltd. TOSCAT-3100 charge / discharge evaluation device. Next, obtain the capacitance per unit weight from the discharge curve when discharging, and calculate the capacitance per unit volume by multiplying the obtained capacitance per unit weight by the obtained density. It can ask for.

Furthermore, the electric double layer capacitor of the present invention has a small decrease in capacitance even when rapidly charged / discharged when the capacitance at the time of charging / discharging at a constant current (300 mA, 0-2.3 V) is 100, If the electrolyte is a propylene carbonate solution of 1 mol-L of 1-ethyl-3-methylimidazolium BF ₄ salt, the decrease in capacitance is usually less than 5% even when rapidly charged and discharged at 4000 mA / g. Preferably, it has excellent electrical characteristics of staying at 3% or less.

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

Example 1
(Synthesis Example of Compound (1))
Production of tetramethylcalix [4] resorcinarenes (compound (1): MCRA) In a four-necked flask, 30.0 g of resorcinol, 120 ml of ethanol and 12.1 g of acetaldehyde were placed in a nitrogen stream and cooled with ice, and 36% with stirring. Hydrochloric acid 53.7 g was added dropwise. After completion of dropping, the temperature was raised to 65 ° C., and then kept at that temperature for 5 hours. 320 g of water was added to the resulting reaction mixture, and the resulting precipitate was collected by filtration, washed with water until the filtrate became neutral, dried, recrystallized from a mixed solvent of water-ethanol, and tetramethylcalix [4 ] 13.1 g of resorcinarene (MCRA) was obtained.

Mass spectrometry value of MCRA (FD-MS) m / z 544
¹ HNMR (DMSO-d ⁶ ) of MCRA: δ 1.29 (s, 12H), 4.45 (q, 4H), 6.14 (s, 4H), 6.77 (s, 4H), 8.53 (S, 8H)

(Production example of activated carbon)
MCRA was fired (carbonized) at 1000 ° C. for 4 hours in an argon atmosphere, and then fired (activated) at 1000 ° C. for 2 hours in a carbon dioxide atmosphere. Subsequently, it grind | pulverized with the ball mill (Agate ball, 28 rpm, 5 minutes). Since this activated carbon is not in contact with metal, it contains almost no metal content including metal ions.
It was calculated that the total pore volume of the obtained activated carbon was 0.68 ml / g, the micropore volume was 0.43 ml / g, and the mesopore volume was 0.25 ml / g.
Here, the total pore volume is calculated from the amount of nitrogen adsorbed in the vicinity of 0.95 relative pressure on the nitrogen adsorption isotherm at liquid nitrogen temperature using AUTOSORB manufactured by Yuasa Ionics, and the micropore volume is 0 relative pressure. Calculated from around 30.

(Production example of electrode and electric double layer capacitor)
Mixture of 80 parts by weight of the activated carbon, 10 parts by weight of acetylene black (Electrochemical Co., Ltd. Denka Black 50% press product), and 10 parts by weight (solid content) of polytetrafluoroethylene (60% solid content aqueous dispersion) Was kneaded and then formed into a 0.28 mm sheet and dried to obtain an electrode. Bipolar electricity filled with a 1 mol / L tetraethylammonium BF ₄ salt (organic electrolyte) propylene carbonate solution after putting cellulose for capacitor (thickness 50 μm) as a separator between the two obtained electrodes A double layer capacitor (FIG. 5) was created.
The constant current charge / discharge measurement using the capacitor (300 mA / g, 0 to 2.8 V) revealed that the activated carbon had a capacitance per unit volume of 16.3 F / ml and the activated carbon had a capacitance per unit weight of 24. It was 7F / g.
In addition, the electrostatic capacity of the activated carbon is obtained by kneading a mixture of 80 parts by weight of the activated carbon and 10 parts by weight (solid content) of polytetrafluoroethylene (containing about 60% by weight aqueous dispersion), and then in a container having a diameter of 13 mm. Then, pressurizing and molding at 162 kgf / cm ² , the density (g / cc) of the molded product was obtained, and subsequently, 300 mA / The electrostatic capacity per unit weight is obtained from the discharge curve when charging to 2.8 V at a constant current of g and then discharging, and the electrostatic capacity per unit volume is obtained as the electrostatic capacity per unit weight. Calculated by multiplying by the density. The same applies hereinafter.

(Examples 2-9)
It implemented according to Example 1 except setting the kind of compound (1), the calcination time of activation, and the electric quantity of constant current charging / discharging measurement in Table 1. The results are shown in Table 1 together with Example 1.

＊１：化合物（１）の製造において、実施例１のエタノール１２０ｍｌの代わりにメタノール６０ｍｌ、水６０ｍｌの混合溶媒を用い再結晶を実施しなかった。化合物（１）として立体異性体の混合物を用いた。
＊２：レーザー回折式粒度分布測定装置ＳＡＬＤ２０００Ｊ（登録商標、島津製作所製）を用いて測定された体積平均粒径は約５μｍであった。当該活性炭の累積粒子径分布は表２に示した。また、フレーム原子吸光光度計ＡＡ−２２０ＦＳ（登録商標：バリアン）を用いて測定されたアルカリ金属は、検出されなかった。
＊３：化合物（１）を空気中で３００℃にて１時間、炭化したのち、アルゴン雰囲気下に１０００℃で４時間焼成（炭化）して、次いで二酸化炭素存在下に１０００℃で２時間焼成（賦活）を行い活性炭を得た。
＊４：活性炭の製造において、二酸化炭素存在下において、４時間焼成（炭化及び賦活）を行なった。

* 1: In the production of compound (1), recrystallization was not carried out using a mixed solvent of 60 ml of methanol and 60 ml of water instead of 120 ml of ethanol in Example 1. A mixture of stereoisomers was used as compound (1).
* 2: The volume average particle diameter measured using a laser diffraction particle size distribution analyzer SALD2000J (registered trademark, manufactured by Shimadzu Corporation) was about 5 μm. The cumulative particle size distribution of the activated carbon is shown in Table 2. Moreover, the alkali metal measured using flame | frame atomic absorption photometer AA-220FS (trademark: Varian) was not detected.
* 3: Compound (1) was carbonized in air at 300 ° C. for 1 hour, then calcined (carbonized) at 1000 ° C. for 4 hours in an argon atmosphere, and then calcined at 1000 ° C. for 2 hours in the presence of carbon dioxide. (Activation) was performed to obtain activated carbon.
* 4: In the production of activated carbon, firing (carbonization and activation) was performed for 4 hours in the presence of carbon dioxide.

(Examples 10 to 11: Production examples of electric double layer capacitors containing an inorganic electrolyte)
Complying with Example 1 except that the type of compound (1) is replaced with the compounds listed in Table 2 and the electrolyte is 1 mol / L sulfuric acid water instead of 1 mol / L tetraethylammonium BF ₄ salt propylene carbonate solution. And carried out. The results are shown in Table 3.

(Example 12: Decrease in electrostatic capacity due to rapid charge / discharge)
Between two electrodes obtained in Example 3 and putting cellulose for a capacitor as a separator, 3 mol / L of 1-ethyl-3-methylimidazolium BF ₄ salt (organic electrolyte) in propylene carbonate solution A bipolar electric double layer capacitor (B) filled with was prepared.
The capacitor was charged with a constant current of 3000 mA / g for 1 minute and discharged for 1 minute. The amount of electricity stored in the capacitor at the first time was 32 F / g. This operation was further repeated 4 times, and the stored electricity amount of the capacitor at the 5th time in total was 32 F / g, and no decrease in the stored electricity amount was observed even when the rapid charge / discharge was repeated 5 times.

Further, the electric double layer capacitor (B) was measured for capacitance per unit volume by constant current charge / discharge measurement (1000 to 8000 mA / g), and the capacitance of constant current charge / discharge measured value 300 mA / g was set to 100. Table 4 shows the ratio of the electrostatic capacity in the case of%. The same ratio was examined for the same electric double layer capacitor (A) except that 1 mol / L of a propylene carbonate solution of tetraethylammonium BF ₄ salt (organic electrolyte) was filled as an electrolyte. It can be seen that a capacitance equivalent to constant current charge / discharge can be obtained even with rapid charge / discharge.

  Further, in the electric double layer capacitor (B), an application characteristic test ((B) was allowed to stand at a temperature of 70 ° C. for 300 hours, and then a constant current charge / discharge measurement (300 mA / g, 0 to 2.3 V)) was performed. As a result, the retention rate of the unit weight and the capacitance per unit volume from the constant current charge / discharge measurement value of 300 mA / g was 86%.

電極は実施例３と同じ活性炭で得られた電極を用いた。
（Ａ）の電解液：１ｍｏｌ／ＬのテトラエチルアンモニウムＢＦ_４塩（有機系電解質）の
プロピレンカーボネート溶液
（Ｂ）の電解液：３ｍｏｌ／Ｌの１−エチル−３−メチルイミダゾリウムＢＦ_４塩（有機
系電解質）のプロピレンカーボネート溶液

As the electrode, an electrode obtained from the same activated carbon as in Example 3 was used.
(A) Electrolytic solution: 1 mol / L of tetraethylammonium BF ₄ salt (organic electrolyte)
Electrolyte of propylene carbonate solution (B): 3 mol / L 1-ethyl-3-methylimidazolium BF ₄ salt (organic
-Based electrolyte) in propylene carbonate solution

(Comparative Examples 1-4)
Comparative Examples 1 to 3 were carried out according to Example 1 except that the types of the compounds (1) listed in Table 5 were used and the compounds (1) were not activated. The results are shown in Table 5.
In Comparative Example 4, activated carbon obtained by preparing a resorcinol-formaldehyde resin according to Patent Document 1 and carbonizing and activating it was used. The results are also shown in Table 5.

(Synthesis example of resorcinol-formaldehyde resin and activated carbon of the resin)
In a reaction vessel, 33.0 g of resorcinol, 48.7 g of 37% by weight formalin, 0.03 g of sodium carbonate, and 66 g of distilled water were mixed, and kept at 50 ° C. for 24 hours to obtain an organic aerogel wetted with water.
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, calcined at 1000 ° C. under an argon atmosphere, and then activated at 1000 ° C. for 4 hours under a carbon dioxide atmosphere. Got. The obtained activated carbon had a pore volume of 2.39 ml / g.

The electrode of the present invention is used for, for example, an electrode of a dry battery, a redox capacitor, a hybrid capacitor, an electric double layer capacitor, etc. Among them, it is suitable for an electrode of an electric double layer capacitor because of its excellent electrostatic capacity.
The electric double layer capacitor of the present invention can be used for storing an energy source. In particular, because of its excellent characteristics, it can be used for storing 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 (11)

An electrode containing activated carbon obtained by carbonizing and activating the compound represented by formula (1).

(In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, and the hydrocarbon group is a hydroxyl group, an alkyl group, an alkoxyl group, an aryl group, an aryloxy group, a sulfonyl group, a halogen atom, a nitro group, or a thioalkyl group. , A cyano group, a carboxyl group, an amino group or an amide group, R ′ represents a hydrogen atom or a methyl group, and n represents 4, 6 or 8.)   The electrode according to claim 1, wherein R ′ of the compound is a hydrogen atom.   The electrode according to claim 1 or 2, wherein the total pore volume of the activated carbon is less than 0.95 ml / g.   The electrode according to any one of claims 1 to 3, wherein the content of alkali metal and alkaline earth metal in the activated carbon is 100 ppm or less.   The electrical double layer capacitor containing the electrode in any one of Claims 1-4.   Furthermore, the electric double layer capacitor of Claim 5 containing a separator and electrolyte solution.   The separator is at least one separator selected from the group consisting of papermaking, electrolytic paper, kraft paper, manila paper, mixed paper, polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, manila hemp sheet and glass fiber sheet. The electric double layer capacitor described in 1.   The electric double layer capacitor according to claim 5, wherein the electrolytic solution is an aqueous sulfuric acid solution.   The electric double layer capacitor according to claim 5, wherein the electrolytic solution is a solution containing an organic quaternary cation, an inorganic anion, and an organic polar solvent. An electrode containing activated carbon having an alkali metal content and an alkaline earth metal content of 100 ppm or less and a total pore volume of less than 0.95 ml / g, an organic quaternary cation, an inorganic anion, and an organic polar solvent. An electric double layer capacitor comprising an electrolytic solution containing an electrostatic capacity per unit volume of activated carbon (capacitance per unit volume is a mixture of 80 parts by weight of activated carbon and 10 parts by weight of polytetrafluoroethylene (solid content) After kneading, put into a 13mm diameter container and pressurize and mold at 162kgf / cm ² to obtain the density (g / cc) of the molded product, then Toyo System Co., Ltd. TOSCAT-3100 In the evaluation device, the molded product is charged to 2.8 V at a constant current of 300 mA / g and then discharged to a capacitance per unit weight obtained from a discharge curve. Electric double layer capacitor is a value calculated by multiplying the density obtained above.) Is 15F / ml or more.   The electric double layer capacitor according to claim 10, wherein the capacitance per unit weight of the activated carbon is 19 F / g or more.

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