CN101180691A - Electric double layer capacitor - Google Patents
Electric double layer capacitor Download PDFInfo
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- CN101180691A CN101180691A CN 200680011609 CN200680011609A CN101180691A CN 101180691 A CN101180691 A CN 101180691A CN 200680011609 CN200680011609 CN 200680011609 CN 200680011609 A CN200680011609 A CN 200680011609A CN 101180691 A CN101180691 A CN 101180691A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relats to an electric double-layer capacitor comprising an electrode containing an activated carbon, an electrolytic solution containing an electrolyte and a separator, wherein the electrolyte is an imidazolium salt, and the activated carbon is produced by carbonizing an organic aerogel obtained by polymerizing a phenolic compound having at least one hydroxyl group in its molecule with an aldehyde compound in an aqueous solvent in the presence of a basic catalyst.
Description
Technical field
The present invention relates to double electric layer capacitor.
Background technology
At present, store at dark liquid electric power, the power failure countermeasure with fields such as accessory power supplys in, requirement can store the apparatus for storing electrical energy of a large amount of electric energy, in terminal field such as the portable electronic of the rechargeable field of transport vehicles of electric automobile, hybrid vehicle etc., notebook computer, mobile phone, portable audiofrequency apparatus etc., for small size and work long hours, the big apparatus for storing electrical energy of electric energy that requires per unit volume to store.
The expectation double electric layer capacitor is as apparatus for storing electrical energy, and it is made of electrode, dividing plate and electrolyte, is adsorbed onto on the electrode owing to be dissolved in the electrolyte of electrolyte, so the interface that forms between electrolyte and electrode (electric double layer) goes up store electrical energy.Energy stored is by 1/2CV
2(wherein, C represents static capacity (F), and V represents current potential) expression in order to store a large amount of electric energy, must increase the static capacity of apparatus for storing electrical energy, for miniaturization and store a large amount of electric energy, requires to improve the static capacity of unit volume.
Activated carbon is general as the electrode of double electric layer capacitor, particularly, can enumerate: by the activated carbon of micropore (pore diameter 20 are following) main body that raw material carbonization such as palm shell and activation are obtained.The mol ratio (R/C) that discloses in No. 4873218 communique (table 1) of United States Patent (USP) at resorcinol (R) and base catalyst (C) is 200 to 410 times, resorcinol (R) is the activated carbon of the organic aerogel that polymerization obtains under 0.027～0.067 times of condition with the weight ratio (R/W) of aqueous solvent (W), Japanese Unexamined Patent Application Publication 2002-511899 communique (claim 1, embodiment 1～4) in to disclose at R/C be more than 2000, R/W is the activated carbon of the organic aerogel that polymerization obtains under 0.39 to 0.56 times of condition, but the double electric layer capacitor of the activated carbon of the static capacity that can further improve per unit volume is used in the hope exploitation.
In addition, in recent years, by in the presence of base catalyst and aqueous solvent with resorcinol and oxymethylene polymerization, the organic aerogel that is had mesopore (more than pore diameter 20 ) equably, use organic solvent washing then, aqueous solvent is replaced into organic solvent, dry then, the carbonization subsequently and activated carbon of the mesopore main body that obtains is known, and the electrode that discloses the big double electric layer capacitor of the static capacity that can be used as Unit Weight uses (with reference to Japanese kokai publication hei 9-328308 communique ([0017]), Japanese Unexamined Patent Application Publication 2002-511899 communique (p35)).
Use the tetraethyl ammonium salt as electrolyte in the Japanese kokai publication hei 9-328308 communique ([0017]), use potassium hydroxide as electrolyte in the Japanese Unexamined Patent Application Publication 2002-511899 communique, but when using the such aqueous electrolyte of hydroxide first as electrolyte, exist proof voltage (current potential) low, the problem that can energy stored diminishes.
People of the present invention study the double electric layer capacitor of record in the Japanese kokai publication hei 9-328308 communique ([0017]), find that the static capacity of per unit volume is insufficient.
People of the present invention study for the few double electric layer capacitor of the problems referred to above, found that, the static capacity that contains certain electrolytical double electric layer capacitor or contain the double electric layer capacitor per unit volume of certain activated carbon improves.
Summary of the invention
The double electric layer capacitor that the purpose of this invention is to provide the static capacity raising of per unit volume.
That is, the invention provides following [1] to [12].
[1] a kind of double electric layer capacitor comprises electrode, electrolyte and dividing plate, and described electrode contains activated carbon, and described electrolyte contains electrolyte, wherein:
Electrolyte is formula (I)
(in the formula, R and R ' represent the alkyl of carbon number 1 to 6, R independently of one another
1～R
3The alkyl of representing hydrogen atom or carbon number 1 to 6 independently of one another, X
-The expression counter ion counterionsl gegenions)
The imidazolium salts of expression, activated carbon is the activated carbon by the organic aerogel carbonization is obtained, and described organic aerogel obtains by phenoloid and the aldehyde compound polymerization that has at least one hydroxyl in the presence of aqueous solvent and base catalyst in molecule.
[2] according to [1] described double electric layer capacitor, wherein electrolytical counter ion counterionsl gegenions are for being selected from by trifluoroacetic acid root (CF
3CO
2 -) and tetrafluoroborate (BF
4 -) at least a ion in the group formed.
[3] according to [1] or [2] described double electric layer capacitor, wherein phenoloid is a resorcinol.
[4] according to [1] to [3] each described double electric layer capacitor, wherein activated carbon is the activated carbon by using 0.25 to 1000 mole of phenoloid with respect to 1 mole of base catalyst, using 0.5 to 5 weight portion phenoloid to obtain with respect to aqueous solvent 1 weight portion.
[5] according to [1] to [4] each described double electric layer capacitor, wherein activated carbon is the activated carbon that obtains 650 to 850 ℃ of following carbonizations.
[6] according to [1] to [5] each described double electric layer capacitor, wherein activated carbon is the following activated carbon of void content 1.5cc/g.
[7] the following activated carbon of a kind of void content 1.5cc/g, it is to carry out carbonization by the organic aerogel that the phenoloid that has at least one hydroxyl in the molecule and aldehyde compound polymerization will be obtained to obtain.
[8] according to the activated carbon of [7], wherein phenoloid is a resorcinol.
[9] a kind of electrode, it contains [7] or [8] described activated carbon.
[10] a kind of double electric layer capacitor, it contains [9] described electrode, dividing plate and electrolyte.
[11] a kind of activated carbon manufacture method, carry out carbonization by the organic aerogel that the phenoloid that has at least one hydroxyl in the molecule and aldehyde compound polymerization will be obtained and make activated carbon, wherein, use 0.25 to 1000 mole of phenoloid, use 0.5 to 5 weight portion phenoloid to carry out polymerization with respect to 1 mole of base catalyst with respect to aqueous solvent 1 weight portion.
[12] according to [11] described manufacture method, wherein under 650 to 850 ℃, carry out carbonization.
Description of drawings
Fig. 1 is an example (schematic diagram) of Coin shape electric double layer
Fig. 2 is an example (schematic diagram) of convoluted electric double layer
Fig. 3 is an example (schematic diagram) of laminated-type electric double layer
Fig. 4 is an example (schematic diagram) of the laminated-type electric double layer different with Fig. 3
Fig. 5 is an example (schematic diagram) of the laminated-type electric double layer of embodiments of the invention and comparative example use
[symbol description]
11: canister
12: current-collector
13: electrode
14: dividing plate
15: crown cap
16: pad
21: canister
22: current-collector
23: electrode
24: dividing plate
25: the electrode hush panel
26: lead
31: canister
32: current-collector
33: electrode
34: dividing plate
35: lead
36: terminal
37: safety valve
41: increased pressure board and terminal
42: current-collector
43: electrode
44: dividing plate
46: pad
51: increased pressure board
52: current-collector
53: electrode
54: dividing plate
55: insulating material
Embodiment
Below, describe the present invention in detail.
Double electric layer capacitor of the present invention comprises electrode, electrolyte and dividing plate, and described electrode contains activated carbon, and described electrolyte contains electrolyte.
The electrolyte that uses among the present invention is the imidazolium salts by formula (I) expression.
In the formula, R and R ' represent the alkyl of carbon number about 1 to about 6 independently of one another.As the alkyl of carbon number about 1 to about 6, can enumerate for example methyl, ethyl, n-pro-pyl, normal-butyl etc.Wherein, consider preferable methyl and ethyl from tendency this point with the static capacity that increases per unit volume.
In addition, R
1～R
3The alkyl of representing hydrogen atom or carbon number about 1 to about 6 independently of one another.The alkyl of carbon number about 1 to about 6 can be enumerated same as described above those.R
1～R
3It can be mutual different group.
As imidazoles cation, for example can enumerate: 1,3-methylimidazole , 1-ethyl-3-methylimidazole , 1,3-diethyl imidazoles , 1,2,3-tri-methylimidazolium , 1,3,4-tri-methylimidazolium , 1-ethyl-2,3-methylimidazole , 1-ethyl-3,4-methylimidazole , 1-ethyl-3,5-methylimidazole , 2-ethyl-1,3-methylimidazole , 4-ethyl-1,3-methylimidazole , 1,2-diethyl-3-methylimidazole , 1,4-diethyl-3-methylimidazole , 1,5-diethyl-3-methylimidazole , 1,3-diethyl-glyoxal ethyline , 1,3-diethyl-4-methylimidazole , 1,2,3-triethyl group imidazoles , 1,3,4-triethyl group imidazoles , 1,2,3,4-tetramethyl imidazoles , 1-ethyl-2,3,4-tri-methylimidazolium , 1-ethyl-2,3,5-tri-methylimidazolium , 1-ethyl-3,4,5-tri-methylimidazolium , 2-ethyl-1,3,4-tri-methylimidazolium , 4-ethyl-1,2,3-tri-methylimidazolium , 1,2-diethyl-3,4-methylimidazole , 1,3-diethyl-2,4-methylimidazole , 1,4-diethyl-2,3-methylimidazole , 2,4-diethyl-1,3-methylimidazole , 4,5-diethyl-1,3-methylimidazole , 1,2,3-triethyl group-4-methylimidazole , 1,2,4-triethyl group-3-methylimidazole , 1,2,5-triethyl group-3-methylimidazole , 1,3,4-triethyl group-glyoxal ethyline , 1,3,4-triethyl group-5-methylimidazole , 1,4,5-triethyl group-3-methylimidazole , 1,2,3,4,5-pentamethyl imidazoles etc.
Wherein, as imidazoles be the 1-ethyl-3-methylimidazole (EMI of formula (2) expression
+) time, consider it is preferred from tendency with the static capacity that increases per unit volume.
In the electrolytical cation that uses in the double electric layer capacitor of the present invention, can comprise the aliphatic quaternary ammonium salt cation of tetraethyl ammonium, triethyl group ammonium methyl, trimethyl propyl ammonium, 1-ethyl-1-crassitude , 1-methyl isophthalic acid-propyl group piperidines etc.
Their content is about EMI usually
+Molal quantity below.
The electrolytical counter ion counterionsl gegenions that use in the double electric layer capacitor of the present invention can be enumerated: BF usually
4 -, PF
6 -, ClO
4 -, N (CF
3SO
2)
-, CF
3CO
2 -Deng, wherein, consider preferred CF from tendency with the static capacity that increases per unit volume
3CO
2 -And BF
4 -Counter ion counterionsl gegenions can be different types of anionic mixtures.
As being used to dissolve the solvent that electrolyte solution is used, can use polar solvent usually, object lesson can be enumerated:
Carbonates is as the linear carbonate of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, diphenyl carbonate, carbonic acid aminomethyl phenyl ester etc.; Ethylene carbonate, propylene carbonate, 2, the cyclic carbonate of 3-dimethyl ethylene carbonate, butylene carbonate, vinylene carbonate, 2-vinylethylene carbonate etc. etc.;
Carboxylic acid esters is as Ethyl formate, methyl acetate, methyl propionate, ethyl ester ethyl ester, propyl acetate, butyl acetate, pentyl acetate, methyl benzoate, ethyl benzoate, gamma-butyrolacton, gamma-valerolactone, δ-Wu Neizhi etc.;
Ethers, as glycol dimethyl ether, ethylene glycol diethyl ether, glycol monoethyl ether, ethylene glycol monoethyl ether, 1,4-dioxane, 1,3-dioxolanes, oxolane, 2-methyltetrahydrofuran, 2,6-dimethyl-tetrahydrofuran, oxinane etc.;
Nitrile is as acetonitrile, propionitrile, methoxypropionitrile, glutaronitrile, adiponitrile, 2-methyl cellosolve acetate glutaronitrile etc.;
Amide-type, as N-methylformamide, N-ethyl-formamide, N, dinethylformamide, N, N-dimethylacetylamide, N-methyl pyrrolidone etc.;
The sulfone class is as dimethyl sulfone, first and second sulfones, diethyl sulfone, sulfolane, 3-methyl sulfolane, 2,4-dimethylsulfolane etc.;
The sulfoxide class is as methyl-sulfoxide, first and second sulfoxides, ethyl-sulfoxide etc.;
Sulfuric acid ester is as dimethyl suflfate, dithyl sulfate, ethyl sulfate, the inferior propyl ester of sulfuric acid etc.;
Sulfurous esters is as dimethyl sulfite, sulfurous acid diethyl ester, glycol sulfite, the inferior propyl ester of sulfurous acid etc.;
Phosphoric acid ester is as trimethyl phosphate, methyl orthophosphoric acid diethylester, p diethylaminobenzoic acid ester methyl ester, triethyl phosphate etc.;
1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2 (1H)-pyrimidone, 3-methyl-2- oxazolidone, nitromethane etc.
As being used to dissolve electrolytical solvent, can be the mixture of different solvents.
As being used to dissolve electrolytical solvent, preferably use carbonates, carboxylic acid esters, nitrile, amide-type, sulfone class, more preferably use carbonates, carboxylic acid esters.
Electrolytical concentration in the electrolyte is generally about 0.5 to about 5.0mol (electrolyte)/L (electrolyte), the concentration of preferred about 0.7 to about 3.0mol (electrolyte)/L (electrolyte).When electrolyte is the above dissolving of 0.5mol/L, considering it is preferred from the tendency that has static capacity and increase, when be 5.0mol/L, is preferred from the tendency consideration with the viscosity that reduces electrolyte.
Contained moisture in the electrolyte is generally below the 200ppm, below the preferred 50ppm, below the further preferred 20ppm.By suppressing moisture, can avoid the decline of the electrolysis of water to the influence of electrode, particularly proof voltage.
The activated carbon that uses among the present invention will be for carrying out the activated carbon that carbonization obtains by have the phenoloid of at least one hydroxyl and organic aerogel that the aldehyde compound polymerization obtains in molecule in the presence of aqueous solvent and base catalyst.
Phenoloid is the phenoloid that has at least one hydroxyl in the molecule, particularly, can illustration by the compound of formula (3) expression.
In the formula, R
10Expression can be combined with the alkyl of substituent carbon number about 1 to about 12, R
10R is arranged when a plurality of
10Can be different mutually.N represents 0 to 3 integer, and m represents 2 to 5 integer.Wherein, n and m's and be below 5.
As combinable substituting group on the alkyl, for example can enumerate: halogen atom, hydroxyl, cyano group, alkoxyl, carbamoyl, carboxyl, alkoxy carbonyl group, alkyl carbonyl oxy, sulfo group and sulfamoyl etc.
R
10Both can be the straight chain shape, and also prop up chain, can also be ring-type.
R
10For example can enumerate:
Alkyl is as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, n-octyl, nonyl, the tert-butyl group etc.;
The alkyl of hydroxyl combination, as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxy butyl etc.;
The alkyl of cyano group combination is as cyano methyl, 2-cyano ethyl, 3-cyano group propyl group etc.;
The alkyl of alkoxyl combination is as methoxy, ethoxyl methyl, 2-methoxy ethyl, 2-ethoxyethyl group, 3-methoxy-propyl, 3-ethoxycarbonyl propyl, 2-hydroxyl-3-methoxy-propyl etc.;
Haloalkyl is as chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-brombutyl etc.;
Carboxymethyl, the 2-carboxy ethyl, 3-carboxyl propyl group, the 4-carboxybutyl, 1,2-dicarboxyl ethyl, carbamoyl methyl, 2-carbamyl ethyl, 3-carbamyl propyl group, 4-carbamyl butyl, the methoxycarbonyl group methyl, ethoxycarbonylmethyl group, 2-methoxycarbonyl group ethyl, the 2-ethoxycarbonyl-ethyl, 3-methoxycarbonyl group propyl group, 3-carbethoxyl group propyl group, 4-methoxycarbonyl group butyl, 4-carbethoxyl group butyl, methyl carbonyl oxygen methyl, ethyl carbonyl oxygen methyl, 2-methyl carbonyl oxygen ethyl, 2-ethyl carbonyl oxygen ethyl, 3-methyl carbonyl oxygen propyl group, 3-ethyl carbonyl oxygen propyl group, 4-methyl carbonyl oxygen-butyl, 4-ethyl carbonyl oxygen-butyl etc.
R
10Carbon number be generally about 1 to about 12.
R
10Be preferably hydrogen atom or unsubstituted alkyl, more preferably hydrogen atom, methyl, ethyl, n-octyl.
In the formula (1), n preferred 3 or 4, and more preferably 4, m preferred 1 or 2, and more preferably 1.
Object lesson as the compound of formula (3) expression, can enumerate: orthoresol, metacresol, paracresol, 2, the 3-xylenols, 2, the 4-xylenols, 2, the 5-xylenols, 2, the 6-xylenols, 3, the 4-xylenols, 3, the 5-xylenols, o-ethyl phenol, between propylphenol, butylphenol, p-t-butyl phenol, POP, to nonyl phenol, the 2-chlorophenol, the 4-metoxyphenol, 2, the 4-chlorophenesic acid, 3, the 5-chlorophenesic acid, 4-chloro-3-methylphenol, catechol, the 3-methyl pyrocatechol, the 4-tert-butyl catechol, resorcinol, the 2-methylresorcinol, the 4-ethyl resorcinol, the 4-chloro resorcinol, the oreinol diphenol, 2,5-dimethyl resorcinol, 5-methoxyl group resorcinol, 5-amyl group resorcinol, phloroglucin, 1,2,3,-thrihydroxy-benzene etc.
Phenoloid can use separately also and can two or more mixing use.
The preferred especially resorcinol of phenoloid, phloroglucin.
As the aldehyde compound that uses in the organic aerogel manufacturing, for example can enumerate: formaldehyde, paraformaldehyde, acetaldehyde, butyraldehyde, salicylide, benzaldehyde etc.Wherein, preferably use formaldehyde.
The use amount of aldehyde compound is generally about 1 to about 3 moles with respect to 1 mole of phenoloid, preferred about 1.2 to about 2.5 moles.
As the base catalyst that uses in the organic aerogel manufacturing, for example can enumerate: sodium carbonate, potash, lithium carbonate, NaOH, potassium hydroxide, lithium hydroxide, brium carbonate, sodium phosphate, lithium phosphate, potassium phosphate etc.Wherein, preferably use sodium carbonate.
The amount ratio of base catalyst and phenoloid, with respect to per 1 mole of base catalyst, phenoloid is 0.25 to 10000 mole scope, preferred 0.25 to 1000 mole scope usually, further preferred 1 to 500 mole scope.
When being 0.25 to 10000 mole scope, consider it is preferred from having the tendency that static capacity improves with respect to the base catalyst phenoloid.
The aqueous solvent that uses during organic aerogel is made is meant water, the organic solvent that can mix with water with arbitrary proportion or the mixture of this organic solvent and water.At this, this organic solvent can be enumerated particularly: alcohols solvent, as methyl alcohol, ethanol, isopropyl alcohol etc.; Ether solvent is as oxolane etc.These solvents can use separately or two or more mixing is used.
As aqueous solvent, preferably make the mixture of water, carbon number alcohols solvent, water and the alcohols solvent of carbon number below 3 below 3, more preferably make water.
The amount ratio of aqueous solvent and phenoloid, with respect to 1 weight portion water-based solvent, phenoloid is 0.5 to 5 weight portion usually, preferred 1 to 2 weight portion.
When the amount ratio of aqueous solvent and phenoloid is 0.5 to 5 weight portion, consider it is preferred from the tendency that the static capacity with per unit volume improves.
In manufacture method of the present invention, the use amount of aqueous solvent, the use amount of aqueous solvent when being meant polymerization, so contained aqueous solvent also counts in the use amount in phenoloid or the aldehyde compound.For example, if 37% formlinata aquae concentratac, then 63% water calculates as aqueous solvent.
Manufacture method as organic aerogel, for example can enumerate: with the unified mixing of phenoloid, aldehyde compound, base catalyst and aqueous solvent, usually under 0 to 100 ℃, preferred 30 to 90 ℃, stir and obtain wet gel, carry out dry method then; In the mixture that constitutes by phenoloid, base catalyst and aqueous solvent, obtain wet gel at 0 to 100 ℃, preferred 30 to 90 ℃ of following mixed aldehyde compounds usually, carry out dry method then; In the mixture that constitutes by aldehyde compound, base catalyst and aqueous solvent, under 0 to 100 ℃, preferred 30 to 90 ℃, mix phenoloid usually and obtain wet gel, carry out dry method then; In the mixture that constitutes by phenoloid, aldehyde compound and aqueous solvent, obtain wet gel at 0 to 100 ℃, preferred 30 to 90 ℃ of following mixed-alkali catalyst usually, carry out dry method etc. then.
Wherein, preferably in the mixture that constitutes by phenoloid, base catalyst and aqueous solvent the mixed aldehyde compound obtain the method for wet gel.
The drying of wet gel for example can be enumerated: ventilate down or the methods of drying under reduced pressure etc. to about 100 ℃ in room temperature.In addition, the solvent in the wet gel is under the situation of water, can enumerate: with behind the hydrophilic organic solvent replacing water, ventilate down or the methods of drying under reduced pressure etc. to about 100 ℃ in room temperature.
As above-mentioned hydrophilic organic solvent, for example can enumerate: alcohols, as methyl alcohol, ethanol, normal propyl alcohol, the tert-butyl alcohol etc.; The aliphat nitrile is as acetonitrile etc.; The aliphat ketone is as acetone etc.; Aliphat sulfoxide class is as methyl-sulfoxide etc.; Aliphatic carboxylic acid class such as acetate etc.
As hydrophilic organic solvent, preferably use the tert-butyl alcohol, methyl-sulfoxide, acetate, consider the preferred tertiary butanols from angle easy and the water displacement.
In addition, can carry out freeze drying replaces in the method for room temperature to about 100 ℃ of following ventilations or drying under reduced pressure.Cryodesiccated temperature usually in-70 ℃ to 20 ℃ scopes, preferred-30 to 10 ℃ scope.In addition, freeze drying is carried out under vacuum usually.
In addition, as Japanese kokai publication hei 9-328308 communique record, use carbon dioxide etc. carries out drying under supercriticality also passable.
As the drying means of wet gel, consider preferably freeze drying from the void content angle with low uncertainty that drying causes.
The activated carbon that uses among the present invention can carry out carbonization by the organic aerogel that will obtain after the drying and activation obtains.As the concrete manufacture method of this activated carbon, can enumerate:
(I) nitrogen, argon gas, helium, hydrogen etc. to carbon inert gasses atmosphere under, usually under the temperature of 200 to 1500 ℃ scope, preferred 600 to 1100 ℃ scope, roasting (carbonization) about 1 minute to about 24 hours usually is then at H
2O, CO
2, O
2Exist down Deng oxidizing gas, usually under the temperature of 200 to 1500 ℃ scope, preferred 600 to 1100 ℃ scope, roasting (activation) is about 1 minute about 10 hours method extremely usually;
(II) in the presence of oxidizing gas, usually under the temperature of 200 to 1500 ℃ scope, preferred 600 to 1100 ℃ scope, roasting (carbonization and activation) usually about 1 minute to about 24 hours method;
(III) in the presence of the oxidizing gas of air etc., usually below 400 ℃, under preferred 200 to 300 ℃, with compound (1) roasting (carbonization) about 1 minute to about 24 hours usually, then under to carbon inert gasses atmosphere, usually under the temperature of 200 to 1500 ℃ scope, preferred 600 to 1100 ℃ scope, roasting (carbonization) about 1 minute to about 24 hours usually, and then in the presence of oxidizing gas, usually under the temperature of 200 to 1500 ℃ scope, preferred 600 to 1100 ℃ scope, roasting (activation) is about 1 minute about 10 hours method extremely usually;
(IV) in the presence of oxidizing gas such as air, usually below 400 ℃, under preferred 200 to 300 ℃, with compound (1) roasting (carbonization) about 1 minute to about 24 hours usually, then at H
2O or CO
2Existence under, usually under the temperature of 200 to 1500 ℃ scope, preferred 600 to 1100 ℃ scope, roasting (activation) is about 1 minute about 10 hours method extremely usually;
(V) under vacuum, usually under the temperature of 200 to 1500 ℃ scope, preferred 600 to 1100 ℃ scope, with compound (1) roasting (carbonization) about 1 minute to about 24 hours usually, then in the presence of oxidizing gas, usually under the temperature of 200 to 1500 ℃ scope, preferred 600 to 1100 ℃ scope, roasting (activation) is about 1 minute about 10 hours method extremely usually;
(VI) during roasting under the oxidizing gas atmosphere of above-mentioned (II) (carbonization and activation), the method for mixed chlorinated zinc, phosphoric acid, potassium sulfide, potassium hydroxide etc. etc.
Wherein, consider the preferably method of (I) to (V) from metal-free angle, in addition, as oxidizing gas, preferred H
2O, CO
2
Sintering temperature is more than 200 ℃ the time, considers it is preferred from having the tendency that void content improves, and when being below 1100 ℃ the time, considers it is preferred from having the tendency that the activated carbon yield improves.In addition, roasting time is more than 1 minute the time, considers it is preferred from having the tendency that void content improves, and when being below 24 hours the time, considers it is preferred from having the tendency that the activated carbon yield improves.
The activated carbon that uses among the present invention, preferably its void content is below the 1.5cc/g, and more preferably 0.1 to 1.5cc/g, and further preferred 0.3 to 1.0cc/g, and preferred especially 0.3 to 0.6cc/g.When the void content of activated carbon is 1.5cc/g when following, consider it is preferred from the tendency that the static capacity with per unit volume improves.
In addition, when using void content in the double electric layer capacitor of the present invention, preferably use above-mentioned imidazolium salts, still, also can use normally used electrolyte as electrolyte as the activated carbon below the 1.5cc/g.
As above-mentioned imidazolium salts (1) normally used electrolyte in addition, can enumerate the salt of the organic quaternary ammonium cation that comprises carbon number 4 to 12 etc.
Wherein, be fit to use the salt that constitutes by anion and organic quaternary ammonium cation.
As electrolyte, for example can enumerate: BO
3 3-, F
-, PF
6 -, BF
4 -, AsF
6 -, SbF
6 -, ClO
4 -, AlF
4 -, AlCl
4 -, TaF
6 -, NbF
6 -, SiF
6 -, CN
-, F (HF)
N-The combination of the inorganic cation of the inorganic anion of (in this formula, n represents 1 to 4 numerical value) etc. and organic cations described later combination, organic anion described later and organic cations combination, organic anion and lithium ion, sodium ion, potassium ion, hydrogen ion etc.
Organic cation is meant the cationic organic compound, for example can enumerate: organic quaternary ammonium cation, organic season cation etc.
Organic quaternary ammonium cation is meant that the alkyl that is selected from the group that alkyl (carbon number 1 to 20), cycloalkyl (carbon number 6 to 20), aryl (carbon number 6 to 20) and aralkyl (carbon number 7 to 20) form is replaced by nitrogen-atoms and the quaternary ammonium cation that forms, and organic season cation is meant the season cation that is formed by the phosphorus atoms replacement with above-mentioned same alkyl.
On the alkyl that replaces, also can be combined with hydroxyl, amino, nitro, cyano group, carboxyl, ether, aldehyde radical etc.
As main organic quaternary ammonium cation, organic season cation, the compound that illustration is following.
(tetraalkylammonium cation)
Tetramethyl-ammonium, ethyl trimethyl ammonium, the triethyl group ammonium methyl, tetraethyl ammonium, four n-pro-pyl ammoniums, the tetra-n-butyl ammonium, the diethyl-dimethyl ammonium, methyl three n-pro-pyl ammoniums, three normal-butyl ammonium methyls, ethyl three normal-butyl ammoniums, three n-octyl ammonium methyls, ethyl three n-octyl ammoniums, diethylmethyl isopropyl ammonium, diethylmethyl n-pro-pyl ammonium, ethyl dimethyl isopropyl ammonium, ethyl dimethyl n propyl ammonium, diethylmethyl methoxy ethyl ammonium, dimethyl ethyl methoxy ethyl ammonium, benzyltrimethylammon.um, (CF
3CH
2) (CH
3)
3N
+, (CF
3CH
2)
2(CH
3)
2N
+Deng
(ethylene ammonium cation)
N, N, N, N ', N ', N '-hexamethyl ethylene ammonium, N, N '-diethyl-N, N, N ', N '-tetramethyl ethylene ammonium etc.
(the dicyclo ammonium cation that following formula is represented)
(in the formula, X represents nitrogen-atoms or phosphorus atoms, and n, m represent 4 to 6 integer respectively independently)
(guanidine cation) with imidazoline skeleton
2-dimethylamino-1; 3; 4-tri-methylimidazolium quinoline ; 2-diethylamino-1; 3; 4-tri-methylimidazolium quinoline ; 2-diethylamino-1; 3-dimethyl-4-ethyl imidazol(e) quinoline ; 2-dimethylamino-1-methyl-3; 4-diethyl imidazoline ; 2-diethylamino-1-methyl-3; 4-diethyl imidazoline ; 2-diethylamino-1; 3; 4-triethyl group imidazoline ; 2-dimethylamino-1; 3-methylimidazole quinoline ; 2-diethylamino-1; 3-methylimidazole quinoline ; 2-dimethylamino-1-ethyl-3-methylimidazole quinoline ; 2-diethylamino-1; 3-diethyl imidazoline ; 1; 5; 6; 7-tetrahydrochysene-1; 2-dimethyl-12H-0 acid imide [1; 2a] imidazoline ; 1; 5-dihydro-1; 2-dimethyl-2H-acid imide [1; 2a] imidazoline ; 1; 5; 6; 7-tetrahydrochysene-1; 2-dimethyl-2H-pyrimido [1; 2a] imidazoline ; 1; 5-dihydro-1; 2-dimethyl-2H-pyrimido [1; 2a] imidazoline ; 2-dimethylamino-4-cyano group-1; 3-methylimidazole quinoline ; 2-dimethylamino-3-cyano methyl-1-methylimidazole quinoline ; 2-dimethylamino-4-acetyl group-1; 3-methylimidazole quinoline ; 2-dimethylamino-3-acetonyl-1-methylimidazole quinoline ; 2-dimethylamino-4-methyl carbonyl oxygen methyl isophthalic acid; 3-methylimidazole quinoline ; 2-dimethylamino-3-methyl carbonyl oxygen methyl isophthalic acid-methylimidazole quinoline ; 2-dimethylamino-4-methoxyl group-1; 3-methylimidazole quinoline ; 2-dimethylamino-3-methoxy-1-methylimidazole quinoline ; 2-dimethylamino-4-formoxyl-1; 3-methylimidazole quinoline ; 2-dimethylamino-3-formoxyl methyl isophthalic acid-methylimidazole quinoline ; 2-dimethylamino-3-hydroxyethyl-1-methylimidazole quinoline ; 2-dimethylamino-4-hydroxymethyl-1,3-methylimidazole quinoline etc.
(guanidine cation) with imidazoles skeleton
2-dimethylamino-1; 3; 4-tri-methylimidazolium ; 2-diethylamino-1; 3; 4-tri-methylimidazolium ; 2-diethylamino-1; 3-dimethyl-4-ethyl imidazol(e) ; 2-dimethylamino-1-methyl-3; 4-diethyl imidazoles ; 2-diethylamino-1-methyl-3; 4-diethyl imidazoles ; 2-diethylamino-1; 3; 4-triethyl group imidazoles ; 2-dimethylamino-1; 3-methylimidazole ; 2-diethylamino-1; 3-methylimidazole ; 2-dimethylamino-1-ethyl-3-methylimidazole ; 2-diethylamino-1; 3-diethyl imidazoles ; 1; 5; 6; 7-tetrahydrochysene-1; 2-dimethyl-2H-acid imide [1; 2a] imidazoles ; 1; 5-dihydro-1; 2-dimethyl-2H-acid imide [1; 2a] imidazoles ; 1; 5; 6; 7-tetrahydrochysene-1; 2-dimethyl-2H-pyrimido [1; 2a] imidazoles ; 1; 5-dihydro-1; 2-dimethyl-2H-pyrimido [1; 2a] imidazoles ; 2-dimethylamino-4-cyano group-1; 3-methylimidazole ; 2-dimethylamino-3-cyano methyl-1-methylimidazole ; 2-dimethylamino-4-acetyl group-1; 3-methylimidazole ; 2-dimethylamino-3-acetonyl-1-methylimidazole ; 2-dimethylamino-4-methyl carbonyl oxygen methyl isophthalic acid; 3-methylimidazole ; 2-dimethylamino-3-methyl carbonyl oxygen methyl isophthalic acid-methylimidazole ; 2-dimethylamino-4-methoxyl group-1; 3-methylimidazole ; 2-dimethylamino-3-methoxy-1-methylimidazole ; 2-dimethylamino-4-formoxyl-1; 3-methylimidazole ; 2-dimethylamino-3-formoxyl methyl isophthalic acid-methylimidazole ; 2-dimethylamino-3-hydroxyethyl-1-methylimidazole ; 2-dimethylamino-4-hydroxymethyl-1,3-methylimidazole etc.
(guanidine cation) with tetrahydropyrimidine skeleton
2-dimethylamino-1,3,4-trimethyl-1; 4,5,6-tetrahydropyrimidine ; 2-diethylamino-1; 3,4-trimethyl-1,4; 5,6-tetrahydropyrimidine ; 2-diethylamino-1,3-dimethyl-4-ethyl-1; 4,5,6-tetrahydropyrimidine ; 2-dimethylamino-1-methyl-3; 4-diethyl-1,4,5; 6-tetrahydropyrimidine ; 2-diethylamino-1-methyl-3,4-diethyl-1,4; 5,6-tetrahydropyrimidine ; 2-diethylamino-1,3; 4-triethyl group-1,4,5; 6-tetrahydropyrimidine ; 2-dimethylamino-1; 3-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 2-diethylamino-1; 3-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 2-dimethylamino-1-ethyl-3-methyl isophthalic acid; 4,5,6-tetrahydropyrimidine ; 2-diethylamino-1; 3-diethyl-1; 4,5,6-tetrahydropyrimidine ; 1; 3; 4,6,7; 8-six hydrogen-1; 2-dimethyl-2H-acid imide [1,2a] pyrimidine ; 1,3; 4; 6-tetrahydrochysene-1,2-dimethyl-2H-acid imide [1,2a] pyrimidine ; 1; 3; 4,6,7; 8-six hydrogen-1; 2-dimethyl-2H-pyrimido [1,2a] pyrimidine ; 1,3; 4; 6-tetrahydrochysene-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidine ; 2-dimethylamino-4-cyano group-1; 3-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 2-dimethylamino-3-cyano methyl-1-methyl isophthalic acid; 4; 5,6-tetrahydropyrimidine ; 2-dimethylamino-4-acetyl group-1,3-dimethyl-1; 4; 5,6-tetrahydropyrimidine ; 2-dimethylamino-3-acetonyl-1-methyl isophthalic acid, 4; 5; 6-tetrahydropyrimidine ; 2-dimethylamino-4-methyl carbonyl oxygen methyl isophthalic acid, 3-dimethyl-1,4; 5; 6-tetrahydropyrimidine ; 2-dimethylamino-3-methyl carbonyl oxygen methyl isophthalic acid-methyl isophthalic acid, 4,5; 6-tetrahydropyrimidine ; 2-dimethylamino-4-methoxyl group-1; 3-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 2-dimethylamino-3-methoxy-1-methyl isophthalic acid; 4,5,6-tetrahydropyrimidine ; 2-dimethylamino-4-formoxyl-1; 3-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 2-dimethylamino-3-formyl methyl isophthalic acid-methyl isophthalic acid; 4; 5,6-tetrahydropyrimidine ; 2-dimethylamino-3-hydroxyethyl-1-methyl isophthalic acid, 4; 5; 6-tetrahydropyrimidine ; 2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-1,4; 5,6-tetrahydropyrimidine etc.
(guanidine cation) with dihydro-pyrimidin skeleton
2-dimethylamino-1; 3; 4-trimethyl-1; 4 (6)-dihydro-pyrimidin ; 2-diethylamino-1; 3; 4-trimethyl-1; 4 (6)-dihydro-pyrimidin ; 2-diethylamino-1; 3-dimethyl-4-ethyl-1; 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-1-methyl-3; 4-diethyl-1; 4 (6)-dihydro-pyrimidin ; 2-diethylamino-1-methyl-3; 4-diethyl-1; 4 (6)-dihydro-pyrimidin ; 2-diethylamino-1; 3; 4-triethyl group-1; 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-1; 3-dimethyl-1; 4 (6)-dihydro-pyrimidin ; 2-diethylamino-1; 3-dimethyl-1; 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-1-ethyl-1; 4 (6)-dihydro-pyrimidin ; 2-diethylamino-1; 3-diethyl-1; 4 (6)-dihydro-pyrimidin ; 1; 6; 7; 8-tetrahydrochysene-1; 2-dimethyl-2H-acid imide [1; 2a] pyrimidine ; 1; 6-dihydro-1,2-dimethyl-2H-acid imide [1,2a] pyrimidine ; 1; 6; 7,8-tetrahydrochysene-1,2-dimethyl-2H-pyrimido [1; 2a] pyrimidine ; 1; 6-dihydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidine ; 2-dimethylamino-4-cyano group-1; 3-dimethyl-1; 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-3-cyano methyl-1-methyl isophthalic acid, 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-4-acetyl group-1,3-dimethyl-1; 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-3-acetonyl-1-methyl isophthalic acid; 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-4-methyl carbonyl oxygen methyl isophthalic acid, 3-dimethyl-1,4 (6)-dihydro-pyrimidin ; 2-dimethylamino-3-methyl carbonyl oxygen methyl isophthalic acid-methyl isophthalic acid; 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-4-methoxyl group-1; 3-dimethyl-1,4 (6)-dihydro-pyrimidin ; 2-dimethylamino-3-methoxy-1-methyl isophthalic acid, 4 (6)-dihydro-pyrimidin ; 2-dimethylamino-4-formoxyl-1; 3-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 2-dimethylamino-3-formoxyl methyl isophthalic acid-methyl isophthalic acid; 4; 5,6-tetrahydropyrimidine ; 2-dimethylamino-3-hydroxyethyl-1-methyl isophthalic acid, 4; 5; 6-tetrahydropyrimidine ; 2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-1,4 (6)-dihydro-pyrimidin etc.
(pyrrolidines cation)
N, N-dimethyl pyrrolidine , N-ethyl-N-crassitude , N-n-pro-pyl-N-crassitude , N-normal-butyl-N-crassitude , N, N-diethyl pyrrolidines , spiral shell-(1,1 ') two pyrrolidines etc.
(piperidines cation)
N, N-lupetidine , N-ethyl-N-methyl piperidine , N, N-diethyl piperidines , N-n-pro-pyl-N-methyl piperidine , N-normal-butyl-N-methyl piperidine , N-ethyl-N-normal-butyl piperidines etc.
(hexa-methylene imonium cation)
N, N-dimethyl hexa-methylene imonium , N-ethyl-N-methyl hexa-methylene imonium , N, N-diethyl hexa-methylene imonium etc.
(morpholine cation)
N, N-thebaine , N-ethyl-N-methylmorpholine , N-butyl-N-methylmorpholine , N-ethyl-N-butyl morpholine etc.
(piperazine cation)
N, N, N ', N '-tetramethyl piperazine , N-ethyl-N, N ', N '-tri methyl piperazine , N, N '-diethyl-N, N '-lupetazin , N, N, N '-triethyl group-N '-methyl piperazine , N, N, N ', N '-tetraethyl piperazine etc.
(tetrahydropyrimidine cation)
1,3-dimethyl-1,4; 5,6-tetrahydropyrimidine ; 1,2; 3-trimethyl-1,4,5; 6-tetrahydropyrimidine ; 1,3,4-trimethyl-1; 4,5,6-tetrahydropyrimidine ; 1; 3,5-trimethyl-1,4; 5,6-tetrahydropyrimidine ; 1-ethyl-2,3-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 1-ethyl-3; 4-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 1-ethyl-3,5-dimethyl-1,4; 5,6-tetrahydropyrimidine ; 1-ethyl-3,6-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 2-ethyl-1; 3-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 4-ethyl-1,3-dimethyl-1,4; 5,6-tetrahydropyrimidine ; 5-ethyl-1,3-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 1; 2,3,4-tetramethyl-1; 4,5,6-tetrahydropyrimidine ; 1; 2,3,5-tetramethyl-1; 4,5,6-tetrahydropyrimidine ; the 8-methyl isophthalic acid; 8-diazabicyclo [5.4.0]-7-hendecene ; the 5-methyl isophthalic acid, 5-diazabicyclo [4.3.0]-5-nonene ; 8-ethyl-1,8-diazabicyclo [5.4.0]-7-hendecene ; 5-ethyl-1; 5-diazabicyclo [4.3.0]-5-nonene ; the 5-methyl isophthalic acid, 5-diazabicyclo [5.4.0]-5-hendecene ; 5-ethyl-1,5-diazabicyclo [5.4.0]-5-hendecene ; 1; 2,3,4-tetramethyl-1; 4,5,6-tetrahydropyrimidine ; 1; 2,3,5-tetramethyl-1; 4,5,6-tetrahydropyrimidine ; 1-ethyl-2; 3,4-trimethyl-1,4; 5,6-tetrahydropyrimidine ; 1-ethyl-2,3; 5-trimethyl-1,4,5; 6-tetrahydropyrimidine ; 1-ethyl-2,3,6-trimethyl-1; 4,5,6-tetrahydropyrimidine ; 2-ethyl-1; 3,4-trimethyl-1,4; 5,6-tetrahydropyrimidine ; 2-ethyl-1,3; 5-trimethyl-1,4,5; 6-tetrahydropyrimidine ; 4-ethyl-1,2,3-trimethyl-1; 4,5,6-tetrahydropyrimidine ; 4-ethyl-1; 3,5-trimethyl-1,4; 5,6-tetrahydropyrimidine ; 4-ethyl-1,3; 6-trimethyl-1,4,5; 6-tetrahydropyrimidine ; 5-ethyl-1,2,3-trimethyl-1; 4,5,6-tetrahydropyrimidine ; 5-ethyl-1; 3,4-trimethyl-1,4; 5,6-tetrahydropyrimidine ; 1,2-diethyl-3; 4-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 1,2-diethyl-3,5-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 1; 2-diethyl-3,6-dimethyl-1,4; 5,6-tetrahydropyrimidine ; 1,3-diethyl-2; 4-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 1,3-diethyl-2,5-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 1; 4-diethyl-2,3-dimethyl-1,4; 5,6-tetrahydropyrimidine ; 1,4-diethyl-3; 5-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 1,4-diethyl-3,6-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 1; 5-diethyl-2,3-dimethyl-1,4; 5,6-tetrahydropyrimidine ; 1,5-diethyl-3; 4-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 1,5-diethyl-3,6-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 2; 4-diethyl-1,3-dimethyl-1,4; 5,6-tetrahydropyrimidine ; 2,5-diethyl-1; 3-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 4,5-diethyl-1,3-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 4; 6-diethyl-1,3-dimethyl-1,4; 5,6-tetrahydropyrimidine ; 1,2; 3,4,5-pentamethyl-1; 4,5,6-tetrahydropyrimidine ; 1; 2,3,4; 6-pentamethyl-1,4,5; 6-tetrahydropyrimidine ; 1,2,3; 4,5, the 6-vegolysen; 4,5,6-tetrahydropyrimidine ; 4-cyano group-1; 2,3-trimethyl-1,4; 5,6-tetrahydropyrimidine ; 3-cyano methyl-1,2-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 2-cyano methyl-1; 3-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 4-acetyl group-1,2,3-trimethyl-1; 4,5,6-tetrahydropyrimidine ; 3-acetonyl-1; 2-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 4-methyl carbonyl oxygen methyl isophthalic acid, 2,3-trimethyl-1; 4,5,6-tetrahydropyrimidine ; 3-methyl carbonyl oxygen methyl isophthalic acid; 2-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 4-methoxyl group-1,2,3-trimethyl-1; 4,5,6-tetrahydropyrimidine ; 3-methoxy-1; 2-dimethyl-1; 4,5,6-tetrahydropyrimidine ; 4-formoxyl-1; 2; 3-trimethyl-1,4,5; 6-tetrahydropyrimidine ; 3-formyl methyl isophthalic acid; 2-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 3-hydroxyethyl-1; 2-dimethyl-1,4,5; 6-tetrahydropyrimidine ; 4-hydroxymethyl-1; 2,3-trimethyl-1,4; 5; 6-tetrahydropyrimidine ; 2-hydroxyethyl-1,3-dimethyl-1,4; 5,6-tetrahydropyrimidine etc.
(dihydro-pyrimidin cation)
1; 3-dimethyl-1; 4-or 1; 6-dihydro-pyrimidin (is expressed as 1 with them; 3-dimethyl-1; 4 (6)-dihydro-pyrimidin , below identical); 1,2; 3-trimethyl-1; 4 (6)-dihydro-pyrimidin ; 1,2,3; 4-tetramethyl-1; 4 (6)-dihydro-pyrimidin ; 1,2,3; 5-tetramethyl-1; 4 (6)-dihydro-pyrimidin ; the 8-methyl isophthalic acid, 8-diazabicyclo [5.4.0]-7,9 (10)-11 carbon diene ; the 5-methyl isophthalic acid; 5-diazabicyclo [4.3.0]-5; 7 (8)-nonadiene ; 4-cyano group-1,2,3-trimethyl-1; 4 (6)-dihydro-pyrimidin ; 3-cyano methyl-1; 2-dimethyl-1,4 (6)-dihydro-pyrimidin ; 2-cyano methyl-1,3-dimethyl-1; 4 (6)-dihydro-pyrimidin ; 4-acetyl group-1; 2,3-trimethyl-1,4 (6)-dihydro-pyrimidin ; 3-acetonyl-1; 2-dimethyl-1; 4 (6)-dihydro-pyrimidin ; 4-methyl carbonyl oxygen methyl isophthalic acid, 2,3-trimethyl-1; 4 (6)-dihydro-pyrimidin ; 3-methyl carbonyl oxygen methyl isophthalic acid; 2-dimethyl-1,4 (6)-dihydro-pyrimidin ; 4-methoxyl group-1,2; 3-trimethyl-1; 4 (6)-dihydro-pyrimidin ; 3-methoxy-1,2-dimethyl-1,4 (6)-dihydro-pyrimidin ; 4-formoxyl-1; 2; 3-trimethyl-1,4 (6)-dihydro-pyrimidin ; 3-formyl methyl isophthalic acid, 2-dimethyl-1; 4 (6)-dihydro-pyrimidin ; 3-hydroxyethyl-1; 2-dimethyl-1,4 (6)-dihydro-pyrimidin ; 4-hydroxymethyl-1,2; 3-trimethyl-1; 4 (6)-dihydro-pyrimidin ; 2-hydroxyethyl-1,3-dimethyl-1,4 (6)-dihydro-pyrimidin ; and 2 hydrogen atoms of above-mentioned dihydro-pyrimidin cationoid are replaced by fluorine atom and cation of forming etc.
1,3,4,6,7,8-six hydrogen-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidine
(pyridine cation)
N-picoline , N-ethylpyridine , N-n-pro-pyl pyridine , N-normal-butyl pyridine , N-methyl-4-picoline , N-ethyl-4-picoline , N-n-pro-pyl-4-picoline , N-normal-butyl 4-picoline , N-methyl-3-picoline , N-ethyl-3-picoline , N-n-pro-pyl-3-picoline , N-normal-butyl-3-picoline , N-methyl-2-picoline , N-ethyl-2-picoline , N-n-pro-pyl-2-picoline , N-normal-butyl-2-picoline , N-methyl-2,4-lutidines , N-ethyl-2,4-lutidines , N-n-pro-pyl-2, the 4-diformazan is at pyridine , N-normal-butyl-2,4-lutidines , N-methyl-3,5-lutidines , N-ethyl-3,5-lutidines , N-n-pro-pyl-3,5-lutidines , N-normal-butyl-3,5-lutidines , N-methyl-4-dimethylaminopyridine , N-ethyl-4-dimethylaminopyridine , N-n-pro-pyl-4-dimethylaminopyridine , N-normal-butyl-4-dimethylaminopyridine etc.
(picoline cation)
N-methyl pyridine , N-aldehydine etc.
(imidazoline cationoid)
1,2,3-tri-methylimidazolium quinoline ; 1; 2,3,4-tetramethyl imidazoline ; 1; 3,4-trimethyl-2-ethyl imidazol(e) quinoline ; 1,3-dimethyl-2; 4-diethyl imidazoline ; 1,2-dimethyl-3,4-diethyl imidazoline ; 1-methyl-2; 3,4-triethyl group imidazoline ; 1,2; 3,4-tetraethyl imidazoline ; 1,3-dimethyl-2-ethyl imidazol(e) quinoline ; 1-ethyl-2; 3-methylimidazole quinoline ; 1,2,3-triethyl group imidazoline ; 1; 1-dimethyl-2-heptyl imidazoline ; 1,1-dimethyl-2-(2 '-heptyl) imidazoline ; 1,1-dimethyl-2-(3 '-heptyl) imidazoline ; 1; 1-dimethyl-2-(4 '-heptyl) imidazoline ; 1,1-dimethyl-2-lauryl imidazoline ; 1,1-methylimidazole quinoline ; 1; 1,2-tri-methylimidazolium quinoline ; 1,1; 2,4-tetramethyl imidazoline ; 1,1; 2,5-tetramethyl imidazoline ; 1,1; 2,4,5-pentamethyl imidazoline ; 1; 2,3-tri-methylimidazolium quinoline ; 1,3; 4-tri-methylimidazolium quinoline ; 1,2,3; 4-tetramethyl imidazoline ; 1,2,3; 4-tetraethyl imidazoline ; 1,2,3; 5-pentamethyl imidazoline ; 1,3-dimethyl-2-ethyl imidazol(e) quinoline ; 1-ethyl-2,3-methylimidazole quinoline ; 1-ethyl-3; 4-methylimidazole quinoline ; 1-ethyl-3,5-methylimidazole quinoline ; 4-ethyl-1,3-methylimidazole quinoline ; 1; 2-diethyl-3-methylimidazole quinoline ; 1,4-diethyl-3-methylimidazole quinoline ; 1,5-diethyl-3-methylimidazole quinoline ; 1; 3-diethyl-glyoxal ethyline quinoline ; 1; 3-diethyl-4-methylimidazole quinoline ; 1,2,3-triethyl group imidazoline ; 1-ethyl-2; 3; 4-tri-methylimidazolium quinoline ; 1-ethyl-2,3,5-tri-methylimidazolium quinoline ; 1-ethyl-3; 4; 5-tri-methylimidazolium quinoline ; 2-ethyl-1,3,4-tri-methylimidazolium quinoline ; 4-ethyl-1; 2; 3-tri-methylimidazolium quinoline ; 1,2-diethyl-3,4-methylimidazole quinoline ; 1; 3-diethyl-2; 4-methylimidazole quinoline ; 1,4-diethyl-2,3-methylimidazole quinoline ; 2; 4-diethyl-1; 3-methylimidazole quinoline ; 4,5-diethyl-1,3-methylimidazole quinoline ; 3; 4-diethyl-1; 2-methylimidazole quinoline ; 1,2,3-triethyl group-4-methylimidazole quinoline ; 1; 2; 4-triethyl group-3-methylimidazole quinoline ; 1,2,5-triethyl group-3-methylimidazole quinoline ; 1; 3; 4-triethyl group-glyoxal ethyline quinoline ; 1,3,4-triethyl group-5-methylimidazole quinoline ; 1; 4; 5-triethyl group-3-methylimidazole quinoline ; 2,3,4-triethyl group-1-methylimidazole quinoline ; 4-cyano group-1; 2; 3-tri-methylimidazolium quinoline ; 3-cyano methyl-1,2-methylimidazole quinoline ; 2-cyano methyl-1,3-methylimidazole quinoline ; 4-acetyl group-1; 2; 3-tri-methylimidazolium quinoline ; 3-acetyl group methyl isophthalic acid, 2-methylimidazole quinoline ; 4-methyl carbonyl oxygen methyl isophthalic acid, 2; 3-tri-methylimidazolium quinoline ; 3-methyl carbonyl oxygen methyl isophthalic acid; 2-methylimidazole quinoline ; 4-methoxyl group-1,2,3-tri-methylimidazolium quinoline ; 3-methoxy-1; 2-methylimidazole quinoline ; 4-formoxyl-1; 2,3-tri-methylimidazolium quinoline ; 3-formoxyl methyl isophthalic acid, 2-methylimidazole quinoline ; 3-hydroxyethyl-1; 2-methylimidazole quinoline ; 4-hydroxymethyl-1; 2,3-tri-methylimidazolium quinoline ; 2-hydroxyethyl-1,3-methylimidazole quinoline ; and 2 hydrogen atoms of above-mentioned imidazoline cationoid are replaced by fluorine atom and cation of forming etc.
(quinoline cation)
N-methylquinoline , N-ethyl quinoline etc.
(bipyridilium cation)
N-methyl-2,2 '-bipyridilium, N-ethyl-2,2 '-bipyridilium etc.
(other ammonium cation)
N-methylthiazol , N-ethyl thiazole , N-methyl azoles , N-ethyl azoles , N-methyl-4-methylthiazol , N-ethyl-4-methylthiazol , N-ethyl isothiazole , 1,4-dimethyl-1,2,4-triazole , 1,4-diethyl-1,2,4-triazole , 1-methyl-4-ethyl-1,2,4-triazole , 1-ethyl-4-methyl isophthalic acid, 2,4-triazole , 1,2-dimethyl pyrazole , 1,2-diethyl pyrazoles , 1-methyl-2-ethyl pyrazoles , N-methylpyrazine , N-ethyl pyrazine , N-methyl pyridazine , N-ethyl pyridazine etc.
(tetraalkyl cation)
Tetramethyl , ethyl-trimethyl , triethyl group methyl , tetraethyl , diethyl-dimethyl , trimethyl n-pro-pyl , trimethyl isopropyl , ethyl dimethyl n propyl group , ethyl dimethyl isopropyl , diethylmethyl n-pro-pyl , diethylmethyl isopropyl , dimethyl di , dimethyl n propyl group isopropyl , dimethyl diisopropyl , triethyl group n-pro-pyl , normal-butyl trimethyl , isobutyl group trimethyl , tert-butyl group trimethyl , triethyl group isopropyl , ethyl-methyl di , ethyl-methyl n-pro-pyl isopropyl , ethyl-methyl diisopropyl , normal-butyl ethyl dimethyl , isobutyl group ethyl dimethyl , tert-butyl group ethyl dimethyl , diethyl di , diethyl n-pro-pyl isopropyl , diethyl diisopropyl , methyl three n-pro-pyl , methyl di isopropyl , methyl n-pro-pyl diisopropyl , normal-butyl triethyl group , isobutyl group triethyl group , tert-butyl group triethyl group , di-n-butyl dimethyl , diisobutyl dimethyl , di-t-butyl dimethyl , normal-butyl isobutyl group dimethyl , normal-butyl tert-butyl group dimethyl , isobutyl group tert-butyl group dimethyl , three n-octyl methyl , ethyl three n-octyl etc.
Organic anion is meant and comprises the anion that can have substituent alkyl, for example can enumerate: be selected from N (SO
2R
f)
2-, C (SO
2R
f)
3-, R
fCOO
-And R
fSO
3-(R
fThe perfluoroalkyl of expression carbon number 1 to 12) anion in the group of forming and from organic acid shown below (carboxylic acid, organic sulfonic acid, organic phosphoric acid) or phenol, remove anion that reactive hydrogen atom forms etc.
(carboxylic acid)
◆ 2 to 4 valency polybasic carboxylic acids of carbon number 2 to 15: aliphat polybasic carboxylic acid [saturated polybasic carboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, pentacosandioic acid, hexadecandioic acid (hexadecane diacid), methylmalonic acid, ethyl malonic acid, propylmalonic acid, butylmalonic acid, amyl malonic acid, the hexyl malonic acid, dimethyl malonic acid, diethyl malonic acid, the methyl-propyl malonic acid, the methyl butyl malonic acid, the ethyl propyl malonic acid, the dipropyl malonic acid, dimethyl succinic acid, ethyl succinic acid, 2, the 2-dimethyl succinic acid, 2, the 3-dimethyl succinic acid, the 2-methylglutaric acid, the 3-methylglutaric acid, 3-methyl-3-ethylglutaric acid, 3, the 3-diethyl glutarate, dimethyl succinic acid, the 2-methylglutaric acid, the 3-methylglutaric acid, 3, the 3-dimethylated pentanedioic acid, 3-methyl adipic acid etc.), unsaturated polybasic carboxylic acid (cyclobutane-1, the 2-dicarboxylic acids, 4-methyl cyclobutane-1, the 2-dicarboxylic acids, cyclopentene-1, the 2-dicarboxylic acids, 5-methyl cyclopentene-1, the 2-dicarboxylic acids, dicyclo [2,2,1] hept-2-ene"-2, the 3-dicarboxylic acids, 1-methyl bicycle [2,2,1] hept-2-ene"-2, the 3-dicarboxylic acids, 6-methyl bicycle [2,2,1] hept-2-ene"-2, the 3-dicarboxylic acids, dicyclo [2,2,1] heptan-2,5-diene-2, the 3-dicarboxylic acids, 1-methyl bicycle [2,2,1] heptan-2,5-diene-2, the 3-dicarboxylic acids, 6-methyl bicycle [2,2,1] heptan-2,5-diene-2, the 3-dicarboxylic acids, furans-2, the 3-dicarboxylic acids, 5-methylfuran-2, the 3-dicarboxylic acids, 4-methylfuran-2, the 3-dicarboxylic acids, 4,5-dihydroxy furans-2, the 3-dicarboxylic acids, 4,5-dihydroxy-4-methylfuran-2, the 3-dicarboxylic acids, 4,5-dihydroxy-5-methylfuran-2, the 3-dicarboxylic acids, 2,5-dihydroxy furans-3, the 4-dicarboxylic acids, 2,5-dihydroxy-2-methylfuran-3,4-dicarboxylic acids etc.Wherein preferred cyclobutane-1, the 2-dicarboxylic acids, 4-methyl cyclobutane-1, the 2-dicarboxylic acids, cyclopentene-1, the 2-dicarboxylic acids, 5-methyl cyclopentene-1, the 2-dicarboxylic acids, dicyclo [2,2,1] hept-2-ene"-2, the 3-dicarboxylic acids, dicyclo [2,2,1] heptan-2,5-diene-2,3-dicarboxylic acids, furans-2, the 3-dicarboxylic acids, 5-methylfuran-2, the 3-dicarboxylic acids, 4-methylfuran-2, the 3-dicarboxylic acids, 5-methylfuran-2, the 3-dicarboxylic acids, 4,5-dihydroxy furans-2,3-dicarboxylic acids, 2,5-dihydroxy furans-3, the 4-dicarboxylic acids, maleic acid, fumaric acid, itaconic acid, citraconic acid, 1,2-cyclobutadiene-1, the 2-dicarboxylic acids, the 4-methyl isophthalic acid, 2-cyclobutadiene-1,2-dicarboxylic acids, 1,2-cyclopentadiene-1, the 2-dicarboxylic acids, the 5-methyl isophthalic acid, 2-cyclopentadiene-1,2-dicarboxylic acids, 1,2-cyclohexadiene-1, the 2-dicarboxylic acids, the 6-methyl isophthalic acid, 2-cyclohexadiene-1,2-dicarboxylic acids, the 5-methyl isophthalic acid, 2-cyclohexadiene-1, the 2-dicarboxylic acids, furans-3, the 4-dicarboxylic acids, 2-methylfuran-3,4-dicarboxylic acids etc.Wherein preferred 1,2-cyclobutadiene-1,2-dicarboxylic acids, 4-methyl isophthalic acid, 2-cyclobutadiene-1,2-dicarboxylic acids, 1,2-cyclopentadiene-1,2-dicarboxylic acids, 5-methyl isophthalic acid, 2-cyclopentadiene-1,2-dicarboxylic acids, furans-3,4-dicarboxylic acids, 2-methylfuran-3,4-dicarboxylic acids etc.)], aromatic series polybasic carboxylic acid [phthalic acid, M-phthalic acid, terephthalic acid (TPA), trihemellitic acid, pyromellitic acid etc.], sulfur-bearing polybasic carboxylic acid [thiodipropionic acid etc.];
◆ the hydroxycarboxylic acid of carbon number 2 to 20: aliphatic hydroxyl carboxylic acid [glycolic acid, lactic acid, tartaric acid, Castor Oil Fatty Acid etc.]; Aromatic hydroxy-carboxylic [salicylic acid, mandelic acid, 4-hydroxybenzoic acid, 1-hydroxyl-2-naphthoic acid, 3-hydroxyl-2-naphthoic acid, 6-hydroxyl-2-naphthoic acid etc.];
◆ the monocarboxylic acid of carbon number 1 to 30: aliphat monocarboxylic acid [saturated monocarboxylic acid (formic acid, acetate, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, laurate, myristic acid, stearic acid, behenic acid, hendecanoic acid etc.), unsaturated monocarboxylic acid (acrylic acid, methacrylic acid, crotonic acid, oleic acid, squaric acid, 4,5-dihydroxy-4-cyclopentene-1,3-diketone, 2,3-dihydroxy-2-cyclohexene-1,4-diketone etc.)]; Aromatic series monocarboxylic acid [benzoic acid, cinnamic acid, naphthoic acid, toluic acid, ethyl benzoate, propylbenzoic acid, isopropyl acid, butylbenzoic acid, isobutyl-benzene formic acid, sec-butylbenzene formic acid, p t butylbenzoic acid, hydroxybenzoic acid, ethoxybenzoic acid, propoxy benzoic acid, the isopropoxy benzoic acid, butyl phenyl ether formic acid, the isobutoxy benzoic acid, the sec-butoxy benzoic acid, the tert-butoxy benzoic acid, amino benzoic Acid, N-methylamino benzoic acid, N-ethylamino benzoic acid, N-propyl group amino benzoic Acid, N-isopropyl amino benzoic Acid, N-butyl amino benzoic Acid, N-isobutylamino benzoic acid, N-sec-butyl amino benzoic Acid, N-tert-butyl group amino benzoic Acid, N, the N-dimethylaminobenzoic acid, N, N-diethyl amino yl benzoic acid, nitrobenzoic acid, fluobenzoic acid etc.]
(phenol)
◆ 1 yuan of phenol (comprising phenol, aphthols): phenol, alkyl (carbon number 1 to 15) phenol (cresols, xylenols, ethyl-phenol, n-pro-pyl or isopropyl-phenol, Permethyl 99A base phenol etc.), methoxyl group phenols (eugenol, guaiacol etc.), alpha-Naphthol, betanaphthol, cyclohexylphenol etc.;
◆ polyhydric phenols: catechol, resorcinol, 1,2,3,-thrihydroxy-benzene, phloroglucin, bisphenol-A, Bisphenol F, bisphenol S etc.
(phosphate that has the alkyl of 1 to 2 carbon number 1 to 15 in the molecule)
Monomethyl and dimethyl phosphate, an isopropyl and diisopropyl phosphate, monobutyl and dibutylphosphoric acid ester, (2-ethylhexyl) and di-(2-ethylhexyl)phosphoric acid ester, an isodecyl and diiso decyl phosphate etc.
(organic sulfonic acid)
Alkyl (carbon number 1 to 15) benzene sulfonic acid (p-methyl benzenesulfonic acid, nonyl benzene sulfonic acid, DBSA etc.), sulfosalicylic acid, methanesulfonic acid, trifluoromethanesulfonic acid etc.
(organic acid) with triazole, tetrazolium skeleton
1-H-1,2,4-triazole, 1,2,3-triazoles, 1,2,3-BTA, carboxyl benzotriazole, 3-sulfydryl-1,2,4-triazole, 1,2,3-triazoles-4,5-dicarboxylic acids, 3-sulfydryl-5-methyl isophthalic acid, 2,4-triazole, 1,2,3,4-tetrazolium etc.
(boracic organic acid)
Boron two (oxalic acid), boron two (glycolic acid), boron two (2-hydroxy-iso-butyric acid), alkylboronic acids, aryl boric acid, methane boric acid, ethane boric acid, phenylboric acid etc.
The anion that following formula is represented
[(R
f)
kBF
4-k]
-
(in the formula, k represents 1 to 4 integer; R
fIdentical with aforementioned implication).
Trifluoromethyl three borofluorides, two (trifluoromethyl boron difluoride hydrochlorate, three (trifluoromethyl) borofluoride, four (trifluoromethyl) borate, pentafluoroethyl group three borofluorides, two (pentafluoroethyl group) three borofluorides, three (pentafluoroethyl group) borofluoride, four (pentafluoroethyl group) borate etc.
The anion that following formula is represented
(in the formula, R ' expression can have alkyl or the hydrogen atom or the fluorine atom of the substituent carbon number 1 to 10 that is selected from hydroxyl, amino, nitro, cyano group, chloro, fluorine-based, formoxyl or band ehter bond group.R ' mutually can be identical or different.R ' can be used as the alkylidene combination and the formation ring mutually)
The anion that following formula is represented
(in the formula, R " the expression implication identical with R '.R " mutually can be identical or different.R " can be used as the alkyl combination mutually and the formation ring)
The anion that following formula is represented
(in the formula, R
1And R
2The fluorine-containing 1 valency organic group of expression carbon number 1 to 4; R
1And R
2Identical can be identical or different.R
3The fluorine-containing divalent organic group of expression carbon number 2 to 8)
As anion, preferred inorganic anion, especially preferred BF
4 -, AsF
6 -, SbF
6 -, wherein from having the especially preferred BF of tendency consideration that static capacity increases
4 -
The electrolyte that contains organic bath can use with the solvent of organic polar solvent as principal component, and the water content that contains in the electrolyte of organic polar solvent is generally below the 200ppm, below the preferred 50ppm, below the further preferred 20ppm.Water content by in the electrolyte that suppresses to contain organic polar solvent can suppress the influence of water electrolysis to electrode, the particularly decline of proof voltage.
Be used to dissolve the solvent of electrolyte solution, can use with aforesaid imidazoles cation in the identical solvent that uses.
As electrolytical concentration in the electrolyte, can enumerate with aforementioned imidazoles cation in identical concentration when using.
As the method for the electrode that uses the activated carbon obtain like this to use as double electric layer capacitor, for example can enumerate: the method for using with the proterties former state after the carbonization; The method of the activated carbon after the use fragmentation; Activated carbon after the fragmentation is configured as the method used behind the different shape of material, fibrous, felted, textile-like or sheet etc. etc.The particle diameter of the active carbon particle that uses in the manufacturing process, pulverizing usually is below the 50 μ m, below the preferred 30 μ m, the average grain diameter that especially preferred 10 μ m are following.By bulk density, can reduce internal resistance with activated carbon raising electrode in small, broken bits.
In the breaking method, suitable use is the pulverizer of fine pulverizing usefulness such as impact friction pulverizer, centrifugal force pulverizer, ball mill (tube mill, compound mill, cylindroconical ball mill, rod mill), vibration milling, colloid mill, friction circle mill, jet mill for example.
In the breaking method, generally use ball mill, when using ball mill, for fear of the pick-up metal powder, ball or crushing container are preferably with nonmetal making such as aluminium oxide, zirconia, agates.
Electrode of the present invention is characterised in that and contains aforementioned activated carbon.Usually to be configured as electrode easily in order making, in electrode, also to contain adhesive, conductive agent etc.
As the manufacture method of electrode, the mixture that normally will contain activated carbon, adhesive, conductive agent etc. forms on current-collector.Particularly, for example can enumerate: with the slurry that in activated carbon, adhesive, conductive agent etc., adds solvent and mix by scraping coating such as the skill in using a kitchen knife in cookery or being dispersed on the collector body method of drying then; For example: activated carbon, adhesive, conductive agent etc. are added to carry out mixing, shaping, drying in the solvent, resulting sheet material is bonded in the current-collector surface by conductive adhesive, suppress method then with the heat treatment drying; For example: the mixture that activated carbon, adhesive, conductive agent and aqueous lubricant etc. are constituted is removed aqueous lubricant after being shaped on the current-collector, then, resulting sheet-like formed thing is carried out the method for single shaft or the stretch processing of multiaxis direction etc.
When electrode forming was sheet, its thickness was about 50 to about 1000 μ m.
As the material of current-collector, for example can enumerate: the metal of nickel, aluminium, titanium, copper, gold, silver, platinum, aluminium alloy, stainless steel etc.; For example: by on material with carbon element, activated carbon fiber, nickel, aluminium, zinc, copper, tin, lead or their alloy being carried out the material that plasma spray coating or arc spraying form; For example: dispersed electro-conductive agent in rubber, styrene-ethylene-butylene-styrene copolymer resins such as (SEBS) and conducting film of forming etc.Special preferred weight is light, the aluminium of excellent conductivity, electrochemical stability.
As the shape of current-collector, for example can enumerate: paper tinsel, tabular, mesh-like, netted, lath-shaped, perforation shape or embossing shape, perhaps shape that they are combined (for example netted flat board etc.) etc.
The current-collector surface can form concavo-convex by corrosion treatment.
Conductive agent for example can be enumerated: the conductive carbon material of graphite, carbon black, acetylene black, Kai Jinhei (ケ Star チ エ Application グ Block ラ Star Network), activated carbon different with the present invention etc.; Graphite-like conductive agents such as native graphite, thermal expansion graphite, flaky graphite, expanded graphite; The carbon fiber of gas-phase growth of carbon fibre etc.; The metal microparticle or the metallic fiber of aluminium, nickel, copper, silver, gold, platinum etc.; The conducting metal oxide of ruthenium-oxide or titanium oxide etc.; The conducting polymer of polyaniline, polypyrrole, polythiophene, polyacetylene, polyacene etc. etc.
Consider preferred especially carbon black, acetylene black and Kai Jinhei from the viewpoint that improves conductivity on a small quantity and effectively.
The combined amount of conductive agent in the electrode with respect to activated carbon 100 weight portions of the present invention, is generally about 5 to about 50 weight portions, and preferred about 10 to about 30 weight portions.
As adhesive, for example can enumerate: the polymer of fluorine compounds.As fluorine compounds, for example can enumerate: (methyl) acrylic acid fluorinated alkyl (carbon number 1 to 18) ester, (methyl) perfluoroalkyl acrylate [for example, (methyl) acrylic acid perfluor dodecyl ester, (methyl) acrylic acid perfluor n-octyl ester, (methyl) acrylic acid perfluor n-butyl], the Arrcostab that (methyl) acrylic acid perfluoroalkyl replaces [for example, (methyl) acrylic acid perfluoro hexyl ethyl ester, (methyl) acrylic acid perfluoro capryl ethyl ester], (methyl) acrylic acid perfluoro alkoxy alkyl ester [for example, (methyl) acrylic acid perfluor dodecyloxy ethyl ester and (methyl) acrylic acid perfluor oxygen in last of the ten Heavenly stems base ethyl ester etc.], crotonic acid fluorinated alkyl (carbon number 1 to 18) ester, maleic acid fluorinated alkyl (carbon number 1 to 18) ester and fumaric acid fluorinated alkyl (carbon number 1 to 18) ester, itaconic acid fluorinated alkyl (carbon number 1 to 18) ester, alkene (the carbon number about 2 to about 10 that fluorinated alkyl replaces, number of fluorine atoms about 1 to about 17), perfluoro hexyl ethene for example, carbon number about 2 to about 10 and number of fluorine atoms about 1 combine the fluorinated olefins of fluorine atom to about 20 the double key carbon, tetrafluoroethene, trifluoro-ethylene, vinylidene fluoride, hexafluoropropylene etc.
Other illustration as adhesive, can enumerate: the addition polymer of the monomer that contains olefinic double bond of contain fluorine atoms not, described monomer for example can be enumerated: (ring) alkyl (carbon number 1 to 22) (methyl) acrylate [(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid stearyl etc.]; Contain aromatic ring (methyl) acrylate [(methyl) benzyl acrylate, (methyl) phenyl acrylate etc.]; Contract list (methyl) acrylate [(methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, diethylene glycol list (methyl) acrylate] of two alkylene glycol (carbon number 2 to 4 of alkylene base) of alkylene glycol or; List (methyl) acrylate of (gathering) glycerine (degree of polymerization 1 to 4); (methyl) acrylic ester monomer of multifunctional (methyl) acrylate [(gathering) ethylene glycol (degree of polymerization 1 to 100) two (methyl) acrylate, (gathering) propylene glycol (degree of polymerization 1 to 100) two (methyl) acrylate, 2, two (4-ethoxy phenyl) propane two (methyl) acrylate of 2-, trimethylolpropane tris (methyl) acrylate etc.] etc.; (methyl) acrylamide monomers of (methyl) acrylamide, (methyl) acryloyl amide derivatives [N-methylol (methyl) acrylamide, DAAM etc.] etc.; The cyano-containing monomer of (methyl) acrylonitrile, (methyl) 2 cyanoethyl acrylate, 2-cyano group ethyl ester acrylamide etc.; The styrene monomer of the styrene derivative of styrene and carbon number 7 to 18 [AMS, vinyltoluene, para hydroxybenzene ethene and divinylbenzene etc.] etc.; The dienes monomer of the alkadienes of carbon number 4 to 12 [butadiene, isoprene, chlorobutadiene etc.] etc.; The thiazolinyl esters monomer of carboxylic acid (carbon number 2 to 12) vinyl acetate [vinyl acetate, propionate, vinyl butyrate and sad vinyl acetate etc.], carboxylic acid (carbon number 2 to 12) (first generation) allyl ester [acetate (first generation) allyl ester, propionic acid (first generation) allyl ester and sad (first generation) allyl ester etc.] etc.; Glycidyl (methyl) acrylate and (first generation) allyl glycidyl ether etc. contain the epoxy radicals monomer; The monoene hydro carbons of the monoolefine of carbon number 2 to 12 [ethene, propylene, 1-butylene, 1-octene and 1-laurylene etc.]; Chloride, bromine or iodine atom monomer be the monomer of the halogen atom beyond the contain fluorine atoms of vinyl chloride and vinylidene chloride etc. for example; (methyl) acrylic compounds of acrylic acid, methacrylic acid etc.; The monomer that contains conjugated double bond of butadiene, isoprene etc. etc.
In addition, as addition polymer, for example can enumerate: the copolymer that comprises multiple monomer of vinyl-vinyl acetate copolymer, Styrene-Butadiene, ethylene-propylene copolymer etc.In addition, the carboxylic acid vinyl ester polymer can resemble partly or completely saponification polyvinyl alcohol etc.
As adhesive, also can be fluorine compounds and the copolymer of the monomer having ethylenic double bond of contain fluorine atoms not.
As other illustration of adhesive, for example can enumerate: the polysaccharide and the derivative thereof of starch, methylcellulose, carboxymethyl cellulose, CMC, carboxyethyl cellulose, carboxy-propyl cellulose, carboxymethyl hydroxyethyl cellulose, NC Nitroncellulose etc.; Phenol resin; Melmac; Polyurethane resin; Urea resin; Polyimide resin; Polyamide-imide resin; Petroleum asphalt; Coal tar pitch etc.
As adhesive, the polymer of preferred fluorinated compound wherein, the polymer poly tetrafluoroethene of especially preferred tetrafluoroethene.
Adhesive also can use multiple adhesive.
The combined amount of adhesive in the electrode with respect to activated carbon 100 weight portions, is generally about 0.5 to about 30 weight portions, and preferred about 2 to about 30 weight portions.
As operable solvent in the adhesive, for example can enumerate: the alcohols of IPA (isopropyl alcohol), ethanol, methyl alcohol etc.; And ethers, ketone etc.During the adhesive height thickness, be coated with to current-collector easily, can use plasticizer in order to make.
So-called electrically conductive adhesive, the mixture of normally aforementioned conductive agent and aforementioned adhesion agent, wherein, the mixture of carbon black and polyvinyl alcohol need not be with an organic solvent, and preparation is easy, and keeping quality is good, therefore is fit to use.
Electrode of the present invention for example can be applied to: the electrode of dry cell, redox capacitor, mixed capacitor, double electric layer capacitor etc.
At this, so-called redox capacitor is meant for example to resemble [big capacity Electricity mood two-fold
The most preceding gland of キ ヤ パ シ (Prison Xiu Tian village hero, the エ ヌ テ イ one エ ス of the capable institute of stool)] the 3rd chapter (p141～) put down in writing like that, to contain active material in the electrode, be the capacitor of feature by the redox reaction electric power storage.By between 2 plate electrodes, sandwich with double electric layer capacitor described later in the identical dividing plate that uses, and filling electrolyte and constituting.Among the present invention, electrolyte is meant the mixture of electrolyte and solvent.
The active material that uses in the redox capacitor can be enumerated transition metal oxide, transition metal hydroxide, conducting polymer of ruthenium etc. etc.The activated carbon of the present invention activated carbon independent or of the present invention and the mixture of above-mentioned illustrative conductive agent and the above-mentioned illustrative adhesive of 2 to 30 weight % that contain 1 to 60 weight % in the electrode.
Electrolyte as the use of redox capacitor,, for example can enumerate during at the transition metal oxide that uses ruthenium etc. or transition metal hydroxide: the use of aqueous sulfuric acid etc. under the condition described in the TOHKEMY 2002-359155 communique as active material.In addition, use organic acid, use when being dissolved in the electrolyte that organic solvent forms, for example can enumerate: the application of the described condition of TOHKEMY 2002-267860 communique etc. as electrolyte.When using conducting polymer,, use the electrolyte that is dissolved in organic solvent and can dissociates to get final product, for example can enumerate: LiBF as electrolyte as active material
4, LiPF
6, LiClO
4Deng lithium salts.Especially, use preferably that degree of ionization is big, the LiPF of favorable solubility
6These electrolyte can use separately, perhaps can be with being used in combination more than 2 kinds wherein.Consider the good reason of ionic conduction degree, the electrolytical concentration in the preferred electrolyte is 0.5 to 1.5mol/L.Electrolytical concentration is 0.5mol/L when above, considers it is preferred from having the tendency that static capacity improves, and when be 1.5mol/L when following, is preferred from the tendency that viscosity descends, the ionic conduction degree the rises consideration with electrolyte.
Contained solvent in the electrolyte that the redox capacitor is used preferably uses illustrated organic polar solvent in the double electric layer capacitor described later.Wherein, preferably use non-proton polar organic solvent, for example, can use the mixed solvent more than a kind or 2 kinds of cyclic carbonate, linear carbonate, cyclic ester etc.Cyclic carbonate can the illustration ethylene carbonate, propylene carbonate etc., and linear carbonate can the illustration dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate etc., and cyclic ether can the illustration gamma-butyrolacton, gamma-valerolactone etc.In these any one can use separately, also can two or more mixing use.Electrolyte requires to have high-k in order to promote electrolytical disassociation, and requires to have low viscosity in order not hinder moving of ion, and requires anti-electrochemical redox height.Therefore, carbonates is particularly suitable as solvent, for example, preferably high dielectric constant solvent ethylene carbonate etc. and low adhesive solvent diethyl carbonate etc. is used in combination.
So-called mixed capacitor, when being meant with charging, lithium ion inserts between the carbon-coating of graphite etc. in negative pole, and electrolytical anion is attracted on the electrode surface and constitutes double electric layer capacitor in positive pole, and electric power storage is the capacitor of feature thus.Negative pole uses the electrode identical with the negative pole of lithium rechargeable battery, the above-mentioned electrode of the present invention of anodal use, the clamping dividing plate identical with double electric layer capacitor described later between positive pole and negative pole, and filling electrolyte and constituting.Negative pole may use the negative pole of [inferior generation type リ チ ウ system secondary Electricity pond (Prison Xiu Tian village hero, the エ ヌ テ イ one エ ス of the capable institute of development)] the 1st chapter the 3rd joint (p25～) record particularly.
The electrolyte that mixed capacitor is used can use the combination of inorganic anion and lithium ion usually, especially preferably from BF
4 -, PF
6 -, ClO
4 -At least a inorganic anion of selecting in the group of forming and the combination of lithium ion.
Contained organic polar solvent in the electrolyte as mixed capacitor can use at least a solvent of selecting with in the group that carbonates and lactone are formed as principal component usually.Particularly, can illustration: the solvent of the linear carbonate class of the cyclic carbonates of propylene carbonate, ethylene carbonate, butylene carbonate etc., dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate etc., gamma-butyrolacton etc., the mixed solvent of preferred ethylene carbonate and the linear carbonate more than a kind, gamma-butyrolacton is independent, the mixed solvent equal solvent of gamma-butyrolacton and the linear carbonate more than a kind.
As additive, can use illustrated additive in the double electric layer capacitor item.
Electrode of the present invention is particularly suitable for double electric layer capacitor because of static capacity is good.Below, be elaborated for double electric layer capacitor.
Double electric layer capacitor of the present invention is characterized in that containing above-mentioned electrode, particularly, for example can enumerate: between the two, having independently dividing plate as the positive pole of above-mentioned electrode and negative pole, be filled with the capacitor of electrolyte between dividing plate and electrode; For example: be filled with capacitor of solid electrolyte (gel electrolyte) etc. between the two as the positive pole of above-mentioned electrode and negative pole.
By charging, anodal band+electricity forms electric double layer by negative electrolyte on the interface of positive pole, and negative pole band-electricity forms electric double layer by positive electrolyte on the interface of negative pole simultaneously, thus can store electrical energy.Even stop charging, electric double layer also is held, but when discharge, electric double layer is eliminated, and electric energy discharges.
Double electric layer capacitor both can be a unit that contains anodal and negative pole, also can be the capacitor that in addition a plurality of unit combination is formed.
So-called solid electrolyte is that electrolyte described later is scattered in the electrolyte that forms in the resin, can further be scattered in the organic polar solvent described later.Particularly, can enumerate [big capacity Electricity mood two-fold
The most preceding gland of キ ヤ パ シ (Prison Xiu Tian village hero, the エ ヌ テ イ one エ ス of the capable institute of stool)] gel electrolyte, TOHKEMY 2004-172346 communique and citing document thereof, TOHKEMY 2004-303567 communique and citing document thereof, TOHKEMY 2003-68580 communique and citing document thereof, the TOHKEMY 2003-257240 communique etc. of p79 record in the solid electrolyte of record.
For double electric layer capacitor of the present invention, has independently dividing plate as the positive pole of above-mentioned electrode and negative pole between the two, the double electric layer capacitor that is filled with electrolyte between dividing plate and electrode is fit to, and below is elaborated for this double electric layer capacitor.
The shape of double electric layer capacitor for example can be enumerated: Coin shape, convoluted, laminated-type, accordion type (snake belly type) etc.
Production Example as Coin shape, can enumerate as shown in Figure 1, go up order lamination current-collector (12), electrode (13), dividing plate (14), electrode (13) and current-collector (12) at the metallic container (11) of stainless steel etc., after the electrolyte filling, cover the method for (15) and pad (16) sealing etc. with metallic.
As convoluted Production Example, can enumerate as shown in Figure 2, go up mixed slurry and the drying that coating contains above-mentioned activated carbon at current-collector (22), the laminate of preparation current-collector (22) and electrode (23), 2 pieces of these sheets are inserted dividing plate (24) therein reel, the method in the metallic container (21) of aluminium, stainless steel etc. of cylinder type etc. of packing into electrode hush panel (25) then.
In addition, have lead in advance on current-collector, the lead of a laminate (26) is made as positive pole, and the lead of another laminate (26) is made as negative pole, charges and discharges.
As laminated-type, can enumerate as shown in Figure 3,, insert then in the metallic container (31) of aluminium, stainless steel etc. the laminate and dividing plate (34) alternatively laminated of current-collector (32) and electrode (33), filling electrolyte, the method that current-collector and lead (35) alternately are connected and seal; As shown in Figure 4, with the laminate and the alternately crimping of dividing plate (44) of current-collector (42) and electrode (43), with sealable outers such as elastomeric materials, and filling electrolyte, then, the method that seals etc.In addition, as be fit to the to have pad dipolar configuration of (46), can be the structure that to set working voltage arbitrarily.
Embodiments of the invention, by as shown in Figure 5, by between increased pressure board (51), the electrode (53), dividing plate (54), electrode (53), current-collector (52) and the insulating material (55) that are configured as sheet are carried out lamination, filling electrolyte between dividing plate (54) and electrode (53), use the fluororesin sealable outer, and implement with the double electric layer capacitor of bolt fastening.In addition, bolt insulate with the current-collector of (52).
The accordion type is 2 pieces of the sheet materials of electrode and current-collector to be inserted dividing plate therein be folded into the accordion shape and carry out lamination simultaneously, then with the same method of making of laminated-type.
The dividing plate that uses in the double electric layer capacitor is used for positive pole is separated with negative pole, and keeps electrolyte, therefore uses to have big ion permeability, the dielectric film with specify mechanical intensity.
As dividing plate, for example can enumerate: viscose glue, the paper that native cellulose etc. are made, electrolytic paper, brown paper, Manila paper, the fiber of cellulose or polyester etc. is copied the mixed paper that paper obtains, the polyethylene nonwoven fabrics, polypropylene non-woven fabric, polyester non-woven fabric, glass fibre, porous polyethylene, porous polypropylene, porous polyester, aramid fibre, the polybutylene terephthalate nonwoven fabrics, contraposition fully aromatic polyamide (パ ラ is an all aromatic Port リ ア ミ De), vinylidene fluoride, tetrafluoroethene, the copolymer of vinylidene fluoride and hexafluoropropylene, the nonwoven fabrics of the fluorine resin of fluorubber etc. etc. or perforated membrane etc.
As dividing plate, can be the shaping thing that ceramic powders particle and aforementioned adhesion agent by silicon dioxide etc. constitute.This shaping thing is integrally formed with positive pole and negative pole usually.In addition, about using the dividing plate of polyethylene or polypropylene etc., can mixed surfactant or silicon dioxide granule in order to improve hydrophily.In addition, in dividing plate, can contain the plasticizer etc. of the organic solvent, dibutyl phthalate (DBP) etc. of acetone etc.
As dividing plate, can use ionic conduction type polymer.
As dividing plate, the paper that especially preferred electrolytic paper, viscose glue or natural fiber are made, copy paper with brown paper, Manila paper, with the fiber of cellulose or polyester and the mixed paper that obtains, polyethylene nonwoven fabrics, polypropylene non-woven fabric, polyester non-woven fabric, abaca sheet material, glass fibre sheet etc.
The aperture of dividing plate is generally about 0.01 to about 10 μ m.The thickness of dividing plate is generally about 1 to about 300 μ m, and preferred about 5 to about 30 μ m.
Dividing plate also can be the dividing plate lamination that porosity is different and the dividing plate that obtains.
Embodiment
Below, illustrate in greater detail the present invention based on embodiment, still, the present invention is not subjected to any restriction of these embodiment.
Embodiment 1
In reaction vessel, mix resorcinol 33.0 grams, 37 weight % formalin 48.7, sodium carbonate 0.16 gram and distilled water 22 grams,, obtain organic aerogel with water-wet 50 ℃ of insulations 24 hours.At this moment, the use amount of per 1 mol alkali catalyst phenoloid is 200 moles, and the use amount of per 1 weight parts water (in the formalin contained water and distilled water sum) phenoloid is 0.63 weight portion.
In the gel that obtains, add tert-butyl alcohol washing, the water in the above-mentioned gel is replaced into the tert-butyl alcohol.Gel after the tert-butyl alcohol displacement after 24 hours, carrying out roasting at 800 ℃-30 ℃ of freeze dryings under argon atmospher under the vacuum, is obtained activated carbon.Its void content of the activated carbon that obtains is 0.47cc/g.
The activated carbon that obtains is pulverized, the mixture of Powdered thing 80 weight portions of gained, carbon black 10 weight portions and polytetrafluoroethylene 10 weight portions is carried out mixing, be configured as sheet then.Between 2 pieces of the sheet materials that obtains, put into paper as dividing plate after, fill 3mol/L EMI
+BF
4 -The polypropylene carbonate ester solution of salt obtains the bipolar system double electric layer capacitor as electrolyte.
Use this capacitor to carry out constant current charge-discharge and measure (100mA/g), the static capacity that records the per unit volume of activated carbon thus is 21.3F/cc, and the static capacity of per unit weight is 20.2F/g.The result is as shown in table 1.
Embodiment 2～3, comparative example 1
In embodiment 1, use resorcinol 27.5 grams, 37 weight % formalin, 40.6 grams, sodium carbonate 0.13 gram and distilled water 55.1 grams, sintering temperature is made as 1000 ℃, and use the described electrolyte of table 1 is filled into the electrolyte that obtains in the propylene carbonate, in addition, implement similarly to Example 1, obtain the bipolar system double electric layer capacitor.The result is as shown in table 1.
Table 1
| Electrolyte | Sintering temperature (℃) | Static capacity | ||||
| Concentration | Cation | Anion | (F/cc) | (F/g) | ||
| Embodiment 1 | 3mol/L | EMI + | BF 4 - | 800 | 21.3 | 20.2 |
| 2 | 1mol/L | EMI + | CF 3CO - | 1000 | 11.5 | 16.5 |
| 3 | 1mol/L | BMI + | BF 4 - | 1000 | 9.1 | 13.0 |
| Comparative example 1 | 1mol/L | TEA + | BF 4 - | 1000 | 6.8 | 9.8 |
EMI
+: 1-ethyl-3-methylimidazole (formula (2))
BMI
+: 1-butyl-3-methylimidazole (formula (3))
TEA
+: tetraethyl ammonium
Embodiment 4 to 7
In embodiment 1, the use amount of per 1 weight parts water (water that formalin is contained and distilled water sum) phenoloid is used the value shown in the table l, and sintering temperature uses the value shown in the table 2, and electrolyte uses tetraethyl ammonium BF
4Salt, electrolyte is adjusted to 1mol/L, carries out the constant current charge-discharge of 30mA/g and measures, and in addition, implements according to embodiment 1.The result is as shown in table 2.
Table 2
| R/W*1 (weight portion) | Sintering temperature (℃) | Void content (cc/g) | Static capacity | ||
| (F/cc) | (F/g) | ||||
| Embodiment 4 | 0.63 | 800 | 0.47 | 21.3 | 20.2 |
| 5 | O.63 | 1000 | 0.43 | 10.7 | 9.7 |
| 6 | 0.66 | 800 | O.53 | 11.8 | 11.9 |
| 7 | 0.70 | 800 | O.41 | 11.1 | 9.8 |
| Comparative example 2 | 0.059 | 1000 | 3.5 | 3.2 | 12.8 |
* 1: the use amount of every l weight parts water (water that formalin is contained and distilled water sum) phenoloid
Comparative example 2
In embodiment 1, the use amount of per 1 weight parts water (water that formalin is contained and distilled water sum) phenoloid is used the value shown in the table 1, and sintering temperature uses the value shown in the table 2, and electrolyte uses tetraethyl ammonium BF
4Salt, electrolyte is adjusted to 1mol/L, carries out the constant current charge-discharge of 30mA/g and measures, and in addition, implements according to embodiment 1.The result is as shown in table 2.
Industrial applicability
Activated carbon of the present invention, can be suitable for such as: used for dry cell electrode, piezoelectric element with the electrode of sensor, the carrier that is used for supported catalyst, chromatographic grade material, adsorbent, double layer capacitor etc., because the static capacity of per unit volume is good so be suitable for the electrode of double layer capacitor.
Double layer capacitor of the present invention because the static capacity of per unit volume is good, therefore can be used for absorption, the storage of the energy. Particularly because its good characteristic, can be suitable for the terminal field of portable electronic or have the absorption, storage etc. of the haulage vehicle energy of charge function.
Claims (12)
1. a double electric layer capacitor comprises electrode, electrolyte and dividing plate, and described electrode contains activated carbon, and described electrolyte contains electrolyte, wherein:
Electrolyte is formula (I)
(in the formula, R and R ' represent the alkyl of carbon number 1 to 6, R independently of one another
1～R
3Represent the alkyl of hydrogen atom or carbon number 1 to 6 independently of one another, X-represents counter ion counterionsl gegenions)
The imidazolium salts of expression, activated carbon is the activated carbon by the organic aerogel carbonization is obtained, and described organic aerogel obtains by phenoloid and the aldehyde compound polymerization that has at least one hydroxyl in the presence of aqueous solvent and base catalyst in molecule.
2. double electric layer capacitor according to claim 1, wherein electrolytical counter ion counterionsl gegenions are for being selected from by trifluoroacetic acid root (CF
3CO
2 -) and tetrafluoroborate (BF
4 -) at least a ion in the group formed.
3. double electric layer capacitor according to claim 1, wherein phenoloid is a resorcinol.
4. double electric layer capacitor according to claim 1, wherein activated carbon is the activated carbon by using 0.25 to 1000 mole of phenoloid with respect to 1 mole of base catalyst, using 0.5 to 5 weight portion phenoloid to obtain with respect to aqueous solvent 1 weight portion.
5. double electric layer capacitor according to claim 1, wherein activated carbon is the activated carbon that obtains 650 to 850 ℃ of following carbonizations.
6. double electric layer capacitor according to claim 1, wherein activated carbon is the following activated carbon of void content 1.5cc/g.
7. the following activated carbon of a void content 1.5cc/g, it is to carry out carbonization by the organic aerogel that the phenoloid that has at least one hydroxyl in the molecule and aldehyde compound polymerization will be obtained to obtain.
8. according to the activated carbon of claim 7, wherein phenoloid is a resorcinol.
9. electrode, it contains the described activated carbon of claim 7.
10. double electric layer capacitor, it contains the described electrode of claim 9, dividing plate and electrolyte.
11. activated carbon manufacture method, carry out carbonization by the organic aerogel that the phenoloid that has at least one hydroxyl in the molecule and aldehyde compound polymerization will be obtained and make activated carbon, wherein, use 0.25 to 1000 mole of phenoloid, use 0.5 to 5 weight portion phenoloid to carry out polymerization with respect to 1 mole of base catalyst with respect to aqueous solvent 1 weight portion.
12. manufacture method according to claim 11 is wherein carried out carbonization under 650 to 850 ℃.
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