TW201142885A - Electric double layer capacitor - Google Patents

Abstract

An electric double layer capacitor which has a high electronic capacity and a low internal resistance, and whose withstanding voltage is high is provided. The present invention provides an electrode for the electric double layer capacitor including an activated carbon particle obtained by steam processing a non-graphitizing particle, a binding material, a Ketchen Black and an acrylic-based compound, and the electric double layer capacitor comprising the electrode.

Description

201142885 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an electric double layer capacitor. [Prior Art] Electric double layer capacitors are expected to be discussed as electric power sources or power sources in the event of an instantaneous power failure. In this case, an electric double layer capacitor is expected to have a high electrostatic capacity and a low internal resistance, and a solvent for dissolving the electrolyte is a water-based solvent (Patent Document 1) or a non-fluorine-based non-aqueous solvent (Patent Document 2). Or a fluorine-based non-aqueous solvent (Patent Document 3). Further, in the non-aqueous solvent, Patent Document 2 also proposes a structure of an electrode, which has a method of activating the molten KOH (alkali activation treatment). The spherical activated carbon and the conductivity imparting agent and the polymer binder which are activated by the specific particle diameter and the pore volume have a specific bulk density, and a high electrostatic capacity and a low internal resistance can be realized. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2007-157976 (Patent Document 2) JP-A-2001-143973 (Patent Document 3) International Publication No. 2008/084846 [The problem to be solved by the invention] The electric double layer capacitor requires not only the above-mentioned high electrostatic capacity and low internal resistance, but also a high withstand voltage corresponding thereto. -5- 201142885 The object of the present invention is to provide an electric double layer capacitor having a high electrostatic capacity and a low internal resistance and having a high withstand voltage. [Means for Solving the Problem] The present invention relates to an activated carbon particle (IA), a binder (IB), a Ketjen black (1C), and an acrylic compound which are obtained by activating water vapor of non-graphitizable carbon. An electrode for an electric double layer capacitor of an electrode layer of (ID). In the electrode of the present invention, the electrode layer is preferably provided on the conductive film formed on the surface of the current collector. Further, the electrode layer has an electrode density of 0.45 g/cm3 or less. The present invention also relates to an electric double layer capacitor comprising the electrode of the present invention. The electric double layer capacitor of the present invention is preferably provided with a nonaqueous electrolytic solution as the electrolytic solution, and preferably a fluorine-based electrolytic solution. [Effect of the Invention] According to the present invention, an electric double layer capacitor having a high electrostatic capacity and a low internal resistance and having a high withstand voltage can be provided. [Embodiment] The electrode for an electric double layer capacitor of the present invention is characterized by comprising activated carbon particles (IA), a binder (IB), and Ketjen black (1C) obtained by activating water vapor of non-graphitizable carbon. An electrode layer of an acrylic compound (ID). Hereinafter, each configuration will be described. (IA) Specific activated carbon particles 201142885 In general, activated carbon particles have a function of increasing the electrostatic capacitance of an electric double layer capacitor. The activated carbon particles used in the present invention are activated carbon particles obtained by activating water vapor of non-graphitizable carbon particles. The activated carbon material has activated carbon (e.g., graphitizable carbon) which is easily graphitized, and activated carbon (hardly graphitizable carbon) which is difficult to graphitize. However, in the present invention, non-graphitizable carbon is used. Further, in order to activate the activated carbon particles, an activation treatment such as a steam activation treatment method or a molten KOH activation treatment method (alkali activation treatment method) may be employed. However, in the present invention, a steam activation treatment method is employed. The activated carbon particles obtained by activating the hardly graphitizable carbon by steam activation are excellent in characteristics such as a decrease in capacity when a high voltage is applied, and the reason is not clear. However, these characteristics are easy to graphitize and use. The case of carbon is improved as compared with the case of activation treatment by the molten KOH activation treatment. The non-graphitizable carbon refers to carbon which is difficult to graphitize even when subjected to high-temperature carbonization in an inert gas atmosphere, and can be distinguished from easily graphitizable carbon which is easily graphitized by the same carbonization treatment. The non-graphitizable carbon is generally one in which a thermosetting resin or a natural organic substance is carbonized, and the easily graphitizable carbon is a carbonized thermoplastic resin or petroleum pitch. Examples of the thermosetting resin which is a raw material of the non-graphitizable carbon include a phenol resin, an epoxy resin, an alkyd resin, a melamine resin, a urea resin, a urethane resin, an unsaturated polyester resin, and a decanoic acid. In addition to the allyl ester resin and the like, a fluorene resin, a polyoxyxylene resin, a furan resin, a fluorene resin, or the like can be given, and activated carbon particles can be obtained by carbonizing the granular material. 201142885 Natural organic matter, which is a raw material for hardly graphitizable carbon, is preferred from the viewpoint of ease of availability of natural coconut shells, and coconut shell carbon can be obtained by carbonizing a person who does not contain harmful impurities. The water vapor activation treatment of the non-graphitizable carbon may be a conventionally known method, and for example, it may be exemplified in a water vapor atmosphere, and the non-graphitizable carbon is preferably 500 to 100 (TC, more preferably 700 to 1). The method of treating at a temperature of 000 ° C for about 5 minutes to 10 hours is not limited by the above conditions. The activated carbon particles obtained by the steam activation treatment are further activated by being porous. The activated carbon particles subjected to steam activation treatment have an average particle diameter of 20 μηι or less, preferably ΙΟμηι or less, and a specific surface area of 1 500, from the viewpoint of obtaining an electric double layer capacitor having a large capacity and a low internal resistance. It is preferable that the activated carbon particles are not more than 3,000 m 2 /g, and the amount of potassium measured by the extraction method is about 0 to 200 ppm, or the activated carbon particles having a pore volume of 1.5 cm 3 /g or less are also preferable. For example, YP50F, YP50FH, YP80F, and YP80FH (all trade names) manufactured by KURARAY CHEMICAL Co., Ltd., etc., may be exemplified, but are not, for example, commercially available products of the non-graphitizable carbon-activated carbon particles of the coconut shell carbon. These limited persons" A commercially available product of a non-graphitizable carbon activated carbon particle which is subjected to steam activation treatment of a phenol resin, for example, an RP made by KURARAY CHEMICAL Co., Ltd., may be used as the phenol resin. -2 0 (trade name), etc., but not limited by them. (IB) Bonding material 201142885 Bonding material (IB) is based on the use of activated carbon particles (A) and Ketjen black added as a conductive material. When the other electrode components (1C) and the like are formed into electrodes, they are used to bind the particles to the user. Therefore, as long as the object can be achieved, there is no particular limitation, and polytetrafluoroethylene (PTFE) is usually used. a fluorine-based resin such as vinylidene fluoride (PVdF); a non-fluorine-based elastomer such as butadiene rubber or styrene-butadiene rubber. Among them, a fluorine-based resin is particularly useful from the viewpoint of good withstand voltage. PTFE is preferred, but the adhesion to the current collector is poor, and the workability or long-term reliability is lowered. Therefore, the pressure resistance is good and the adhesion to the current collector is good. An elastomeric acrylate copolymer is preferred. (1C) In the present invention, Ketjen Black (1C) functions as a conductive material. The conductive material which is an electrode material of a capacitor is an inactive carbon having a large specific surface area and has an effect of imparting electron conductivity, except for Ketchen Black. Further, for example, carbonaceous materials such as carbon black, acetylene black 'natural graphite, artificial graphite, and the like; metal materials such as metal fibers, conductive titanium oxide, and cerium oxide are known, and water-vapor is activated by using non-graphitizable carbon. When the obtained activated carbon particles (IA) are treated, a higher withstand voltage can be imparted by using Ketjen black (1C), and a high electrostatic capacity and a low internal resistance are obtained. As a commercial item of Ketchen Black (1C), for example, carbon ECP600JD manufactured by LION Co., Ltd. can be cited. (ID) Acrylic Compound 201142885 When the electrode is produced, the activated carbon particles (ΙΑ), the binder (IB), the Ketjen (1C), and other additives added as necessary are dispersed in a solvent, for example, dispersed in water to form a slurry. The body is formed by coating on a metal foil or a current collector. At this time, the particles are uniformly dispersed in the slurry, and a tackifier is added in order to adjust the fluidity to an appropriate fluidity. Since the tackifier component remains in the electrode, it has an effect on the electrostatic capacity, the internal resistance, and the withstand voltage. In the present invention, the acrylic compound (ID) is a tackifier as described above, and the components added by the activated carbon particles (IA), the binder (IB), and the ketjen black (1C) are unexpectedly added. Other compounds known as tackifiers, such as carboxymethyl cellulose (CMC), have a high withstand voltage, and have a large effect on the performance improvement of a capacitor using a fluorine-based electrolyte having a high withstand voltage. . Although the reason for this is not clear, it is presumed that one of the reasons is that it is not a carboxyl group which is relatively easily oxidized and has a carboxyl group which is not easily oxidized. Of course, the dispersibility of the other particles which were originally added was also good, and the strength of the produced electrode was also good. The acrylic compound (ID) is a polyacrylic acid or a salt thereof such as sodium or potassium or lithium, or a polyacrylic acid salt, a polyacrylate or an acrylic copolymer, and the like. Specifically, for example, poly Acrylic acid; a single polymer or copolymer of acrylate such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate or isopropyl acrylate. The commercially available product of the acrylic compound is, for example, polyacrylic acid such as Aron A-10H manufactured by Toagos Co., Ltd., and ammonium polyacrylate such as Aron A-30 manufactured by Toagosei Co., Ltd. -10 - 201142885 (IE) Other electrode components in addition to the above activated carbon particles (ΙΑ), binder (IB), Ketjen black (IC) and acrylic compound (ID), can also be used with electrodes for electric double layer capacitors Additives usually formulated. Further, the other additives may, for example, be the above-mentioned conductive materials other than Ketjen black (1C). An ideal additive is, for example, acetylene black, and a commercially available product is, for example, Denka BlackFX-35 manufactured by Electric Chemical Industry Co., Ltd. The electrode component is used in an amount of 2 parts by mass to 20 parts by mass of the binder (IB), 1 to 30 parts by mass of Ketjen black (IC), and an acrylic compound (ID) 1 to 100 parts by mass of the activated carbon particles (IA). 5 parts by mass is preferred. In order to obtain higher electrostatic capacity and lower internal resistance and higher withstand voltage, with respect to 100 parts by mass of activated carbon particles (IA), 3 to 10 parts by mass of the bonding material (iB), Ketjen black (IC) 8~ 20 parts by mass and 2 to 4 parts by mass of the acrylic compound (ID) are more preferable. In the case of the other electrode component (IE), it is 50 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the activated carbon particles (IA). The lower limit is an amount that can be achieved for the purpose of cooperation. In the case of, for example, Ketchen Black (1C) and other conductive materials, good electrical conductivity (low internal resistance) can be obtained, and if too much, the capacitance of the capacitor is reduced, and the total amount of activated carbon particles (IA) is combined. In order to adjust the total amount of Ketjen black (1C) and other conductive materials, it is preferably 1 to 50% by mass. The electrodes can be formed in a variety of ways. For example, activated carbon particles (IA), Ketjen black (1C), and other electrode components (IE) necessary for the reaction, such as other conductive materials, are dry-mixed. The acrylic compound (ID) and water are suitably added and dispersed in the other mixing process. Next, it is suitable to add a mixture of -11 - 201142885 (IB) and water, followed by wet mixing to prepare a homogeneous slurry for electrode formation. This slurry is applied onto a metal foil such as a current collector, and is suitably pressed and dried to prepare an electrode. The bulk density (electrode density) of the electrode produced in the present invention is preferably adjusted to 0.45 g/cm 2 or less. From the viewpoint of increasing the electrostatic capacitance or lowering the internal resistance, it is known that the electrode density is increased (〇6 g/cm 2 or more) (for example, Patent Document 2), but from the viewpoint of the withstand voltage of the capacitor, there is no review about An example of electrode density. The electrode density is preferably 4545 g/cm2 or less, more preferably 4040 g/cm2 or less, from the viewpoint of good withstand voltage. On the other hand, from the viewpoint of maintaining mechanical strength, it is preferably 0.35 g/cm2 or more. The method of adjusting the electrode density is not particularly limited, and for example, the following method can be employed. (1) The method of adjusting the solid content concentration of the slurry for the electrode. For example, it is preferred to adjust the solid content concentration to 15 to 25 mass%, more preferably 18 to 22 mass%. -12- 1 Method of adjusting the pressure at the time of coating the film for the slurry for pressurization after application 2 The pressurizing pressure may be appropriately selected in accordance with the electrode thickness of the purpose. These methods can be carried out either singly or in combination. The current collector may be any one that has chemical or electrochemical corrosion resistance. As the current collector of the polarized electrode mainly composed of activated carbon, stainless steel, aluminum, titanium or molybdenum can be preferably used. Among these, stainless steel or aluminum is the best material on both sides of the characteristics and price of the obtained 201142885 electric layer capacitor. The current collector is preferably formed to form a conductive film in order to be used stably at a high voltage. The conductive film is a method in which graphite particles having an average particle diameter of 塡μηη and a water-based coating of cellulose as a binder are applied to a current collector, and the film thickness is preferably 1 to 30 μm. By making this thickness, the formation of the electrode layer becomes easy, and the internal resistance of the electrode can be suppressed. The electrode of the present invention is preferably formed by forming an electrode layer on the conductive film on which the current collector of the conductive film is formed, from the viewpoint of the withstand voltage of the lift electrode and the high-temperature load characteristics. The electrode system can be an electric double layer capacitor using the above-mentioned electrode as a double pole, and a non-polarized electrode can be used on one side, for example, a positive electrode mainly composed of a battery active material such as a metal acidate, and activated carbon as a main component. The negative electrode of the electrode of the present invention may be combined. Further, the present invention relates to an electric double layer capacitor comprising the electrode of the present invention. The electric double layer capacitor of the present invention has the same structure as the conventionally known electric double layer capacitor, in addition to the electrode of the present invention, in the positive electrode and the negative electrode. The electrolyte can be formed by interposing an electrolyte according to a spacer required. The electrolytic solution may be an aqueous electrolytic solution, but a non-aqueous (organic) electrolytic solution is preferred from the viewpoint of expanding the operating voltage. The nonaqueous electrolytic solution suitably used in the present invention is a fluorine-based electrolytic solution containing a fluorine-based solvent and an electrolyte salt. (ΙΙΑ) Fluorine-based solvent-13-201142885 The fluorine-based solvent used in the electric double layer capacitor of the present invention is, for example, a fluorine-based solvent containing a fluorine-containing cyclic carbonate described in Patent Document 3, and has high electric resistance and It is preferable that the electrolyte solubility is excellent. Fluorine-containing cyclic carbonate to contain formula (1): 〇=c b.

X

ό 2 X 4 X 3 X ό (wherein, X1 to X4 are the same or different, and are all -Η, -F, -CF3' -CHF2, -CH2F, -C2F5 or -CH2CF3; however, X1 to X4 The solvent of the fluorine-containing cyclic carbonate represented by at least one of -F, -CF3, -C2F5 or -CH2CF3) is preferably a viewpoint of a large electrostatic capacity and a high withstand voltage. The fluorine-containing cyclic carbonate contained in the fluorine-based solvent (ΠA) is excellent in solubility and other internal electrolyte resistance from the viewpoint of exhibiting excellent characteristics of high dielectric constant and high withstand voltage. Point of view, and by enhancing the viewpoint of the characteristics of the electric double layer capacitor in the present invention, 1

OMHC o=c 3 Fc

D——c H H b——c ό-c H 1 2 Hc - 3 Fc Η bIc -14- 201142885

CF3-FC-CH2 FHC-CH2,

F2C-CH2 and FHC-CHF are preferably at least one selected from the group consisting of the above. The fluorine content of the fluorine-containing cyclic carbonate is preferably 15 to 55 mass%, more preferably 17 to 44 mass%, from the viewpoint of dielectric constant and oxidation resistance. Other fluorine-containing cyclic carbonates can also be used, for example, the following. B31 o = c o = c Ό — c H - 5 F 2c

2 F ό——c F H-o——c OMnc

onMC

2 F ό-c ό——c F I 3 Fc b — c

2 F -15- 201142885 onnc

OUMC

〇 I 〇 I 〇 I I ch2 I chf2-hc — I CH ο

I ch2f-hc- The content rate of the fluorine-containing cyclic carbonate in the fluorine-based solvent (πa) is preferably from 1 to 2% by volume from the viewpoint of good dielectric constant or viscosity. The volume % is more preferred. The solvent (IIA) may be a fluorine-containing cyclic carbonate represented by the formula (1), or a mixture with another solvent for dissolving the fluorine-containing electrolyte salt or a solvent for dissolving the non-fluorine-based electrolyte salt. Further, the fluorine-containing cyclic carbonate generally has a melting point of ruthenium, and when it exists alone, it may cause an obstacle to the action at a low temperature. In such a case, it is preferred to use a mixture of a fluorine-containing cyclic carbonate represented by the formula (1) and another solvent for dissolving the gas-containing electrolyte salt from the viewpoint of improving oxidation resistance and viscosity. . Examples of the solvent for dissolving the fluorine-containing electrolyte salt used in the co-solvent of the fluorine-containing cyclic carbonate represented by the formula (1) include a fluorine-containing chain carbonate, a fluorine-containing chain ester, and a fluorine-containing chain ether. Fluorine-containing lactone, fluorine-containing cyclobutyl derivative, and the like. Fluorinated chain carbonate, from the viewpoint of good adhesion or oxidation resistance, with the formula (2): [Chemical 4] Ο (2) 4 alkyl or carbon

II R f "-OCOR f (wherein, Rfal and Rfa2 are the same or different carbon number -16 - 201142885 number 1 to 4 of the fluorine-containing alkyl group. However, at least one is: base) is better Among the fluorine-containing chain carbonates, from the viewpoint of the excellent characteristics of the voltage which can be particularly strong, and the viewpoint of the characteristics of the electric double layer capacitors from the viewpoint of other electrolysis and low internal resistance and maintaining low-temperature characteristics, 5] Ο

HCF2CF2CH2-〇-i-〇-CH2C Ο

II CF 3CF2CH2 —〇 — C — Ο — CH2CF; Ο

II CF 3CH2 — 〇 — C — 〇—CH2CF3 0

II cf3 — 〇—C — 〇—CF3 ?Fs ? V3 cf3ch-oco-chcf3 Other fluorine-containing chain carbonates can be used in the gas-filled high-potency, high-resistance salt, such as the following carbon numbers 1 to 4. The solubility and the reduction are preferably as follows. F2cf2h iCFa, and so on. -17- 201142885 [its] ο

II hcf2cf2ch2-o-c-o-ch3, ο hcf2cf2ch2-o-c-o-ch2ch3 ο

II CF3CF2CH2 — 0-0 A O - CH3 , ο

II CF3CF2CH2-〇-C-〇-CH2CH3 ?F3 ? CF3CH-0-C-0-CH3

c f3 O ! II CF3CH-〇-C-〇-CH2CH3 o

II CF3CH2-〇-C~〇-CH2CH3 o

For example, the compound described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Among them, the oxidation resistance and the solubility of the electrolyte salt are good, and the following are preferred. -18- 201142885 [化7] Ο

II CF3CF2CH2-〇-C-〇-CH2CF2CF3 ο

II cf3ch2—Ο—C—ο—ch2cf3 , ο

II HCF2CF 2〇Η2 一Ο一一一一一CH3 ο

II HCF2CF2CH2 - Ο - C - Ο - CH2CH3 , Ο CF3CF2CH2-〇-C-〇一CH3 \ o

II cf3ch2-o-c-o-ch2ch3 , o

(2) cf. The compound of the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Wherein 'the compatibility with other solvents is good and has a suitable viewpoint' to formula (3):

Fluorine-containing chain ethers of Rfcl-0-Rfc2 (3) (wherein Rfel and Rf. 2 are the same or different, both of which are carbon number 2 to 4 -19- 201142885) . In particular, Rfcl may be, for example, -CH2CF2CHF2, -ch2c2f4chf2, -CH2CF3'-CH2C3F6CHF2 > -CH2C2F5, -ch2cf2chfcf3, -ch2cf(cf3)cf2chf2, -c2h4c2f5, -c2h4cf3, etc. Further, Rfc2 is, for example, -cf2cf2h, -cf2chfcf3, -c2f4chf2 ' -c2h4cf3, -CH2CHFCF3, -C2H4C2F5 are preferred. The fluorine-containing chain ester has high flame retardancy and good compatibility with other solvents or oxidation resistance, and is expressed by the formula (4)=

R R Iο 1o = c (wherein, Rfbl and Rfb2 are the same or different, and all are fluorine-containing alkyl groups having 1 to 4 carbon atoms) are preferred. Examples of the fluorine-containing chain ester include cf3c(=o)oc2f5, cf3c(=o)och2cf3, CF3C(=o)och2ch2cf3, CF3C(=0)0CH2C2F5, CF3C(=0)0CH2CF2CF2H, CF3C(=0)0CH (CF3)2 'CF3C(=o)och(cf3)2, etc., in which compatibility with other solvents, viscosity, oxidation resistance, etc. is good, with cf3c(= 〇)〇c2f5, CF3C( = 0) 0CH2C2F5, CF3C(= o)och2cf2cf2h, CF3C(=0)0CH2CF3, CF3C(=0)0CH(CF3)2 are particularly good. The fluorine-containing lactone can be exemplified by the formula (5): -20- 201142885

OMMC

X9X10C o (5) CX7X'

X5X6C (wherein, X5 to xi〇 are the same or different, and are all _H, -F, -Cl, -CH3 or a fluorine-containing methyl group; however, at least one of X5 to X10 is a fluorine-containing methyl group) Fluoride lactone is shown. In addition to those shown in the above formula (5), the fluorine-containing lactone may be, for example, a formula (6): [Chemical 10] Person (6) r fe—xJ1a xx^x1 / \ X14 X15 (wherein A And B is either CX16X17 (X16 and X17 are the same or different, and all are -H, -F, -Cl, -CF3, -CH3 or a nitrogen atom may be substituted by a _ atom and may be contained in the chain The alkyl group of the hetero atom and the other is an oxygen atom; Rfe is a fluorine-containing ether group 'fluorinated alkoxy group or a gas-containing alkyl group having a carbon number of 2 or more; X11 and X12 are the same or different, and all are -H , -F, -Cl, or -CH3; X13~X15 are the same or different, all of which are -H, -F, -C1 or a hydrogen atom which can be substituted by a halogen atom and which may contain a hetero atom in the chain. ; -21 - 201142885 n = 0 or 1) Fluorine-containing vinegar, etc. Among these, from the viewpoint of exhibiting excellent characteristics of high dielectric constant and high withstand voltage, and from the viewpoints of good solubility of other electrolyte salts and deterioration of internal resistance, it is promoted as an electric layer liquid in the present invention. The viewpoint of the characteristics is preferably as follows. [化11]

'οI

OHC

OHC

2 H , cI 'o — H b. c f3ch2-hc-ch2 c f3c f2-hc-ch2

OHC

OHC H sc. d, 2 H VC. c2 f5ch2-hc-ch2 _ 3 F F CIC 3 p c C Η

Η C 〇=c /ο· F C Η

-c 2 H Η c is described as if it is used to make the ester also contain fluorine. -22- 201142885 [Chem. 12]

onNC

OMMC

D——c 2 2 Η H

'c- 2 H

•c 2 H F b-c o=c

C-c H F

2 H Η b——c OHnc o = c

C-c 2 2 F H H b — c

-c. 2 H

, c 2 H F H , oIc

cIc 2 2 F H o = c 2 F bic The fluorine-containing cyclobutyl hydrazine derivative is not limited to the fluorine-containing cyclobutyl hydrazine derivative described in JP-A No. 200 Π 32994, and the following is preferred. [Chem. 13]

F 〇v yO Ο. .〇 〇 〇

F

F

F

F

F 〇\ yCH2C2 F s V°.CHiCF,

o

CH2C F aCHF The solvent for dissolving the non-fluorine-based electrolyte salt used as a co-solvent of the fluorine-containing cyclic carbonate which is not contained in the formula (1), and examples thereof include a non-fluorine-based cyclic carbonate and a non-fluorinated bicarbonate. A chain carbonate, a non-fluorine chain ester, a non-fluorine chain ether, a non-fluoro lactone, a non-fluorocyclobutanine derivative, and a solvent for dissolving other non-fluorine electrolyte salts. Examples of the non-fluorine-based cyclic carbonate include the following. [Chem. 14]

OHMC onnc ό — c H I 3 H c 2 H bIc

2 H ό——c 2 Η b-c

OHC

Ό——c H H b——c is as in the case of salt acid carbon Ϊ _ chain system fluorine non-chemical [Chemical 15]

Ο II (7)

Ral-〇-C-〇-R: wherein Ral and Ra2 are the same or different, and each is an alkyl group having 1 to 4 carbon atoms. It is preferred to hear the chain carbonate. Among the non-fluorine-based chain carbonates, from the viewpoint of exhibiting excellent characteristics of high dielectric constant and high enthalpy voltage, and from the viewpoints of good solubility of other electrolyte salts and a decrease in internal resistance, the present invention is improved. The characteristics of the double-double--24-201142885 electric layer electric grid device are preferably the following. Ο CH3CH2CHa~OC-〇-CH2CH2CH3 Ο CH3CH2-OCO-CH2CH3 0 , II CH3-0-c-〇-ch3 , 9Η3 o ch3I II I CH3CH-0-C-0-CHCH3 o CH3CH2-〇- Other non-fluorine-based chain carbonates of C-〇-CH3 can also be used as described below. [ΠΠ] 〇II CH3CH2CH2-〇-C-〇-CH3, 0II ch3ch2ch2-o-c-o-ch2ch3 Ηc I 0 1OHnc Io 3 I Η H CIC 3 Hc

Hc 2 Hc 1 0 1o=c 1o 3. I Η H CIC 3 Hc The solvent for dissolving the electrolyte salt used as the co-solvent of the fluorine-containing cyclic carbonate represented by the formula (1), which is resistant to oxidation The viscosity is good. From -25,42,885, the solvent for dissolving the fluorine-containing electrolyte salt is preferred, and the fluorine-containing chain carbonate, the fluorine-containing chain ester, and the fluorine-containing chain ether are more preferable. In particular, the solvent (IIA) which is operated at a high voltage of 3.5 V or higher, the fluorine-containing cyclic carbonate represented by the formula (1), and the fluorine-containing chain carbonate and the fluorine-containing chain are selected. It is preferable that at least one of a group of the ester and the fluorine-containing chain ether is formed, and among them, a fluorine-containing chain ether is preferred from the viewpoint of good oxidation resistance. The combination of a fluorine-containing cyclic carbonate and a fluorine-containing chain ether is particularly preferred from the viewpoints of good oxidation resistance and solubility of an electrolyte salt, and is a fluorine-containing cyclic carbonate described below. Ο Ο

〇I 〇〇1 0 1 1 FHC — | ——ch2 2 Shout cf3-hc 1 CH_ Select CF3CF2CH2-O-CF2CFHCF3 ' HCF2CF2CH2-O-CF2CFHCF3 , cf3cf2ch2-〇-cf2cf2h and hcf2cf2ch2-o-cf2cf2h A mixture of at least one of the fluorine-containing chain ethers. (IIB) Electrolyte salt Electrolyte salt (ΠΒ) may, for example, be a conventionally known ammonium salt or a metal salt, and examples thereof include a liquid salt (ionic liquid), an inorganic polymer salt, and an organic polymer salt. Wait. The ammonium salt can be used by a conventionally known one, and examples thereof include a spirocyclic pyridinium salt, an imidazolium salt, a tetraalkyl 4-ammonium salt, an N-alkyl pyridyl salt, and an N,N-di-26-201142885 alkyl group. Pyrrolidine key salt and the like. The spirobipyridine salt is preferably, for example, a formula (1 0-1): [Chem. 19] (Ώ 1 ίτ> t 1\

\_/十\_/ (wherein, Rfl and Rf2 are the same or different, all are C 1~4 alkyl; X old anion; nl is an integer of 0~5; n2 is an integer of 0~5 ) a spirobipyridine key salt, formula (1 〇-2): [Chem. 20]

X0 (wherein Rf3 and Rf4 are the same or different, each is an alkyl group having 1 to 4 carbon atoms; X_ is an anion; n3 is an integer of 0 to 5; n4 is an integer of 0 to 5) Cyclopyridine salt, or formula (1 〇-3):

(10-3) -27- 201142885 (wherein Rf5 and Rf6 are the same or different, each is an alkyl group having 1 to 4 carbon atoms; X_ is an anion; n5 is an integer of 0 to 5; π6 is 0~ A spirobipyridine salt represented by an integer of 5). Further, from the viewpoint of enhancing oxidation resistance, it is preferred that one or all of the hydrogen atoms of the spirobipyridine salt be replaced by a fluorine atom and/or a fluorine-containing alkyl group having 1 to 4 carbon atoms. The anion Χ_ may be an inorganic anion or an organic anion. Examples of the inorganic anion include A1C14_, BF4_, PF6_, AsF6·, TaF6·, Γ, SbF6· and the like. Further, examples of the organic anion include CH3COCT, CF3S03·, (CF3S02)2N·, (C2F5S02)2N· and the like. Among these, from the viewpoint that the dissociation property is high and the internal resistance at high voltage is low, BF4_, PF6_, (cf3so2)2n- or (c2f5so2)2n_ is preferable, especially bf4-, pf6- Better. Preferable specific examples of the spirobipyridyl key salt include the following. [化22]

-28- 201142885 This spirobipyridine salt is excellent in solubility in a solvent, oxidation resistance, and ion conductivity. The imidazole key salt is preferably, for example, a formula (1 1): [Chem. 23] / R81 (11) \N 〆 χ θ

(wherein, Rgi and Rg2 are the same or different, each are an alkyl group having 1 to 6 carbon atoms; and 乂 is an anion). Further, from the viewpoint of enhancing oxidation resistance, it is preferred that one or all of the hydrogen atoms of the imidazole salt are replaced by a fluorine atom and/or a fluorine-containing alkyl group having 1 to 4 carbon atoms. A preferred specific example of the anion X_ is the same as the spirobipyridine salt. Preferred examples of the imidazolium salt include, for example, the formula (1 2):

HSC Χ θ (12) Ethylmethylimidazole key salt, etc. This imidazole key salt has low viscosity and is excellent in solubility in a solvent. The tetraalkyl 4-based ammonium salt is preferably, for example, a formula (1 3 ): -29 - 201142885 [Chem. 25]

Rh 1

I ® A

Rh2_N_Rh4 (13)

I

Rh3 (wherein, Rhl, Rh2 'Rh and Rh4 are the same or different, and each is an alkyl group which may contain an ether having a carbon number of 1 to 6; X. is an anion). Further, from the viewpoint of enhancing oxidation resistance, it is preferred that one or all of the hydrogen atoms of the tetraalkyl 4-membered ammonium salt be replaced by a fluorine atom and/or a fluorine-containing alkyl group having 1 to 4 carbon atoms. Specific examples include the formula (13-1): [Chem. 26] (Rhl), (Rh2), ΝΘ Χ θ (13-1> (wherein, Rhl, Rh2, and the plant are the same as the formula (13): χ and y Is the same or different, 整数~4 integer, and x+y=4) is a tetraalkyl 4- toluene salt, formula (13-2): [Chem. 27]

h R

φ N HR

Θ X ο

h R 2 - 3 (wherein Rh 5 is an alkyl group having a carbon number of 1 to 6.), Rh 6 is a divalent hydrocarbon group having a carbon number of 丨 to 6; and Rh 7 is an alkyl group having a carbon number: 2 is 1 or 2; The alkyl ether group-containing trialkylammonium salt represented by anion) -30- 201142885 <• can be reduced in viscosity by introducing an alkyl ether group. A preferred specific example of the anion X· is the same as the spirobipyridinium salt. Specific examples of the tetraalkyl 4-grade ammonium salt include Et4NBF4 ' Et4NC104 , Et4NPF6 , Et4NAsF6 , Et4NSbF6 , Et4NCF3S03 , Et4N(CF3S02) 2N , Et4NC4F9S03 , Et3MeBF4 , Et3MeC104 , Et3MePF6 , Et3MeAsF6 , Et3MeSbF6 , Et3MeCF3S03 ' E13 M e (CF 3 SO 2) 2 N, E13 M e C 4 F 9 SO 3 , etc., particularly preferably Et4NBF4, Et4NPF6, Et4NSbF6, Et4NAsF6 (Me is methyl, Et is ethyl) and the like. The N-alkylpyridyl key salt is preferably, for example, a formula (14):

(1 4) (wherein Rn is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; X is an anion). Further, from the viewpoint of enhancing oxidation resistance, it is preferred that one or all of the hydrogen atoms of the N-alkylpyridine salt are replaced by a fluorine atom and/or a fluorine-containing alkyl group having 1 to 4 carbon atoms. A preferred specific example of the anion X_ is the same as the spirobipyridine salt. Preferred examples thereof include, for example, the following. -31 - 201142885 [Chem. 29]

bf4Q

Pf6®

Pf60 F θ This N-alkylpyridinium salt has low viscosity and excellent solubility in a solvent. The N,N-dialkylpyrrolidine key salt is preferably, for example, a formula (15): [Chem. 30] RJ 2 RJ »

(wherein, Rjl and Rj2 are the same or different, each are an alkyl group having 1 to 6 carbon atoms; -32- 201142885 X- is an anion) represented by an N,N-dialkylpyrrolidine key salt. Further, from the viewpoint of improving oxidation resistance, one or all of the hydrogen atoms of the N,N-dialkylpyrrolidine salt are replaced by fluorine atoms and/or fluorine-containing alkyl groups having 1 to 4 carbon atoms. It is better. A preferred specific example of the anion X_ is the same as the spirobipyridine gun salt. Preferred examples of the preferred embodiment include the following. [化31] CH3 ^ch3

bf4Q

Pf6°

33- 201142885

The N,N-dialkylpyrrolidine salt has low viscosity and excellent solubility in a solvent. Among these ammonium salts, the spirobipyridinium salt and the imidazolium salt are preferably from the viewpoints of solubility in the solvent, oxidation resistance, and ion conductivity, and are preferably the following. -34- 201142885 [Chem. 33]

(where X ' is BF4, PF6, (CF3S〇2) 2N_ or (c2f5S〇2) 2N-, especially PF6· is preferred), or [34]

(wherein X- is BF4-, PF6-, (CF3S02)2N· or (C2F5S02)2N·, especially BFr and PF6_ are preferred). Further, the electrolyte salt may be a lithium salt. The lithium salt is preferably LiPF6, LiBF4, LiAsF6, LiSbF6 or LiN(S02C2H5)2, for example. Further, in order to increase the electrostatic capacity, a magnesium salt can also be used. The magnesium salt is preferably Mg (C104) 2, Mg (OOC2H5) 2 or the like, for example. In particular, when the fluorine-containing cyclic carbonate of the above formula (1) is used as the fluorine-based solvent (IIA), the ring is composed of an anion of BF4-, PF6-, N(02SC2F5)2 or N(02SCF3). Level 4 key salt is preferred. The amount of the electrolyte salt (IIB) varies depending on the required current density, the use, the type of the electrolyte salt, and the like, and is equivalent to the fluorine-containing cyclic carbonate (the total amount of the solvent used for dissolving other electrolyte salts) 100 parts by mass -35 - 201142885 'It is 1 part by mass or more' 1 part by mass or more is more preferable, 5 parts by mass or more is particularly good' and 200 parts by mass or less, and 1 part by mass or less is more preferable. 50 parts by mass or less is particularly preferred. The electrolytic solution used in the present invention is prepared by dissolving an electrolyte salt (ΙΙΒ) in a fluorine-based solvent. Further, in the present invention, the electrolytic solution may be dissolved in the solvent used in the electrolytic solution of the present invention or combined with the swollen polymer material to form a gel-like (plasticized) gel electrolyte. The polymer material may be a conventionally known polyethylene oxide or polypropylene oxide, and the modified materials thereof (Japanese Patent Laid-Open Publication No. Hei 8-222270, No. 2002-10 04 05); A fluororesin such as an acrylate polymer, a polyacrylonitrile, or a polyvinylidene fluoride or a difluoroethylene-hexafluoropropylene copolymer (Japanese Patent Publication No. 4-506726, Japanese Patent Application No. 8-5074〇7) Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. Hei 1 1 - No. Bulletin) and so on. In particular, it is preferred to use a polyvinylidene fluoride-containing or a difluoroethylene-hexafluoropropylene copolymer as a polymer material for a gel electrolyte. Others may use the ion-conducting compound described in the specification of Japanese Patent Application No. 2004-301 934. The electrolytic solution used in the present invention may be blended with other additives as needed. Other additives include, for example, metal oxides, glass, and the like. In this way, the electrolyte can not only maintain the low-temperature characteristics, but also improve the flame retardancy, the solubility of the electrolyte salt, and the compatibility with the hydrocarbon solvent, and can obtain the stability characteristics under a withstand voltage of 3.5 V or more. It is excellent in 36-201142885 as an electrolyte for electric double layer capacitors. An electric double layer capacitor is generally known as a wound battery type electric double layer capacitor, a laminated electric double layer capacitor, a coin type electric double layer capacitor, etc., and the electric double layer capacitor of the present invention can also be in the form of these. For example, in a wound battery type electric double layer capacitor, a positive electrode and a negative electrode including a laminate (electrode) of a current collector and an electrode layer are separated by a spacer and wound into a wound element, and the wound element is placed. The outer casing of aluminum or the like is filled with an electrolyte, preferably a non-aqueous electrolyte, and then sealed by sealing with a rubber seal. Since the electrode of the present invention has sufficient mechanical properties, particularly bending resistance, by incorporating an acrylic compound (ID), it can be easily and stably produced as a wound element, and its durability is also excellent. In the present invention, conventionally known materials and constituents can be used as the spacer. For example, a polyethylene porous film, a polypropylene fiber or a glass fiber, a nonwoven fabric of cellulose fibers, or the like can be given. Further, by a known method, a laminated electric double layer capacitor in which a sheet-like positive electrode and a negative electrode which are separated by an electrolyte and a spacer are laminated may be formed or fixed by a gasket to be passed through an electrolyte and an interval. The positive electrode and the negative electrode separated by the separator are formed into a coin type coin-type electric double layer capacitor. [Examples] Hereinafter, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the examples. Example 1 (Production of Electrode) -37- 201142885 (Preparation of slurry for electrode) Non-graphitizable activated carbon particles activated by steam (YP50F, KURARAY CHEMICAL, specific surface area: 1600 m2/g, average 100 parts by weight of a particle size of 6 parts by weight, acetylene black (Denka Black, manufactured by Electric Chemical Industry Co., Ltd.) as a conductive auxiliary agent, 3 parts by weight of Konica Green (Carbon ECP600JD manufactured by LION Co., Ltd.), and an elastomer 6 parts by weight of a binder (manufactured by Essence Co., Ltd.) and 6 parts by weight of a tackifier (manufactured by Toago Corporation Co., Ltd.) were mixed to prepare a slurry for an electrode. (Production of Electrode) An etched aluminum (20 CB, thickness: about 20 μm) manufactured as a current collector was prepared, and a conductive coating was applied to both sides of the current collector using a coating device. (Varniphite Τ 602, manufactured by Japan Graphite Industries Co., Ltd.), and a conductive layer (thickness: 2 μηι) was formed. Next, the above-mentioned prepared electrode slurry was applied onto the conductive layer formed on both faces of the current collector by using a coating device to form an electrode layer (thickness: ΙΙΟμηη), thereby producing an electrode of the invention. With respect to this electrode, when the electrode density and the bending resistance were investigated by the following requirements, the electrode density was 0.41 g/cm3, and the bending resistance was evaluated as 〇. (1) Electrode density The weight or outer dimension of an etched aluminum sheet (substrate) coated with a conductive layer cut to a predetermined size was measured in advance, and an electrode layer was coated on the upper portion thereof. The weight of the substrate after drying from 140 ° C for 1 hour minus the weight of the substrate is taken as the weight of the electrode, and the volume outside the coating is subtracted from the volume of the substrate -38-201142885, and the electrode is used as an electrode. Outer size. The electrode density was calculated based on the weight and shape of the electrode calculated above. (2) Coating film bending test According to JIS K54 00, a bending tester (film bending tester manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was used, and measurement was performed under the condition of Φ2. The evaluation was carried out on the basis of the following criteria. 〇: Visually, no cracks were found at all. X: Visually, cracks were found. Example 2 (Production of Capacitor) The electrode fabricated in Example 1 was cut to a width of 31111111. This electrode was wound with a separator (TF45-300, width 34 cm, manufactured by Nippon Paper Industries Co., Ltd.) in the same manner as in the EDLC, and a cylindrical wound body having a diameter of 16 mm was produced. At this time, the counter electrode is gap-connected to the lead wire for electrode extraction. Next, the cylindrical winding body and the cylindrical aluminum shell 'rubber gasket are vacuum-dried, and then the cylindrical winding body is inserted into the cylindrical aluminum shell in the drying chamber, and then the electrolyte shown below is injected. A capacitor of a wound battery type (φ 18 mm x 40 mm) was produced by sealing with a rubber gasket. (Preparation of Electrolyte) The cyclobutanol and hcf2cf2ch2ocf2cf2h and dimethyl carbonate were mixed at a volume ratio of 65/1 5/20 to prepare a solvent for dissolving the electrolyte salt. The solvent for dissolving the electrolyte salt was added to a concentration of K2 mol/liter to add a -39-201142885 tetrafluoroborate spiropyridine salt to form a homogeneous solution, and this solution was used as an electrolyte. For the fabricated capacitor, investigate the initial characteristics (electrostatic capacity (F), internal resistance (ηιΩ)), low-temperature characteristics (electrostatic capacity retention (%), resistance increase rate (time)), and withstand voltage (by the following methods). Long-term reliability evaluation with 3V and 3.1 V). The results are shown in Table 1. (3) Initial characteristics After the electronic battery is connected to the wound battery of the capacitor, the winding battery is charged at a constant current and the charging voltage is raised to a predetermined voltage. The charging voltage reaches a predetermined voltage and is maintained at a constant voltage of 1 〇 minutes. After confirming that the charging current has sufficiently decreased and becomes saturated, the constant current discharge is started, and the battery voltage is measured every 0.1 second. The electrostatic capacity (F) and internal resistance (ιηΩ) of the capacitor are measured in accordance with the measurement method of RC23 77 of the JEITA. (Measurement conditions under JEITA's RC2377)

Power supply voltage: 3.0 and 3.IV Discharge current: 500 mA (measured electrostatic capacity of the fabricated wound battery is 50 F) (4) Low temperature characteristics (-10 ° C) Place a capacitor in the temperature -1 (TC thermostat bath) The electrostatic capacity and the internal resistance 値 at the respective temperatures were measured, and the electrostatic capacity retention ratio (%) and the internal resistance increase rate (time) were calculated according to the following calculation formula: -40- 201142885 Electrostatic capacity retention ratio (%) = (- 1 静电 ° C electrostatic capacity / 25 ° C electrostatic capacity) χ 1 00 internal resistance increase rate (time) = (_10 ° C internal resistance / 25 ° C internal resistance) electrostatic capacity retention rate of 70% or more (4) Withstand voltage (long-term reliability test) The wound battery type capacitor is placed in a thermostat bath at a temperature of 70 °C. The electrostatic capacity and internal resistance were measured by applying a voltage of 3.0 V and 3.1 V for 1 000 hours. The measurement time was initial (〇 hour), 157 hours, 327 hours, 500 hours, and 1,000 hours.値, calculate the electrostatic capacity retention rate (%) and within the following calculation formula The rate of increase in resistance (%). The results are shown in Table 1. Electrostatic capacity retention ratio (%) = (electrostatic capacity at each hour / electrostatic capacity before evaluation (initial)) χΐ〇〇 internal resistance increase rate (%) ) = (internal resistance at each hour / internal resistance before the start of evaluation (initial)) χ 1 〇〇尙, the electrostatic capacity retention rate after 500 hours is 70% or more, and the internal resistance increase rate is 400% or less. That is, it is excellent in load characteristics at high temperature (70 ° C), and is excellent in cycle characteristics or efficiency performance in use at normal temperature, and has long-term reliability. Example 3 As an electrolytic solution, except for ring oxime And hcf2cf2ch2ocf2cf2h -41 - 201142885 is mixed with dimethyl carbonate in a volume ratio of 65/1 5/20 to prepare a solvent for dissolving an electrolyte salt, and the solvent for dissolving the electrolyte salt is added to a concentration of 1.2 m/liter. In the same manner as in Example 2, a battery-type capacitor was produced in the same manner as in Example 2 except that ethyl ether was used as the electrolyte solution. The obtained capacitor was produced in the same manner as in Example 2. Determination The initial characteristics, the low-temperature characteristics, and the withstand voltage were as follows. The results are shown in Table 1. Example 4 A solvent for dissolving an electrolyte salt was prepared by mixing cyclobutane with HCF2CF2CH2OCF2CF2H at a volume ratio of 75/25. A solvent for dissolving was used in the same manner as in Example 2 except that a homogeneous solution obtained by adding a tetrafluoroborate serotonate salt to a concentration of 1.2 mol/liter was used as the electrolytic solution, thereby producing a wound battery type capacitor. The obtained capacitor was measured in the same manner as in Example 2, and its initial characteristics, low-temperature characteristics, and withstand voltage were measured. The results are shown in Table 1. Example 5 100 parts by weight of water-steam-activated non-graphitizable activated carbon particles (YP50FH, specific surface area: 1 600 m 2 /g, average particle diameter: 6 μm) manufactured by Kuraray Chemical Co., Ltd., and acetylene black as a conductive auxiliary agent ( 3 parts by weight of Denka Black manufactured by Electrochemical Industry Co., Ltd., 16 parts by weight of Ketchen Black (Carbon ECP600JD manufactured by LION Co., Ltd.), and an elastomer adhesive (ΑΖ-9001, manufactured by Nippon Co., Ltd.) 6 weight 3 parts by weight of a tackifying material (manufactured by East Asia Synthetic Co., Ltd.) was mixed to prepare a slurry for an electrode. 42-201142885 An electrode was produced in the same manner as in Example 1 except that the slurry for the electrode was used. When the electrode density and the bending resistance were examined, the electrode density was 0.35 g/cm3, and the bending resistance was evaluated as "〇". A wound battery type capacitor was produced in the same manner as in Example 2 except that this electrode was used. The obtained capacitor was measured in the same manner as in Example 2, and its initial characteristics, low-temperature characteristics, and withstand voltage were measured. The results are shown in Table 1. Example 6 100 parts by weight of non-graphitizable activated carbon particles (Kuraray Chemical Co., Ltd. YP80F, specific surface area: 2000 m 2 /g, average particle size 6 μηι) activated by steam, acetylene black as a conductive auxiliary agent (electrical 3 parts by weight of Denka Black manufactured by Chemical Industry Co., Ltd., 16 parts by weight of Ketchen Black (Carbon ECP600JD manufactured by LION Co., Ltd.), and an elastomer adhesive (AZ-900 1 manufactured by Nippon Co., Ltd.) 6 weight 3 parts by weight of a part of a tackifier (A10H manufactured by Toagos Co., Ltd.) was mixed and prepared into a slurry for an electrode. An electrode was produced in the same manner as in Example 1 except that the slurry for the electrode was used. When the electrode density and the bending resistance were examined, the electrode density was 0.35 g/cm3, and the bending resistance was evaluated as 〇. A wound battery type capacitor was produced in the same manner as in Example 2 except that this electrode was used. The obtained capacitor was measured in the same manner as in Example 2, and its initial characteristics, low-temperature characteristics, and withstand voltage were measured. The results are shown in Table 1. Example 7 -43- 201142885 100 parts by weight of non-graphitizable activated carbon particles (RPURA, manufactured by KURARAY CHEMICAL Co., Ltd., specific surface area: 1 800 m 2 /g, average particle diameter 8 μηι) activated by steam 3 parts by weight of acetylene black (Denka Black, manufactured by Electric Chemical Industry Co., Ltd.), 16 parts by weight of Ketchen Black (Carbon ECP600JD manufactured by LION Co., Ltd.), and an elastomer binder (manufactured by Nippon Co., Ltd.) AZ-900 1) 6 parts by weight of a heavy-duty and tackified material (10 Η made by East Asian Synthetic Co., Ltd.) was mixed to prepare a slurry for an electrode. An electrode was produced in the same manner as in Example 1 except that the slurry for the electrode was used. When the electrode density and the bending resistance were examined, the electrode density was 0.4 1 g/cm3, and the bending resistance was evaluated as 〇. A wound battery type capacitor was produced in the same manner as in Example 2 except that this electrode was used. The obtained capacitor was measured in the same manner as in Example 2, and its initial characteristics, low-temperature characteristics, and withstand voltage were measured. The results are shown in Table 1. Comparative Example 1 Alkali-activated graphitizable activated carbon particles (NK261 manufactured by KURARAY CHEMICAL Co., Ltd., specific surface area: 2300 m 2 /g, average particle diameter 6 μmη) were used in an amount of 1 part by weight, and acetylene black as a conductive auxiliary agent ( 3 parts by weight of Denka Black manufactured by Electrochemical Industry Co., Ltd., 16 parts by weight of Ketchen Black (Carbon ECP600JD manufactured by LION Co., Ltd.), and elastomer adhesive (AZ-9001, manufactured by Japan ZEON Co., Ltd.) 6 weight 3 parts by weight of a tackifier (A 10H manufactured by Toagos Co., Ltd.) was mixed to prepare a slurry for an electrode. An electrode was produced in the same manner as in Example 1 except that the slurry for the electrode was used. When the electrode density and the bending resistance were examined, the electrode density was -44 - 201142885 0.40 g/cm3, and the bending resistance was evaluated as 〇. A wound battery type capacitor was produced in the same manner as in Example 2 except that this electrode was used. The obtained capacitor was subjected to the characteristics of the period, the low-temperature characteristics, and the withstand voltage in the same manner as in the second embodiment. The results are shown in Table 1 [Table 1], and the system is measured at the beginning -45- 201142885

rH Ο Ο CO ΙΟ 〇S5 1 1 MS« i | 1 〇2 1 1 1 Ο Ο 10 ΙΟ 2^§S CD inch Ο co ς〇ISSSS BSS^S ΙΟ ΙΟ Ο C0 ζ〇255SS5S Side ο ο ιο ι秧§§§§S^S§ CO ο ο ιο ιη 〇SS5S^ §»§^« s^His <N ο ο ιη ιο 〇5 w §ssst §§§(f) mim 踏趣e pIi 丄_ s #ι拗S tn赃运 gg sedan scales to ss3 transport (9) § 2 recorded | to § 23 Meng (five) ss fun Huquu Quu · · — CO CO As can be seen from Table 1, the use of water vapor-activated hard graphitization In the case of activated carbon particles, the initial electrical characteristics are excellent (low resistance), and low-temperature characteristics are maintained, and long-term reliability can be sufficiently achieved. -46-

Claims (1)

201142885 VII. Patent application scope: i-~ kinds of electrodes for electric double layer capacitors, which are provided with electrode layers containing activated carbon particles, binders, ketjen black and acrylic compounds obtained by activating water vapor of non-graphitizable carbon. . [2] The electrode of claim 1, wherein the electrode layer is disposed on the conductive film formed on the surface of the current collector. 3. The electrode of claim 1 or 2, wherein the non-graphitizable carbon is coconut shell carbon, phenol resin. 4. The electrode according to any one of claims 1 to 3, wherein the conductive film contains carbon and a resin. An electric double layer capacitor is provided with an electrode according to any one of claims 1 to 4. 6. The electric double layer capacitor of claim 5, which has a non-aqueous electrolyte. 7. The electric double layer capacitor of claim 6, wherein the non-aqueous electrolyte is a fluorine-based electrolyte. -47- 201142885 IV Designated representative map: (1) The representative representative of the case is: None. (II) Simple description of the symbol of the representative figure: None 201142885 V If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none