WO2004019356A1 - 電気二重層キャパシタ - Google Patents
電気二重層キャパシタ Download PDFInfo
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- WO2004019356A1 WO2004019356A1 PCT/JP2003/010630 JP0310630W WO2004019356A1 WO 2004019356 A1 WO2004019356 A1 WO 2004019356A1 JP 0310630 W JP0310630 W JP 0310630W WO 2004019356 A1 WO2004019356 A1 WO 2004019356A1
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- WIPO (PCT)
- Prior art keywords
- electric double
- double layer
- ionic liquid
- activated carbon
- layer capacitor
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to an electric double layer capacity, and more particularly, to an electric double layer capacity having excellent low-temperature characteristics and high capacitance.
- the non-aqueous electrolyte type electric double layer capacity has the feature that it can be charged and discharged with a large current, so it is promising as an energy storage device for electric vehicles and auxiliary power supplies.
- non-aqueous electrolyte type electric double layer capacitors are composed of positive and negative polarizable electrodes mainly composed of carbonaceous material such as activated carbon and non-aqueous electrolyte. It is known that the composition of the non-aqueous electrolyte has a large effect on the capacity.
- non-aqueous electrolyte is composed of an electrolyte salt and a non-aqueous organic solvent.
- electrolyte salts and non-aqueous organic solvents have been studied so far.
- electrolyte salt quaternary ammonium salts (Japanese Patent Application Laid-Open Nos. Sho 61-32509, Sho 63-173332, Hei 10-557) No. 17) and quaternary phosphonium salts (Japanese Patent Application Laid-Open No. Sho 62-252927), etc., have poor solubility and dissociation degree in organic solvents and an electrochemical stability range. It is often used because of its size.
- electric double-layer capacitors using a solid quaternary salt as the electrolyte salt can be used at low temperatures, especially at extremely low temperatures of less than 120 ° C.
- a quaternary salt is easily precipitated, and even if it does not precipitate, there is a problem that a significant decrease in electric conductivity is caused.
- a dialkylimidazolym salt which is an ionic liquid
- a mixed system with an inorganic salt is sensitive to moisture in the air and is difficult to handle, and the melting point of the imidazolyl salt itself is low. It has the disadvantages that it is not so low and that the potential window is relatively narrow.
- activated carbon is generally used as a polarizable electrode.
- This activated carbon is made of natural products such as coconut shells and wood chips, synthetic resins such as phenolic resins and polyimide resins, coal and petroleum pitch, and mesophase power. Carbonization of various raw materials such as carbon fiber, waste tires, etc., followed by activation (gas activation of water vapor, carbon dioxide, etc., chemical activation using zinc chloride, potassium hydroxide, phosphoric acid, etc.) Have been. In this case, there is a tendency that the larger the specific surface area of the activated carbon, the larger the capacitance, but it cannot be said that the study has been sufficiently conducted.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide an electric double layer capacitor having excellent low-temperature characteristics and high capacitance. Disclosure of the invention
- the present inventors have conducted intensive studies focusing on the relationship between the electrolyte salt and the pore distribution of activated carbon at a low temperature in order to achieve the above object.
- the ionic liquid especially in this case, A quaternary ammonium salt and a quaternary phosphonium salt having at least one alkoxyalkyl group as a substituent are used as the electrolyte salt, and the activated carbon constituting the polarizable electrode has a pore diameter distribution of micropores determined by the MP method.
- the inventors have found that by using a material having a peak within a predetermined range, it is possible to obtain a charge / discharge characteristic at a low temperature and to obtain an electric double layer capacity having a low internal impedance at a low temperature, and thus completed the present invention.
- An electric double layer capacity including a pair of polarizable electrodes, a separator interposed between the polarizable electrodes, and an electrolyte, wherein the polarizable electrodes are micropores obtained by an MP method.
- activated carbon having a pore radius distribution peak within a range of 4.0 X 10 — 1 () to 8.0 X 10 — 1 ° m.
- An electric double layer capacity characterized by containing an ionic liquid as an electrolyte salt,
- R 1 to R 4 are the same or different and are each an alkyl group having 1 to 5 carbon atoms, or an alkoxyalkyl group represented by R′_ ⁇ (CH 2) n — (R ′ is methyl And n is an integer of 1 to 4.), and any two of R 1 , R 2 , R 3 and R 4 may form a ring . However,! ⁇ 1 ⁇ ! At least one of ⁇ 4 is the above alkoxyalkyl group.
- X represents a nitrogen atom or a phosphorus atom
- Y represents a monovalent anion.
- Me represents a methyl group
- Et represents an ethyl group
- the concentration of the ionic liquid in the electrolytic solution is 0.5 to 2.0 mO 1 / L, wherein the electric double layer capacitor according to any one of 1 to 5,
- FIG. 1 is a chart showing an NMR spectrum of compound (2).
- FIG. 2 is a chart showing an NMR spectrum of the compound (11). The best mode for carrying out the invention
- the electric double layer capacitor according to the present invention is an electric double layer capacitor including a pair of polarizable electrodes, a separator interposed between these polarizable electrodes, and an electrolyte.
- polar electrode as a main component an activated carbon peak of the pore radius distribution of the micropores is in the range of 4. 0 X 1 0- 1 ° ⁇ 8. 0 X 1 0- 1 () m determined by the MP method
- the electrolyte solution contains an ionic liquid as an electrolyte salt.
- the ionic liquid is not particularly limited, but is preferably a quaternary ammonium salt or a quaternary phosphonium salt, and particularly preferably an ionic liquid having the following general formula (1).
- R i R 4 are the same or different alkyl groups having 1 to 5 carbon atoms, or an alkoxyalkyl group represented by R′— ⁇ — (CH 2 ) n— (R ′ is a methyl group Or n is an ethyl group, and n is an integer of 1 to 4.), and any one of R 1 , R 2 , R 3 and R 4 may form a ring. Absent. However, 1 ⁇ ! At least one of ⁇ 4 is the above alkoxyalkyl group.
- X represents a nitrogen atom or a phosphorus atom
- Y represents a monovalent anion.
- examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a 2-propyl group, a butyl group, a pentyl group, and the like.
- 1 ⁇ ! At least one of ⁇ 4 is preferably a methyl group, an ethyl group or a propyl group, particularly preferably a methyl group or an ethyl group.
- these ethyl group or propyl group may form a ring with another alkyl group.
- n— examples include a methoxy or ethoxymethyl group, a methoxy or ethoxyethyl group, a methoxy or ethoxypropyl group, a methoxy or ethoxybutyl group. Is mentioned.
- any two groups of Ri ⁇ R 4 forms a ring in the case of employing the nitrogen atom and X is an aziridine ring, Azechiji down ring, pyrrolidine ring, piperidine A quaternary ammonium salt having a ring and the like, and a quaternary phosphonium salt having a pentamethylenephosphine (phosphorinane) ring and the like when a phosphorus atom is employed for X are exemplified.
- a quaternary ammonium salt and a quaternary Specific examples of the phosphonium salt include the following compounds (2) to (11) (where Me represents a methyl group and Et represents an ethyl group), and particularly, methyl as a substituent.
- This ionic liquid is used as an electrolyte salt.
- the Anion Y of the monovalent is not particularly limited, BF 4 -, PF 6 _ , A s F 6 -, S b F 6 ⁇ A 1 C 1 4 -, HS_ ⁇ 4 -, C 1 0 4 —, CH 3 S ⁇ 3 —, CF 3 S ⁇ 3 —, CF 3 C ⁇ 2 —, (CF 3 SO 2) 2 N—, CI—, Br—, I— Although but cut with, the degree of dissociation of the non-aqueous organic solvent, considering the stability and mobility, etc.
- BFPF (CF 3 S_ ⁇ 2) 3 ⁇ 4 NCFSOCF 3 C_ ⁇ 2 one Among these, (CF 3 S ⁇ 2 ) 2 N— is preferred because it can lower the viscosity of the ionic liquid and improve the handling properties. It is preferable to use BF 4 — because it is less affected by water and easier to handle than PF 6 —.
- the general synthesis method of the above quaternary ammonium salt is as follows. First, a tertiary ammonium halide is mixed with an alkyl halide or dialkyl sulfate, and heated as necessary to obtain a quaternary ammonium halide salt. When a compound having low reactivity such as alkoxyethyl halide or alkoxymethyl halide is used, it is preferable to carry out the reaction under pressure using an autoclave or the like.
- the quaternary ammonium halide salt is soluble in an organic solvent, the halide salt is reacted with a silver salt of a required anion type to undergo anion exchange reaction to obtain a quaternary ammonium salt. Is also possible.
- a method for synthesizing quaternary ammonium tetrafluoroporate is as follows: quaternary ammonium halide is dissolved in water, salt exchange is performed by adding silver oxide, and quaternary ammonium hydroxide is produced. After being converted into a salt, the desired product can be obtained by reacting with borofluoric acid.
- This method is effective for synthesizing high-purity quaternary ammonium tetrafluoroborate because silver halide generated by salt exchange can be easily removed when a quaternary ammonium hydroxide salt is produced.
- Quaternary phosphonium salts like quaternary ammonium salts, are prepared by mixing tertiary phosphines with alkyl halide or dialkyl sulfate, etc., and generally synthesized by heating as necessary. Can be.
- the quaternary phosphonium halide (salt) is used in the same manner as the quaternary ammonium salt. Chloride, bromide, and iodide) are dissolved in an aqueous medium and reacted with a reagent that generates a required anion species, and an anion exchange reaction may be performed.
- the ionic liquid has a melting point of 50 ° C. or lower, preferably 30 ° C. or lower, particularly preferably 20 ° C. or lower.
- a melting point of 50 ° C. or lower, preferably 30 ° C. or lower, particularly preferably 20 ° C. or lower.
- the melting point exceeds 50 ° C.
- ionic liquid is precipitated in the electrolyte at a low temperature, and there is a high possibility that the ionic conductivity decreases.
- the lower the melting point of the ionic liquid, the better, and the lower limit is not particularly limited.
- the ionic liquid has a lower melting point than the ionic liquid containing imidazolyl ions, which has been widely used in the past, the use of an electrolyte containing the ionic liquid makes it possible to obtain a lower temperature characteristic. Thus, it is possible to obtain an electric double layer capacitor having excellent characteristics.
- the ionic liquid since the ionic liquid has a wider potential window than the ionic liquid having imidazonium ions, the ionic liquid is less susceptible to reduction decomposition during charging and discharging, and has a highly stable electric double layer capacity. Can be obtained.
- the electrolytic solution of the electric double layer capacity of the present invention comprises an ionic liquid and a non-aqueous organic solvent, and the non-aqueous organic solvent can dissolve the ionic liquid.
- the non-aqueous organic solvent can dissolve the ionic liquid.
- nitriles such as acetonitrile and propionitrile, dibutyl ether, 1,2-dimethoxyethane, 1,2-ethoxymethoxetane, methyldiglyme, methyltriglyme, methyltetraglyme, etylglyme, etyldiglyme, and butyltyl Chain ethers such as diglyme, glycol ethers (ethylcellsorb, ethylcarbitol butylcellsolve, butylcarbitol, etc.), tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dithiol Heterocyclic ethers such as quinolane, 4,4-dimethyl-1,3-dioxane, arbutyrrolactone, varvalerolacton, ⁇ -valerolactone, 3-methyl-1,3-oxazolidine 1-2-one, 3- Butylolactone
- the concentration of the ionic liquid in the electrolyte is not particularly limited, but is preferably 0.5 to 2.Omol ZL, more preferably 0.75 to 17.5mo1XL, and still more preferably, 0.9 to 1.5 mol ZL.
- the concentration of the ionic liquid is less than 0.5 mo 1 ZL, the loss may increase due to an increase in the internal resistance.
- the concentration exceeds 2.0 mo 1 / L, the viscosity may increase. In such a case, there is a possibility that problems such as a decrease in electric conductivity due to an increase in the electric current may occur.
- the peak of the pore radius distribution of the micropores as determined by the MP method is 4. 0 X 1 0 -. 1 0 ⁇ 8 0 X 1 0 - 1 ° m (4.0-8.OA), preferably 4.5 X 1 0 one 1. ⁇ 7. 0 X 1 0 - 1 ° m (. 4. 5 ⁇ 7 OA), more preferably 4. 5 X 1 0 - 1 0 ⁇ 6. 5 X 1 0 "1 ° m (4. 5 ⁇ 6 . 5 a), even more preferably 4 ⁇ 5 X 1 0- 1 0 ⁇ 5 ⁇ 0 X 1 0 - 1 ° m (4. 5 ⁇ 5, OA) as a main component an activated carbon which is within the range of It is.
- the MP method is a method generally used for the analysis of micropores.
- the results of the BET measurement are plotted for t times, and the pore radius distribution and its peak are analyzed by the curvature analysis near the bend. Is a method of calculating.
- the above-mentioned pore radius distribution and peak are values obtained from the results of BET measurement by nitrogen gas adsorption.
- charge-discharge characteristics at low temperatures is poor, whereas, if it is 8. 0 X 1 0- 1 Q m or more, is difficult to maintain a large specific surface area of the activated carbon, the specific surface area
- the capacitance may decrease due to the decrease in the capacitance.
- the raw material of the activated carbon is not particularly limited as long as the peak of the micropore size distribution can be within the above range.
- the synthetic resin various known raw materials that can be used as a raw material of activated carbon can be used.
- synthetic polymers phenolic resins, furan resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyimide resins , Polyamide resin, liquid crystal polymer, plastic waste, waste tires, etc., but considering price, versatility, ease of activation, etc., phenol resin and Z or polycarboimide resin are used.
- synthetic polymers phenolic resins, furan resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyimide resins , Polyamide resin, liquid crystal polymer, plastic waste, waste tires, etc., but considering price, versatility, ease of activation, etc., phenol resin and Z or polycarboimide resin are used.
- phenol resin and Z or polycarboimide resin are used.
- the activation method is not particularly limited, and known methods such as chemical activation using potassium hydroxide, zinc chloride, phosphoric acid, etc., and gas activation using carbon dioxide gas, oxygen, water vapor, etc. Various activation methods can be used. However, it is preferable to use the steam activation method because it is easy to control the pore radius of the activated carbon within the above range.
- the shape of the activated carbon includes various shapes such as crushing, granulation, granules, fibers, felt, woven fabric, and sheet shape, and any of them can be used in the present invention.
- the polarizable electrode one obtained by applying a polarized electrode composition comprising activated carbon having the above-mentioned micropore size distribution as a main component and further blending a binder polymer to the activated carbon onto a current collector is used.
- the binder polymer is not particularly limited as long as it is a polymer that can be used for the purpose, and various known binder polymers can be used. Examples thereof include polytetrafluoroethylene and polyfluoroethylene. Vinylidene fluoride, carboxymethylcellulose, fluoroolefin copolymer crosslinked polymer, polyvinyl alcohol ', polyacrylic acid, polyimide, petroleum pitch, coal pitch, phenolic resin and the like can be used.
- the addition amount of these binder polymers is preferably 0.5 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, based on 100 parts by weight of the activated carbon.
- the method for preparing the polarizable electrode composition is not particularly limited.
- the activated carbon and the binder polymer may be prepared in a solution.
- the solution may be prepared by adding a solvent as needed. You can also.
- a polarizable electrode By coating the polarizable electrode composition thus obtained on a current collector, a polarizable electrode can be obtained.
- the method of application is not particularly limited, and a known application method such as a doctor blade or an air knife may be appropriately employed.
- the positive and negative electrodes composing the current collector those usually used for electric double layer capacities can be arbitrarily selected and used, but aluminum foil or aluminum oxide should be used as the positive electrode current collector.
- the negative electrode current collector a copper foil, a nickel foil or a copper-coated film having a surface is also available. Alternatively, it is preferable to use a metal foil formed of a nickel plating film.
- the shape of the foil constituting each of the above current collectors can be a thin foil shape, a sheet shape spreading in a plane, a stampable sheet shape having holes formed therein, and the like. Usually, it is about 1 to 200 m, but in consideration of the density of the activated carbon occupying the whole electrode and the strength of the electrode, it is preferably 8 to 100 m, and more preferably 8 to 30 m.
- the polarizable electrode can also be formed by melt-kneading the polarizable electrode composition and then extruding a film.
- a conductive material can be added to the activated carbon.
- the conductive material is not particularly limited as long as it can impart conductivity to activated carbon.
- One of these fibers can be used alone, or two or more can be used in combination.
- ketjen black and acetylene black which are a kind of Rippon black, are preferable.
- the average particle size of the conductive material is not particularly limited, but is 1 O nm to: L 0 m, preferably 10 to: LOO nm, and more preferably 20 to 40 nm. It is preferable that the average particle size of the activated carbon is 1/500 to 1/2, particularly 17100 to 110.
- the amount of addition is not particularly limited, but is 0.1 to 20 parts by weight, preferably 100 to 100 parts by weight, based on the above-mentioned activated carbon in consideration of the capacitance and the effect of imparting conductivity. Is 0.5 to 10 parts by weight.
- separator one which is usually used as a separator for electric double layer capacity can be used.
- the electric double-layer capacity structure of the present invention is obtained by stacking, folding, or winding an electric double-layer capacity structure in which a separator is interposed between a pair of polarizable electrodes obtained as described above.
- the electric double layer capacitor of the present invention can be used as a memory backup power supply for mobile phones, notebook computers, portable terminals, etc., a power supply for mobile phones, portable audio equipment, etc.
- the present invention can be suitably used for various small-current storage devices such as a single-leveling power source by combining with solar power generation, wind power generation, and the like.
- An electric double-layer capacitor capable of charging and discharging with a large current can be suitably used as a large-current storage device requiring a large current, such as an electric vehicle or an electric tool.
- the electric double layer capacity of the present invention uses, as a polarizing electrode, a material having, as a main component, activated carbon having a peak having a pore radius distribution of predetermined micropores, and an electrolytic solution. Since a material containing an ionic liquid is used, the charge / discharge characteristics at low temperatures are excellent, and the internal impedance at low temperatures can be reduced.
- ionic liquids composed of quaternary ammonium salts and quaternary phosphonium salts have a wider potential window than imidazolium- and pyridinium-based ionic liquids.
- an electric double layer capacitor having a high energy density can be obtained.
- Jetilamine manufactured by Kanto Chemical Co., Ltd.
- 2-methoxyl chloride manufactured by Kanto Chemical Co., Ltd.
- the reaction was carried out at 00 ° C. for 24 hours. At this time, the internal pressure was 0.127 MPa (1.3 kgf / cm 2 ).
- 200 ml of an aqueous solution of 56 g of potassium hydroxide was added to the mixture of the precipitated crystals and the reaction solution.
- the separated organic layer was separated into two layers. Separation was performed with a separating funnel.
- NMR 2-methoxylethyl tylamine
- FIG. 1 shows an NMR chart (solvent: double-mouthed form) of compound (2).
- FIG. 2 shows an NMR chart (solvent: heavy dimethyl sulfoxide) of the compound (11).
- Activated carbon 1 which is obtained by steam-activating phenolic resin carbide for 2 hours and has a specific surface area and a pore distribution peak value shown in Table 1, conductive agent (HS-100, manufactured by Denki Kagaku Kogyo Co., Ltd.), Pinda 1 (PV dF900, manufactured by Kureha Chemical Industry Co., Ltd.) was prepared at a compounding ratio of 90: 5: 5 (mass ratio), respectively.
- This slurry was applied to a 30 m aluminum foil at an electrode thickness of 100 / zm.After drying under reduced pressure at 140 ° C for 3 days, a stress of 30 MPa was applied using a roll press. .
- Example 3 An electric double layer capacity was prepared in the same manner as in Example 1 except that activated carbon 2 obtained by steam-activating phenol resin carbide for 3 hours was used as the activated carbon in the electrode, and compound (11) was used as the electrolyte salt in the electrolyte. An evening sample was prepared. [Example 3]
- Example 2 The same procedure as in Example 1 was repeated except that activated carbon 3 (MS P _20, manufactured by Kansai Thermal Chemical Co., Ltd.) was used as the activated carbon in the electrode, and the pore diameter was increased by steam activation for 1 hour. An electric double layer capacity sample was prepared.
- activated carbon 3 MS P _20, manufactured by Kansai Thermal Chemical Co., Ltd.
- Activated carbon 3 (MSP_20, manufactured by Kansai Thermal Chemical Co., Ltd.) was used as the activated carbon in the electrode, and the pore size was increased by steam activation for 1 hour.
- the compound (1) was used as the electrolyte salt in the electrolyte.
- An electric double layer capacitor sample was prepared in the same manner as in Example 1 except that 1) was used.
- An electric double layer capacitor sample was prepared in the same manner as in Example 1 except that alkali-activated activated carbon (MS P-20, manufactured by Kansai Thermal Chemical Co., Ltd.) was used as the activated carbon in the electrode (activated carbon 4).
- alkali-activated activated carbon MS P-20, manufactured by Kansai Thermal Chemical Co., Ltd.
- TEA tetraethylammonium tetrafluoroborate
- An electric double layer capacitor sample was prepared in the same manner as in Example 1, except that activated carbon 5 in which phenol resin carbide was steam-activated for 6 hours was used as the activated carbon in the electrode. [table 1 ]
- the evaluation method was as follows: Initial capacity confirmation test: charging at a current density of 0.88 mA / cm 2 , a set voltage of 2.50 V, a constant voltage time of 15 minutes (end condition) at room temperature, and a current density of 0 Discharge was performed at 88 mA / cm 2 and a final voltage of 0.0 V.
- the polarizable electrode, activated carbon in the peak of the pore radius distribution of the micropores as determined by the MP method is 4. ⁇ ⁇ ⁇ ⁇ ⁇ . 0 X 1 0- 1 () m in within range Since it is an electric double layer capacitor that is composed as a main component and contains an ionic liquid as an electrolyte salt, it has excellent charge / discharge characteristics at low temperatures and low internal impedance at low temperatures. can do.
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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AT03792799T ATE526672T1 (de) | 2002-08-23 | 2003-08-22 | Elektrischer doppelschichtkondensator |
US10/525,201 US7342769B2 (en) | 2002-08-23 | 2003-08-22 | Electric double-layer capacitor |
AU2003262276A AU2003262276A1 (en) | 2002-08-23 | 2003-08-22 | Electric double-layer capacitor |
JP2004530603A JP4548592B2 (ja) | 2002-08-23 | 2003-08-22 | 電気二重層キャパシタ |
EP03792799A EP1536440B1 (en) | 2002-08-23 | 2003-08-22 | Electric double-layer capacitor |
CA002496544A CA2496544A1 (en) | 2002-08-23 | 2003-08-22 | Electric double-layer capacitor |
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JP2002243236 | 2002-08-23 | ||
JP2002/243236 | 2002-08-23 |
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WO2004019356A1 true WO2004019356A1 (ja) | 2004-03-04 |
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PCT/JP2003/010630 WO2004019356A1 (ja) | 2002-08-23 | 2003-08-22 | 電気二重層キャパシタ |
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US (1) | US7342769B2 (ja) |
EP (1) | EP1536440B1 (ja) |
JP (1) | JP4548592B2 (ja) |
KR (1) | KR101016268B1 (ja) |
CN (1) | CN100468587C (ja) |
AT (1) | ATE526672T1 (ja) |
AU (1) | AU2003262276A1 (ja) |
CA (1) | CA2496544A1 (ja) |
WO (1) | WO2004019356A1 (ja) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2007116101A (ja) * | 2005-09-26 | 2007-05-10 | Nisshinbo Ind Inc | 電気二重層キャパシタ |
JP2007116102A (ja) * | 2005-09-26 | 2007-05-10 | Nisshinbo Ind Inc | 電気二重層キャパシタ |
JP2007266248A (ja) * | 2006-03-28 | 2007-10-11 | Osaka Gas Co Ltd | 電気二重層キャパシタ用炭素材料、電気二重層キャパシタ用電極、及び電気二重層キャパシタ |
JP2008108979A (ja) * | 2006-10-26 | 2008-05-08 | Kansai Coke & Chem Co Ltd | 電気二重層キャパシタ用電極材料、およびその製造方法 |
JP2011129794A (ja) * | 2009-12-21 | 2011-06-30 | Panasonic Corp | 電気化学素子用活性炭、及びこれを用いた電気化学素子 |
JP5573673B2 (ja) * | 2008-06-24 | 2014-08-20 | パナソニック株式会社 | 電気化学素子 |
WO2015045389A1 (ja) | 2013-09-25 | 2015-04-02 | 国立大学法人東京大学 | アルカリ金属、アルカリ土類金属又はアルミニウムをカチオンとする塩と、ヘテロ元素を有する有機溶媒とを含む、電池、キャパシタ等の蓄電装置用電解液、及びその製造方法、並びに当該電解液を具備するキャパシタ |
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US8907133B2 (en) | 2008-07-14 | 2014-12-09 | Esionic Es, Inc. | Electrolyte compositions and electrochemical double layer capacitors formed there from |
CN103620714A (zh) * | 2011-05-10 | 2014-03-05 | Cap-Xx有限公司 | 电解液 |
CN105164777A (zh) * | 2012-12-05 | 2015-12-16 | 伊赛欧尼克公司 | 电解质组合物和由其形成的电化学双层电容器 |
WO2017201167A1 (en) | 2016-05-20 | 2017-11-23 | Avx Corporation | Electrode configuration for an ultracapacitor |
KR102635455B1 (ko) | 2016-05-20 | 2024-02-13 | 교세라 에이브이엑스 컴포넌츠 코포레이션 | 고온용 울트라커패시터 |
WO2017201173A1 (en) | 2016-05-20 | 2017-11-23 | Avx Corporation | Nonaqueous electrolyte for an ultracapacitor |
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JP2007116101A (ja) * | 2005-09-26 | 2007-05-10 | Nisshinbo Ind Inc | 電気二重層キャパシタ |
JP2007116102A (ja) * | 2005-09-26 | 2007-05-10 | Nisshinbo Ind Inc | 電気二重層キャパシタ |
JP2007266248A (ja) * | 2006-03-28 | 2007-10-11 | Osaka Gas Co Ltd | 電気二重層キャパシタ用炭素材料、電気二重層キャパシタ用電極、及び電気二重層キャパシタ |
JP2008108979A (ja) * | 2006-10-26 | 2008-05-08 | Kansai Coke & Chem Co Ltd | 電気二重層キャパシタ用電極材料、およびその製造方法 |
JP5573673B2 (ja) * | 2008-06-24 | 2014-08-20 | パナソニック株式会社 | 電気化学素子 |
JP2011129794A (ja) * | 2009-12-21 | 2011-06-30 | Panasonic Corp | 電気化学素子用活性炭、及びこれを用いた電気化学素子 |
WO2011077663A1 (ja) * | 2009-12-21 | 2011-06-30 | パナソニック株式会社 | 電気化学素子用活性炭、及びこれを用いた電気化学素子 |
WO2015045389A1 (ja) | 2013-09-25 | 2015-04-02 | 国立大学法人東京大学 | アルカリ金属、アルカリ土類金属又はアルミニウムをカチオンとする塩と、ヘテロ元素を有する有機溶媒とを含む、電池、キャパシタ等の蓄電装置用電解液、及びその製造方法、並びに当該電解液を具備するキャパシタ |
KR20180103193A (ko) | 2013-09-25 | 2018-09-18 | 고쿠리츠다이가쿠호징 도쿄다이가쿠 | 알칼리 금속, 알칼리 토금속 또는 알루미늄을 양이온으로 하는 염과, 헤테로 원소를 갖는 유기 용매를 포함하는, 전지, 커패시터 등의 축전 장치용 전해액 및, 그의 제조 방법, 그리고 당해 전해액을 구비하는 커패시터 |
US10686223B2 (en) | 2013-09-25 | 2020-06-16 | Kabushiki Kaisha Toyota Jidoshokki | Nonaqueous electrolyte secondary battery |
US11011781B2 (en) | 2013-09-25 | 2021-05-18 | The University Of Tokyo | Nonaqueous electrolyte secondary battery |
Also Published As
Publication number | Publication date |
---|---|
KR20050056971A (ko) | 2005-06-16 |
AU2003262276A1 (en) | 2004-03-11 |
EP1536440B1 (en) | 2011-09-28 |
CA2496544A1 (en) | 2004-03-04 |
JPWO2004019356A1 (ja) | 2005-12-15 |
JP4548592B2 (ja) | 2010-09-22 |
EP1536440A1 (en) | 2005-06-01 |
US20060176646A1 (en) | 2006-08-10 |
ATE526672T1 (de) | 2011-10-15 |
EP1536440A4 (en) | 2009-02-25 |
KR101016268B1 (ko) | 2011-02-25 |
CN100468587C (zh) | 2009-03-11 |
US7342769B2 (en) | 2008-03-11 |
CN1679126A (zh) | 2005-10-05 |
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