WO2011070924A1 - Condensateur électrique bicouche - Google Patents

Condensateur électrique bicouche Download PDF

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Publication number
WO2011070924A1
WO2011070924A1 PCT/JP2010/071121 JP2010071121W WO2011070924A1 WO 2011070924 A1 WO2011070924 A1 WO 2011070924A1 JP 2010071121 W JP2010071121 W JP 2010071121W WO 2011070924 A1 WO2011070924 A1 WO 2011070924A1
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Prior art keywords
electrode
fluorine
electric double
double layer
layer capacitor
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PCT/JP2010/071121
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English (en)
Japanese (ja)
Inventor
謙三 高橋
明天 高
舞 小山
絵美 宮永
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ダイキン工業株式会社
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Publication of WO2011070924A1 publication Critical patent/WO2011070924A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to an electric double layer capacitor.
  • the electric double layer capacitor is expected to be used as a power source for electric vehicles and instantaneous power outages, and various studies have been made. Such an electric double layer capacitor is desired to have a high capacitance and a low internal resistance.
  • a solvent for dissolving the electrolyte an aqueous solvent (Patent Document 1), a non-fluorine-based non-aqueous solvent (Patent Document 2), or a fluorine-based capacitor is used.
  • Non-aqueous solvent Patent Document 3 is used.
  • Patent Document 2 also proposes a configuration of an electrode, a spherical activated carbon having a specific particle size and pore volume activated by a molten KOH activation treatment method (alkali activation treatment method), and conductivity imparting. It is stated that a high capacitance and a low internal resistance can be realized by making the agent and the polymer binder have a specific bulk density.
  • the electric double layer capacitor is required to have the above-mentioned high capacitance and low internal resistance, and also needs a high withstand voltage corresponding thereto.
  • An object of the present invention is to provide an electric double layer capacitor having a high capacitance, a low internal resistance, and a high withstand voltage.
  • the present invention provides an electrode comprising an electrode layer containing activated carbon particles (IA), binder (IB), ketjen black (IC) and acrylic acid compound (ID) obtained by steam activation of non-graphitizable carbon.
  • the present invention relates to an electrode for a multilayer capacitor.
  • the electrode layer is preferably provided on a conductive film formed on the surface of the current collector.
  • the electrode density of the electrode layer is preferably 0.45 g / cm 3 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 preferably comprises a non-aqueous electrolyte, particularly a fluorine electrolyte, as the electrolyte.
  • an electric double layer capacitor having a high capacitance, a low internal resistance, and a high withstand voltage.
  • the electrode for an electric double layer capacitor of the present invention includes activated carbon particles (IA), binder (IB), ketjen black (IC) and acrylic acid compound (ID) obtained by steam activation of non-graphitizable carbon.
  • IA activated carbon particles
  • IB binder
  • IC ketjen black
  • ID acrylic acid compound
  • activated carbon particles have a role of increasing the capacitance of an electric double layer capacitor.
  • the activated carbon particles used in the present invention are activated carbon particles obtained by steam activation of hardly graphitized carbon particles.
  • the activated carbon material there are activated carbon which is easily graphitized (easily graphitized carbon) and activated carbon which is not easily graphitized (non-graphitizable carbon).
  • non-graphitized carbon is used.
  • activation treatment such as a steam activation treatment method or a molten KOH activation treatment method (alkali activation treatment method) is performed.
  • a steam activation treatment method is adopted.
  • Activated carbon particles obtained by steam activation of non-graphitizable carbon have excellent properties such as low capacity degradation when high voltage is applied, and the reason is not clear, but these properties are easily graphitized. Compared to the case of using carbon or the case of activation treatment by the molten KOH activation treatment method.
  • Non-graphitizable carbon refers to carbon that is difficult to graphitize even when carbonized at high temperatures in an inert gas atmosphere, and can be classified as easily graphitized carbon that is easily graphitized by the same carbonization treatment.
  • the non-graphitizable carbon generally includes those obtained by carbonizing a thermosetting resin or a natural organic substance, and the graphitizable carbon is obtained by carbonizing a thermoplastic resin or petroleum pitch.
  • Thermosetting resins as raw materials for non-graphitizable carbon include, for example, phenol resins, epoxy resins, alkyd resins, melamine resins, urea resins, urethane resins, unsaturated polyester resins, diallyl phthalate resins, as well as furfural resins and silicones. Resin, furan resin, xylene resin and the like can be mentioned, and activated carbon particles can be obtained by carbonizing the granular material.
  • natural coconut shells are preferable from the viewpoint of easy availability, and coconut husk charcoal can be obtained by carbonizing a material containing no harmful impurities.
  • the steam activation treatment of the hardly graphitized carbon may be a conventionally known method.
  • the hardly graphitized carbon is preferably heated at a temperature of 500 to 1000 ° C., more preferably 700 to 1000 ° C. for about 5 minutes to 10 hours in a steam atmosphere.
  • the method of processing can be illustrated, it is not limited to this condition.
  • the activated carbon particles obtained by the steam activation treatment are activated by being made porous.
  • the activated carbon particles subjected to the steam activation treatment are activated carbon particles having an average particle size of 20 ⁇ m or less, preferably 10 ⁇ m or less, and a specific surface area of 1500 to 3000 m 2 / g from the viewpoint of obtaining a large capacity and low internal resistance electric double layer capacitor. Is preferred. Further, activated carbon particles having a potassium content measured by an extraction method of about 0 to 200 ppm or a pore volume of 1.5 cm 3 / g or less are also preferable.
  • Examples of commercially available non-graphitized carbon activated carbon particles that have been subjected to water vapor activation treatment derived from coconut shell charcoal include YP50F, YP50FH, YP80F, and YP80FH (all trade names) manufactured by Kuraray Chemical Co., Ltd. It is not limited.
  • a phenol resin is also exemplified.
  • examples of commercially available non-graphitized carbon activated carbon particles that have been subjected to water vapor activation treatment derived from phenol resin include RP-20 (trade name) manufactured by Kuraray Chemical Co., Ltd., but are not limited thereto. .
  • the binder (IB) is formed by forming activated carbon particles (IA) and other electrode components such as ketjen black (IC) added as a conductive material into the electrodes. Used to join.
  • a fluorine resin such as polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVdF); a non-fluorine resin such as butadiene rubber or styrene butadiene rubber. Elastomer is used.
  • a fluororesin particularly PTFE
  • PTFE a fluororesin
  • an acrylate copolymer which is a non-fluorine-based elastomer is preferable from the viewpoint of good pressure resistance and good adhesion to a current collector.
  • Ketjen Black plays a role as a conductive material.
  • the conductive material as the capacitor electrode material is an activated carbon with a large specific surface area and has the role of imparting electron conductivity.
  • carbonaceous materials such as carbon black, acetylene black, natural graphite, artificial graphite, etc.
  • Materials Inorganic materials such as metal fibers, conductive titanium oxide, and ruthenium oxide are known.
  • Ketjen Black (IC ) Is When activated carbon particles (IA) obtained by steam activation of non-graphitizable carbon are used, Ketjen Black (IC ) Is used in combination, it provides a higher withstand voltage, and also has a high capacitance and a low internal resistance.
  • Ketjen Black for example, Carbon ECP600JD manufactured by Lion Corporation can be cited.
  • the acrylic compound (ID) is a component added in addition to the activated carbon particles (IA), the binder (IB) and the ketjen black (IC) as such a thickener, which is surprising.
  • it has a higher withstand voltage than other compounds known as thickeners, such as carboxymethylcellulose (CMC), and plays a major role in improving the performance of capacitors using a fluorine-based electrolyte having a high withstand voltage. Plays.
  • CMC carboxymethylcellulose
  • the reason for this is not clear, but it is presumed that it has a carboxyl group that is not easily oxidized but is not easily oxidized, and is not easily oxidized.
  • the dispersibility of other particles which is the original purpose of addition, is also good, and the strength of the produced electrode is also good.
  • acrylic acid compound (ID) examples include polyacrylic acid or a salt thereof such as sodium, potassium and lithium; one or more of polyacrylic acid salt, polyacrylic acid ester, acrylic acid copolymer and the like. Specific examples include polyacrylic acid; homopolymers or copolymers of acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and isopropyl acrylate.
  • acrylic acid compounds examples include polyacrylic acid such as Aron A-10H manufactured by Toagosei Co., Ltd .; and ammonium polyacrylate such as Aron A-30 manufactured by Toagosei Co., Ltd.
  • IE Other electrode components
  • IA activated carbon particles
  • IB binder
  • ketjen black IC
  • ID acrylic acid compound
  • Additives may be blended. Examples of other additives include the conductive materials other than ketjen black (IC).
  • a preferable additive is, for example, acetylene black, and a commercially available product is, for example, Denka Black FX-35 manufactured by Denki Kagaku Kogyo Co., Ltd.
  • Electrode components are based on 100 parts by mass of activated carbon particles (IA), 2-20 parts by mass of binder (IB), 1-30 parts by mass of Ketjen Black (IC), acrylic compound (ID) Is preferably blended in an amount of 1 to 5 parts by mass.
  • IA activated carbon particles
  • binder IB
  • Ketjen Black IC
  • acrylic compound ID
  • Is preferably blended in an amount of 1 to 5 parts by mass.
  • 3 to 10 parts by weight of binder (IB) and 8 parts of ketjen black (IC) are used per 100 parts by weight of activated carbon particles (IA). More preferably, 20 parts by mass and 2-4 parts by mass of an acrylic acid compound (ID) are blended.
  • the activated carbon particles (IA) are used so as to obtain good conductivity (low internal resistance) and, if too much, the capacitance of the capacitor is reduced. Is preferably adjusted so that the total amount of ketjen black (IC) and other conductive material is 1 to 50% by mass.
  • the electrode can be formed by various methods. For example, activated carbon particles (IA), ketjen black (IC) and, if necessary, other electrode components (IE) such as other conductive materials are dry mixed. In the mixing process, acrylic acid compound (ID) and water are added as appropriate to disperse the particles. Next, a binder (IB) and water are added as appropriate, followed by wet mixing to prepare a homogeneous electrode forming slurry. This slurry is applied on a metal foil such as a current collector, pressed as appropriate, and dried to produce an electrode.
  • IA activated carbon particles
  • IC ketjen black
  • IE other electrode components
  • the bulk density (electrode density) of the produced electrode it is preferable to adjust the bulk density (electrode density) of the produced electrode to 0.45 g / cm 3 or less.
  • the electrode density is increased (0.6 g / cm 3 or more) from the viewpoint of improvement in capacitance and reduction in internal resistance (for example, Patent Document 2). There is no example of examining the electrode density.
  • Electrode density is preferably 0.45 g / cm 3 or less from the viewpoint withstand voltage is good, more is 0.40 g / cm 3 or less. On the other hand, 0.35 g / cm 3 or more is preferable from the viewpoint of maintaining the mechanical strength.
  • the method for adjusting the electrode density is not particularly limited, and for example, the following method can be adopted.
  • Method of adjusting solid content concentration of electrode slurry For example, it is preferable to adjust the solid content concentration to 15 to 25% by mass, preferably 18 to 22% by mass.
  • the pressing pressure may be appropriately selected according to the target electrode thickness and the like.
  • the current collector may be any material that is chemically and electrochemically resistant to corrosion.
  • the conductive coating is obtained by applying graphite particles having an average particle diameter of 10 ⁇ m as a filler and a water paint of cellulose as a binder on a current collector, and preferably has a thickness of 1 to 30 ⁇ m. By setting it as this thickness, formation of an electrode layer becomes easy and increase of the internal resistance of an electrode can be suppressed.
  • the electrode layer is formed on the conductive film of the current collector on which the conductive film is formed, from the viewpoint of improvement in the withstand voltage of the electrode, high temperature load characteristics, and the like.
  • the electrode may be an electric double layer capacitor using the above electrodes for both electrodes, but a configuration using a non-polarizable electrode on one side, for example, a positive electrode mainly composed of a battery active material such as a metal oxide, and activated carbon mainly A configuration in which the negative electrode of the electrode of the present invention is combined is also possible.
  • the present invention also relates to an electric double layer capacitor comprising the electrode of the present invention.
  • the structure of the electric double layer capacitor of the present invention may be the same as that of a conventionally known electric double layer capacitor except that the electrode of the present invention is provided, and if necessary between the positive electrode and the negative electrode, an electrolyte is filled through a separator. Composed.
  • the electrolytic solution may be an aqueous electrolytic solution, but a non-aqueous (organic) electrolytic solution is preferable because the operating voltage can be widened.
  • the non-aqueous electrolyte suitably used in the present invention is a fluorine electrolyte and includes a fluorine solvent (IIA) and an electrolyte salt (IIB).
  • fluorinated solvent (IIA) used in the electric double layer capacitor of the present invention for example, a fluorinated solvent containing a fluorinated cyclic carbonate described in Patent Document 3 has a high electric resistance and a wide electrolyte. It is preferable from the viewpoint of excellent solubility.
  • the formula (1) As the fluorine-containing cyclic carbonate, the formula (1): (Wherein X 1 to X 4 are the same or different and all are —H, —F, —CF 3 , —CHF 2 , —CH 2 F, —C 2 F 5 or —CH 2 CF 3 ; At least one of X 1 to X 4 is —F, —CF 3 , —C 2 F 5 or —CH 2 CF 3 ). This is preferable from the viewpoint of high withstand voltage.
  • the fluorine-containing cyclic carbonate contained in the fluorine-based solvent (IIA) has particularly excellent characteristics such as a high dielectric constant and a high withstand voltage, and also has a good ability to reduce the solubility of the electrolyte salt and internal resistance. From the point that the characteristics as an electric double layer capacitor in the present invention is improved, It is preferably at least one selected from the group consisting of:
  • the fluorine content of the fluorine-containing cyclic carbonate is preferably 15 to 55% by mass, more preferably 17 to 44% by mass from the viewpoint of dielectric constant and oxidation resistance.
  • Etc. can also be used as the fluorine-containing cyclic carbonate.
  • the content of the fluorinated cyclic carbonate in the fluorinated solvent (IIA) is preferably 100 to 20% by volume, more preferably 90 to 20% by volume, from the viewpoint of good dielectric constant and viscosity.
  • the fluorinated cyclic carbonate represented by the formula (1) may be used alone or as a mixture with other fluorinated electrolyte salt dissolving solvent or non-fluorinated electrolyte salt dissolving solvent. May be.
  • a fluorine-containing cyclic carbonate generally has a high melting point, it may cause an obstacle to operation at a low temperature by itself. In such a case, it should be used as a mixture of the fluorine-containing cyclic carbonate represented by the formula (1) and another solvent for dissolving the fluorine-containing electrolyte salt from the viewpoint of improving oxidation resistance and viscosity and maintaining low temperature characteristics. Is preferred.
  • Solvents for dissolving the fluorine-containing electrolyte salt used as a co-solvent for the fluorine-containing cyclic carbonate represented by the formula (1) include fluorine-containing chain carbonates, fluorine-containing chain esters, fluorine-containing chain ethers, fluorine-containing lactones, And fluorine sulfolane derivatives.
  • Rf a1 and Rf a2 are the same or different and are an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms, provided that at least one of them is a fluorine-containing group having 1 to 4 carbon atoms.
  • Those represented by (which are alkyl groups) are preferred.
  • fluorine-containing chain carbonates this is because it has excellent characteristics such as high dielectric constant and high withstand voltage, and it can improve the solubility of electrolyte salts, reduce internal resistance, and maintain low-temperature characteristics. From the point that the characteristics as an electric double layer capacitor in the invention are improved, Etc. are preferable.
  • Etc fluorine-containing chain carbonate
  • compounds described in JP-A-06-21992, JP-A-2000-327634, JP-A-2001-256983 and the like can be mentioned.
  • fluorine-containing chain ether examples include, for example, Japanese Patent Application Laid-Open Nos. 08-037024, 09-097627, 11-026015, 2000-294281, and 2001-052737. Examples thereof include compounds described in JP-A-11-307123.
  • Rf c1 -O-Rf c2 (3) (Wherein, Rfc1 and Rfc2 are the same or different and both are fluorine-containing alkyl groups having 2 to 4 carbon atoms).
  • Rf c1 includes, for example, —CH 2 CF 2 CHF 2 , —CH 2 C 2 F 4 CHF 2 , —CH 2 CF 3 , —CH 2 C 3 F 6 CHF 2 , —CH 2 C 2 F 5 , —CH 2 CF 2 CHFCF 3 , —CH 2 CF (CF 3 ) CF 2 CHF 2 , —C 2 H 4 C 2 F 5 , —C 2 H 4 CF 3 and the like, and Rf c2
  • —CF 2 CF 2 H, —CF 2 CHFCF 3 , —C 2 F 4 CHF 2 , —C 2 H 4 CF 3 , —CH 2 CHFCF 3 , —C 2 H 4 C 2 F 5 are preferable.
  • fluorine-containing chain ester examples include CF 3 C ( ⁇ O) OC 2 F 5 , CF 3 C ( ⁇ O) OCH 2 CF 3 , CF 3 C ( ⁇ O) OCH 2 CH 2 CF 3 , and CF 3.
  • CF 3 C ( ⁇ O) OC 2 F 5 , CF 3 C ( ⁇ O) are preferred because they have good compatibility with other solvents, viscosity, and oxidation resistance.
  • OCH 2 C 2 F 5 , CF 3 C ( ⁇ O) OCH 2 CF 2 CF 2 H, CF 3 C ( ⁇ O) OCH 2 CF 3 , CF 3 C ( ⁇ O) OCH (CF 3 ) 2 are particularly preferred. .
  • fluorine-containing lactone for example, formula (5): (Wherein X 5 to X 10 are the same or different and all are —H, —F, —Cl, —CH 3 or a fluorine-containing methyl group; provided that at least one of X 5 to X 10 is fluorine-containing methyl
  • fluorine-containing lactone examples include those represented by the formula (6): (In the formula, either one of A and B is CX 16 X 17 (X 16 and X 17 are the same or different, and all are —H, —F, —Cl, —CF 3 , —CH 3 or a hydrogen atom) may be substituted with a halogen atom include a hetero atom in the chain is also an alkyl group), the other is an oxygen atom; Rf e is a fluorine-containing ether group, a fluorine-containing alkoxy group or having two or more carbon atoms containing Fluoroalkyl group; X 11 and X 12 are the same or different, all are —H, —F, —Cl, —CF 3 or —CH 3 ; X 13 to X 15 are the same or different and both are —H, Examples thereof include -F, -Cl or an alkyl group in which a hydrogen atom may be substituted with a
  • Etc. can also be used.
  • fluorine-containing sulfolane derivative examples include the fluorine-containing sulfolane derivatives described in JP-A-2003-132994, Is preferred.
  • Solvents for dissolving the non-fluorinated electrolyte salt used as a co-solvent for the fluorine-containing cyclic carbonate represented by the formula (1) include non-fluorinated cyclic carbonates, non-fluorinated chain carbonates, non-fluorinated chain esters, non-fluorine Examples thereof include chain ethers, non-fluorine lactones, non-fluorine sulfolane derivatives, and other solvents for dissolving non-fluorine electrolyte salts.
  • non-fluorinated cyclic carbonates examples include: Etc.
  • non-fluorine chain carbonate for example, the formula (7): (Wherein, R a1 and R a2 are the same or different and both are alkyl groups having 1 to 4 carbon atoms).
  • the electric double layer capacitor according to the present invention is particularly advantageous in that it has excellent characteristics such as a high dielectric constant and a high withstand voltage, and also has good solubility in electrolyte salts and a reduction in internal resistance. From the point that the characteristics as Etc. are preferable.
  • non-fluorine chain carbonates include Etc. can also be used.
  • the electrolyte salt dissolving solvent used as a co-solvent for the fluorine-containing cyclic carbonate represented by the formula (1) is preferably a fluorine-containing electrolyte salt dissolving solvent from the viewpoint of good oxidation resistance and viscosity. More preferred are fluorine chain carbonates, fluorine-containing chain esters, and fluorine-containing chain ethers.
  • the solvent (IIA) for operation at a high voltage of 3.5 V or higher includes the fluorine-containing cyclic carbonate represented by the formula (1), the fluorine-containing chain carbonate, the fluorine-containing chain ester, and the fluorine-containing chain. What consists only of at least 1 sort (s) chosen from the group which consists of ether is preferable. Of these, fluorine-containing chain ethers are preferred from the viewpoint of good oxidation resistance.
  • Fluorine-containing cyclic carbonates CF 3 CF 2 CH 2 —O—CF 2 CFHCF 3 , HCF 2 CF 2 CH 2 —O—CF 2 CFHCF 3 , CF 3 CF 2 CH 2 —O—CF 2 CF 2 H and It is a mixture with at least one fluorine-containing chain ether selected from the group consisting of HCF 2 CF 2 CH 2 —O—CF 2 CF 2 H.
  • the electrolyte salt (IIB) includes conventionally known ammonium salts and metal salts, liquid salts (ionic liquids), inorganic polymer type salts, organic polymer type salts, and the like. .
  • ammonium salt conventionally known ones can be used, and examples include spiro-ring bipyridinium salts, imidazolium salts, tetraalkyl quaternary ammonium salts, N-alkylpyridinium salts, N, N-dialkylpyrrolidinium salts and the like.
  • Examples of the spiro ring bipyridinium salt include those represented by the formula (10-1): (Wherein R f1 and R f2 are the same or different and both are alkyl groups having 1 to 4 carbon atoms; X ⁇ is an anion; n1 is an integer of 0 to 5; n2 is an integer of 0 to 5) Spirocyclic bipyridinium salt, formula (10-2): (Wherein R f3 and R f4 are the same or different and both are alkyl groups 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) Spiro ring bipyridinium salt or formula (10-3): (Wherein R f5 and R f6 are the same or different and both are alkyl groups having 1 to 4 carbon atoms; X ⁇ is an anion; n5 is an integer of 0 to 5; n6 is an integer of 0
  • the spiro-ring bipyridinium salt in which part or all of the hydrogen atoms are substituted with a fluorine atom and / or a fluorine-containing alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of improving oxidation resistance.
  • the anion X ⁇ may be an inorganic anion or an organic anion.
  • the inorganic anion include AlCl 4 ⁇ , BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , TaF 6 ⁇ , I ⁇ and SbF 6 ⁇ .
  • the organic anion include CH 3 COO ⁇ , CF 3 SO 3 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , (C 2 F 5 SO 2 ) 2 N ⁇ and the like.
  • BF 4 ⁇ , PF 6 ⁇ , (CF 3 SO 2 ) 2 N ⁇ or (C 2 F 5 SO 2 ) 2 N ⁇ are highly dissociable and have low internal resistance under high voltage. In particular, BF 4 ⁇ and PF 6 ⁇ are more preferable.
  • spirocyclic bipyridinium salt examples include, for example, Etc.
  • This spiro-ring bipyridinium salt is excellent in terms of solubility in a solvent, oxidation resistance, and ion conductivity.
  • an imidazolium salt for example, formula (11): An imidazolium salt represented by the formula (wherein R g1 and R g2 are the same or different and both are alkyl groups having 1 to 6 carbon atoms; X ⁇ is an anion) is preferred.
  • the imidazolium salt in which part or all of the hydrogen atoms are substituted with a fluorine atom and / or a fluorine-containing alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of improving oxidation resistance.
  • Preferred examples of the anion X ⁇ are the same as those of the spiro ring bipyridinium salt.
  • imidazolium salts include, for example, formula (12): And ethylmethylimidazolium salt represented by the formula:
  • This imidazolium salt has low viscosity and is excellent in solubility in a solvent.
  • tetraalkyl quaternary ammonium salt examples include the formula (13): (Wherein R h1 , R h2 , R h3 and R h4 are the same or different, and all are alkyl groups which may contain an ether bond having 1 to 6 carbon atoms; X ⁇ is an anion) Preferred is a quaternary ammonium salt.
  • the tetraalkyl quaternary ammonium salt in which part or all of the hydrogen atoms are substituted with fluorine atoms and / or fluorine-containing alkyl groups having 1 to 4 carbon atoms is preferable from the viewpoint of improving oxidation resistance. .
  • Preferred examples of the anion X ⁇ are the same as those of the spiro ring bipyridinium salt.
  • tetraalkyl quaternary ammonium salt examples include, for example, Et 4 NBF 4 , Et 4 NClO 4 , Et 4 NPF 6 , Et 4 NAsF 6 , Et 4 NSbF 6 , Et 4 NCF 3 SO 3 , Et 4 N (CF 3 SO 2 ) 2 N, Et 4 NC 4 F 9 SO 3 , Et 3 MeBF 4 , Et 3 MeClO 4 , Et 3 MePF 6 , Et 3 MeAsF 6 , Et 3 MeSbF 6 , Et 3 MeCF 3 SO 3 Et 3 Me (CF 3 SO 2 ) 2 N, Et 3 MeC 4 F 9 SO 3, etc., especially Et 4 NBF 4 , Et 4 NPF 6 , Et 4 NSbF 6 , Et 4 NAsF 6 (Me is A methyl group, Et is an ethyl group) and the like are preferable.
  • N-alkylpyridinium salts include, for example, formula (14): N-alkylpyridinium salts represented by the formula (wherein R i1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; X ⁇ is an anion) are preferred.
  • the N-alkylpyridinium salt in which part or all of the hydrogen atoms are substituted with a fluorine atom and / or a fluorine-containing alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of improving oxidation resistance.
  • Preferred examples of the anion X ⁇ are the same as those of the spiro ring bipyridinium salt.
  • This N-alkylpyridinium salt has low viscosity and is excellent in solubility in a solvent.
  • N, N-dialkylpyrrolidinium salts include, for example, formula (15): Preferred examples include N, N-dialkylpyrrolidinium salts represented by the formula (wherein R j1 and R j2 are the same or different and both are alkyl groups having 1 to 6 carbon atoms; X ⁇ is an anion). Further, the oxidation resistance of the N, N-dialkylpyrrolidinium salt in which part or all of the hydrogen atoms are substituted with a fluorine atom and / or a fluorine-containing alkyl group having 1 to 4 carbon atoms is improved. It is preferable from the point.
  • Preferred examples of the anion X ⁇ are the same as those of the spiro ring bipyridinium salt.
  • This N, N-dialkylpyrrolidinium salt has low viscosity and is excellent in solubility in a solvent.
  • spiro-ring bipyridinium salts and imidazolium salts are preferred in terms of solubility in solvents, oxidation resistance, and ionic conductivity.
  • X ⁇ is BF 4 ⁇ , PF 6 ⁇ , (CF 3 SO 2 ) 2 N ⁇ or (C 2 F 5 SO 2 ) 2 N ⁇ , particularly PF 6 ⁇ )
  • X ⁇ is BF 4 ⁇ , PF 6 ⁇ , (CF 3 SO 2 ) 2 N ⁇ or (C 2 F 5 SO 2 ) 2 N ⁇ , particularly BF 4 ⁇ or PF 6 ⁇ .
  • lithium salt for example, LiPF 6, LiBF 4, LiAsF 6, LiSbF 6, LiN (SO 2 C 2 H 5) 2 is preferred.
  • a magnesium salt may be used to improve the capacitance.
  • the magnesium salt for example, Mg (ClO 4 ) 2 , Mg (OOC 2 H 5 ) 2 and the like are preferable.
  • fluorine-containing cyclic carbonate of the formula (1) of the fluorine-based solvent (IIA) is, BF4-, PF 6 -, N of the (O 2 SC 2 F 5) 2 or N (O 2 SCF 3)
  • a cyclic quaternary onium salt composed of an anion is preferred.
  • the amount of electrolyte salt (IIB) blended varies depending on the required current density, application, type of electrolyte salt, etc., but fluorine-containing cyclic carbonate (total amount when other electrolyte salt dissolving solvents are used in combination) 100 mass It is preferably 0.1 parts by mass or more, further 1 part by mass or more, particularly 5 parts by mass or more, 200 parts by mass or less, more preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less.
  • the electrolytic solution used in the present invention is prepared by dissolving the electrolyte salt (IIB) in the fluorine-based solvent (IIA).
  • the electrolytic solution may be a gel (plasticized) gel electrolytic solution in combination with a polymer material that dissolves or swells in the solvent used in the electrolytic solution of the present invention.
  • Examples of such a polymer material include conventionally known polyethylene oxide and polypropylene oxide, modified products thereof (JP-A-8-222270 and JP-A-2002-1000040); polyacrylate polymers, polyacrylonitrile, and polyvinylidene fluoride.
  • Fluorine resins such as vinylidene fluoride-hexafluoropropylene copolymer (JP-A-4-506726, JP-A-8-507407, JP-A-10-294131); Examples thereof include composites with resins (Japanese Patent Laid-Open Nos. 11-35765 and 11-86630).
  • ion conductive compounds described in Japanese Patent Application No. 2004-301934 can also be used.
  • the electrolyte used in the present invention may contain other additives as necessary.
  • other additives include metal oxides and glass.
  • Such an electrolytic solution can simultaneously improve the flame retardancy, the solubility of the electrolyte salt and the compatibility with the hydrocarbon solvent while maintaining the low temperature characteristics, and also stable characteristics at a withstand voltage of 3.5 V or more. Therefore, it is excellent as an electrolytic solution for an electric double layer capacitor.
  • the electric double layer capacitor As the electric double layer capacitor, a wound cell type electric double layer capacitor, a laminate type electric double layer capacitor, a coin type electric double layer capacitor and the like are generally known, and the electric double layer capacitor of the present invention is also in these types. be able to.
  • a positive electrode and a negative electrode made of a laminate (electrode) of a current collector and an electrode layer are wound through a separator to produce a wound element, and the wound element is made of aluminum. And then filled with an electrolytic solution, preferably a non-aqueous electrolytic solution, and then sealed and sealed with a rubber sealing body.
  • the electrode of the present invention contains an acrylic acid compound (ID), it has sufficient mechanical properties, particularly bending resistance, and can easily and stably produce a wound element. Also, it has excellent durability.
  • ID acrylic acid compound
  • separator conventionally known materials and configurations can be used in the present invention.
  • a polyethylene porous film, polypropylene fiber, glass fiber, cellulose fiber non-woven fabric and the like can be mentioned.
  • a laminate type electric double layer capacitor in which a sheet-like positive electrode and a negative electrode are laminated via an electrolytic solution and a separator, or a positive electrode and a negative electrode are made coin-type by fixing with a gasket and an electrolytic solution and a separator.
  • a configured coin type electric double layer capacitor can also be used.
  • Example 1 (Production of electrodes) (Preparation of electrode slurry) 100 parts by weight of steam-activated non-graphitized activated carbon particles (YP50F manufactured by Kuraray Chemical Co., Ltd., specific surface area: 1600 m 2 / g, average particle size 6 ⁇ m), acetylene black (Electrochemical Industry Co., Ltd.) 3 parts by weight of Denka Black (manufactured by Lion Corporation), 16 parts by weight of Carbon ECP600JD (manufactured by Lion Corporation), 6 parts by weight of elastomer binder (AZ-9001 made by ZEON Corporation), thickener 3 parts by weight (A10H manufactured by Toa Gosei Co., Ltd.) was mixed to prepare an electrode slurry.
  • YP50F manufactured by Kuraray Chemical Co., Ltd., specific surface area: 1600 m 2 / g, average particle size 6 ⁇ m
  • acetylene black Electrochemical Industry Co., Ltd.
  • Denka Black manufactured by Lion Corporation
  • Edged aluminum (20CB manufactured by Nihon Densetsu Kogyo Co., Ltd., thickness of about 20 ⁇ m) is prepared as a current collector, and a conductive paint (manufactured by Nippon Graphite Industry Co., Ltd.) is used on both sides of the current collector using a coating device.
  • a bunny height T602 was applied to form a conductive layer (thickness: 2 ⁇ m).
  • the electrode slurry prepared above was applied to the conductive layer formed on both sides of the current collector using a coating apparatus to form an electrode layer (thickness: 110 ⁇ m), thereby producing the electrode of the present invention.
  • the electrode density was 0.41 g / cm 3 and the evaluation of the bending resistance was ⁇ .
  • Electrode density The weight and outer dimensions of etched aluminum (base material) coated with a conductive layer cut to a predetermined size are measured, and an electrode layer is applied to the top.
  • the electrode weight is obtained by subtracting the weight of the substrate from the weight dried at 140 ° C. for 1 hour after coating, and the outer volume of the substrate is subtracted from the outer volume after coating. .
  • the electrode density is calculated from the calculated electrode weight and outer dimensions.
  • Example 2 (Production of capacitor) The electrode produced in Example 1 was cut to a width of 31 mm. This electrode was wound with a separator (TF45-30 manufactured by Nippon Kogyo Paper Industries Co., Ltd., width 34 cm) by a winding machine for EDLC to produce a cylindrical wound body having a diameter of 16 mm. At that time, a tab lead for electrode lead-out was connected to the electrode by caulking.
  • a separator TF45-30 manufactured by Nippon Kogyo Paper Industries Co., Ltd., width 34 cm
  • a wound cell type capacitor ( ⁇ 18 mm ⁇ 40 mm) was produced by sealing through packing.
  • Capacitance retention rate (%) (capacitance at ⁇ 10 ° C./capacitance at 25 ° C.) ⁇ 100
  • Capacitance retention rate (%) (capacitance at each time / capacitance before start of evaluation (initial)) ⁇ 100
  • the capacitance retention after 500 hours is 70% or more and the internal resistance increase rate is 400% or less, which is excellent in load characteristics at high temperature (70 ° C.). It has excellent cycle characteristics and rate performance in use, and has long-term reliability.
  • Example 3 As an electrolytic solution, sulfolane, HCF 2 CF 2 CH 2 OCF 2 CF 2 H, and dimethyl carbonate were mixed at a volume ratio of 65/15/20 to prepare a solvent for dissolving the electrolyte salt, and triethyl was added to the solvent for dissolving the electrolyte salt.
  • a wound cell type capacitor was fabricated in the same manner as in Example 2 except that a homogeneous solution in which methylammonium (TEMA) BF 4 was added to a concentration of 1.2 mol / liter was used as the electrolytic solution.
  • methylammonium (TEMA) BF 4 was added to a concentration of 1.2 mol / liter was used as the electrolytic solution.
  • Example 4 Sulfolane and HCF 2 CF 2 CH 2 OCF 2 CF 2 H were mixed at a volume ratio of 75/25 to prepare a solvent for dissolving the electrolyte salt, and spirobipyridinium tetrafluoroborate was added to the solvent for dissolving the electrolyte salt as 1.2.
  • a wound cell type capacitor was fabricated in the same manner as in Example 2 except that a homogeneous solution added so as to have a mol / liter concentration was used as the electrolyte.
  • Example 5 100 parts by weight of steam-activated non-graphitized activated carbon particles (YP50FH manufactured by Kuraray Chemical Co., Ltd., specific surface area: 1600 m 2 / g, average particle size 6 ⁇ m), acetylene black (Electrochemical Co., Ltd.) 3 parts by weight of Denka Black (manufactured by Lion Corporation), 16 parts by weight of Carbon ECP600JD (manufactured by Lion Corporation), 6 parts by weight of elastomer binder (AZ-9001 made by ZEON Corporation), thickener 3 parts by weight (A10H manufactured by Toa Gosei Co., Ltd.) was mixed to prepare an electrode slurry.
  • YP50FH manufactured by Kuraray Chemical Co., Ltd., specific surface area: 1600 m 2 / g, average particle size 6 ⁇ m 100 parts by weight of steam-activated non-graphitized activated carbon particles (YP50FH manufactured by Kuraray Chemical Co., Ltd., specific surface area: 1600
  • An electrode was prepared in the same manner as in Example 1 except that this electrode slurry was used, and the electrode density and bending resistance were examined.
  • the electrode density was 0.35 g / cm 3. It was ⁇ .
  • a wound cell type capacitor was produced in the same manner as in Example 2 except that this electrode was used.
  • Example 6 100 parts by weight of steam-activated non-graphitized activated carbon particles (YP80F manufactured by Kuraray Chemical Co., Ltd., specific surface area: 2000 m 2 / g, average particle size 6 ⁇ m), acetylene black (Electrochemical Industry Co., Ltd.) 3 parts by weight of Denka Black (manufactured by Lion Corporation), 16 parts by weight of Carbon ECP600JD (manufactured by Lion Corporation), 6 parts by weight of elastomer binder (AZ-9001 made by ZEON Corporation), thickener 3 parts by weight (A10H manufactured by Toa Gosei Co., Ltd.) was mixed to prepare an electrode slurry.
  • YP80F manufactured by Kuraray Chemical Co., Ltd., specific surface area: 2000 m 2 / g, average particle size 6 ⁇ m
  • acetylene black Electrochemical Industry Co., Ltd.
  • Denka Black manufactured by Lion Corporation
  • Carbon ECP600JD manufactured by Lion Corporation
  • An electrode was prepared in the same manner as in Example 1 except that this electrode slurry was used, and the electrode density and bending resistance were examined.
  • the electrode density was 0.35 g / cm 3. It was ⁇ .
  • a wound cell type capacitor was produced in the same manner as in Example 2 except that this electrode was used.
  • Example 7 100 parts by weight of steam-activated non-graphitized activated carbon particles (RP-20 manufactured by Kuraray Chemical Co., Ltd., specific surface area: 1800 m 2 / g, average particle size 8 ⁇ m), and acetylene black (Electrochemical Industry ( 3 parts by weight of Denka Black), 16 parts by weight of Ketjen Black (Carbon ECP600JD made by Lion Corporation), and 6 parts by weight of elastomer binder (AZ-9001 made by Nippon Zeon Co., Ltd.) 3 parts by weight of a sticky material (A10H manufactured by Toa Gosei Co., Ltd.) was mixed to prepare an electrode slurry.
  • RP-20 steam-activated non-graphitized activated carbon particles
  • specific surface area 1800 m 2 / g, average particle size 8 ⁇ m
  • acetylene black Electrochemical Industry
  • 16 parts by weight of Ketjen Black Carbon ECP600JD made by Lion Corporation
  • elastomer binder AZ-9001
  • An electrode was prepared in the same manner as in Example 1 except that this electrode slurry was used, and the electrode density and bending resistance were examined.
  • the electrode density was 0.41 g / cm 3. ⁇ .
  • a wound cell type capacitor was produced in the same manner as in Example 2 except that this electrode was used.
  • Comparative Example 1 100 parts by weight of alkali-activated graphitized activated carbon particles (NK261 made by Kuraray Chemical Co., Ltd., specific surface area: 2300 m 2 / g, average particle size 6 ⁇ m), acetylene black (Electrochemical Co., Ltd.) as a conductive auxiliary 3 parts by weight of Denka Black (manufactured by Lion Corporation), 16 parts by weight of Carbon ECP600JD (manufactured by Lion Corporation), 6 parts by weight of elastomer binder (AZ-9001 made by ZEON Corporation), thickener 3 parts by weight (A10H manufactured by Toa Gosei Co., Ltd.) was mixed to prepare an electrode slurry.
  • NK261 alkali-activated graphitized activated carbon particles
  • specific surface area 2300 m 2 / g, average particle size 6 ⁇ m
  • acetylene black Electrochemical Co., Ltd.
  • Denka Black manufactured by Lion Corporation
  • Carbon ECP600JD
  • An electrode was prepared in the same manner as in Example 1 except that this electrode slurry was used, and the electrode density and bending resistance were examined.
  • the electrode density was 0.40 g / cm 3. ⁇ .
  • a wound cell type capacitor was produced in the same manner as in Example 2 except that this electrode was used.

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  • Microelectronics & Electronic Packaging (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention concerne une électrode pour condensateur électrique bicouche et un condensateur électrique bicouche comprenant ladite électrode. Le condensateur électrique bicouche présente une capacitance élevée, une faible résistance interne et, de plus, une tension de tenue élevée, et comprend une couche d'électrode contenant des particules de carbone actif obtenues en activant à la vapeur un carbone non graphitisant, un matériau de cohésion, un noir de Ketjen et un composé acrylique.
PCT/JP2010/071121 2009-12-11 2010-11-26 Condensateur électrique bicouche WO2011070924A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0613263A (ja) * 1992-06-26 1994-01-21 Matsushita Electric Ind Co Ltd 電気二重層コンデンサ
JP2004193570A (ja) * 2002-11-29 2004-07-08 Honda Motor Co Ltd 電気二重層コンデンサ用分極性電極およびこれを用いた電気二重層コンデンサ
JP2005294575A (ja) * 2004-03-31 2005-10-20 Nippon Zeon Co Ltd 電気二重層キャパシタ電極用バインダー組成物および電気二重層キャパシタ
WO2008084846A1 (fr) * 2007-01-12 2008-07-17 Daikin Industries, Ltd. Condensateur électrique à deux couches
WO2009123031A1 (fr) * 2008-04-01 2009-10-08 日本ゼオン株式会社 Procédé de production d’électrode pour dispositif électrochimique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0613263A (ja) * 1992-06-26 1994-01-21 Matsushita Electric Ind Co Ltd 電気二重層コンデンサ
JP2004193570A (ja) * 2002-11-29 2004-07-08 Honda Motor Co Ltd 電気二重層コンデンサ用分極性電極およびこれを用いた電気二重層コンデンサ
JP2005294575A (ja) * 2004-03-31 2005-10-20 Nippon Zeon Co Ltd 電気二重層キャパシタ電極用バインダー組成物および電気二重層キャパシタ
WO2008084846A1 (fr) * 2007-01-12 2008-07-17 Daikin Industries, Ltd. Condensateur électrique à deux couches
WO2009123031A1 (fr) * 2008-04-01 2009-10-08 日本ゼオン株式会社 Procédé de production d’électrode pour dispositif électrochimique

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