WO2010067772A1 - Condensateur électrique double couche - Google Patents

Condensateur électrique double couche Download PDF

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Publication number
WO2010067772A1
WO2010067772A1 PCT/JP2009/070463 JP2009070463W WO2010067772A1 WO 2010067772 A1 WO2010067772 A1 WO 2010067772A1 JP 2009070463 W JP2009070463 W JP 2009070463W WO 2010067772 A1 WO2010067772 A1 WO 2010067772A1
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Prior art keywords
electrode
fluorine
electrolyte
double layer
layer capacitor
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PCT/JP2009/070463
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English (en)
Japanese (ja)
Inventor
謙三 高橋
明天 高
舞 小山
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ダイキン工業株式会社
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Priority to JP2010542098A priority Critical patent/JPWO2010067772A1/ja
Publication of WO2010067772A1 publication Critical patent/WO2010067772A1/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
    • H01G11/24—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
    • 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
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • 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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • 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
    • 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.
  • Patent Document 1 also proposes a configuration of electrodes. By setting the electrode bulk density (electrode density) to a high density of 0.6 g / cm 3 or more, high capacitance and low internal resistance can be realized. It is stated.
  • 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.
  • the present invention is an electric double layer capacitor comprising an electrode containing activated carbon and a binder and a non-aqueous electrolyte solution, (I) The electrode density of the electrode is 0.45 g / cm 3 or less, (II) The present invention relates to an electric double layer capacitor wherein the non-aqueous electrolyte is a non-aqueous electrolyte having a withstand voltage of 2.5 V or more.
  • non-aqueous electrolyte a fluorine-based electrolyte is preferable.
  • an electric double layer capacitor having a high electrostatic capacity, a low internal resistance, and a high withstand voltage can be provided.
  • the electric double layer capacitor of the present invention includes an electrode (I) containing a specific component and a fluorine-based electrolyte (II). Each configuration will be described below.
  • Electrode (I) used by this invention contains activated carbon (IA) and binder (IB).
  • Activated carbon activation treatment methods include a steam activation treatment method, a molten KOH activation treatment method, and the like, and it is preferable to use activated carbon obtained by a molten KOH activation treatment method in terms of obtaining a larger capacity.
  • activated carbon particles having a potassium content of 0 to 200 ppm measured by an extraction method, and an average particle diameter as described in Patent Document 1 are from 1 to Examples thereof include activated carbon particles having a pore volume of 10 cm and a pore volume of 1.5 cm 3 / g or less.
  • natural graphite artificial graphite, graphitized mesocarbon spherules, graphitized whiskers, gas-phase-grown carbon fibers, a furfuryl alcohol resin fired product, or a novolak resin fired product can be exemplified.
  • the binder (IB) binds the particles when it is formed into an electrode using activated carbon (IA) and other electrode components such as a conductive material added as necessary. Used for.
  • fluorine-based resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF); non-fluorine such as butadiene rubber and styrene-butadiene rubber System rubber is used.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • non-fluorine such as butadiene rubber and styrene-butadiene rubber System rubber is used.
  • a fluorine-based resin, particularly PTFE is preferable from the viewpoint of good pressure resistance and durability
  • non-fluorine rubber is preferable from the viewpoint of good pressure resistance and good adhesion to the current collector.
  • the conductive material is a non-activated carbon having a large specific surface area and has a role of imparting electron conductivity, and for example, carbonaceous materials such as carbon black, ketjen black, acetylene black, natural graphite, and artificial graphite
  • carbonaceous materials such as carbon black, ketjen black, acetylene black, natural graphite, and artificial graphite
  • An inorganic material such as a metal fiber, conductive titanium oxide or ruthenium oxide.
  • IC-2 Thickener
  • activated carbon (IA), binder (IB), and other additives added as necessary are dispersed in a solvent, for example, water to form a slurry, and metal It is applied to a foil or current collector and molded. At that time, a thickener is added to uniformly disperse the particles in the slurry and adjust the fluidity to an appropriate fluidity.
  • thickener examples include conventionally known carboxymethyl cellulose (CMC) and polyacrylic acid. Of these, polyacrylic acid is preferred from the viewpoint of good pressure resistance.
  • CMC carboxymethyl cellulose
  • polyacrylic acid is preferred from the viewpoint of good pressure resistance.
  • Electrode components are preferably blended in an amount of 2 to 6 parts by mass of binder (IB) with respect to 100 parts by mass of activated carbon (IA).
  • binder IB
  • activated carbon IA
  • the capacitance of the capacitor is decreased if the amount is too large so as to obtain good conductivity (low internal resistance). It is preferable to set it as 20 mass%.
  • the thickener (IC-2) when blended, it is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of activated carbon (IA) from the viewpoint of homogenizing the electrode density.
  • the lower limit is an amount that achieves the purpose of blending.
  • the electrode can be formed by various methods. For example, activated carbon (IA) and, if necessary, conductive material (IC-1) are dry mixed. In the mixing process, thickener (IC-2) 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.
  • activated carbon (IA) and, if necessary, conductive material (IC-1) are dry mixed.
  • thickener (IC-2) and water are added as appropriate to disperse the particles.
  • 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.
  • 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 current collector may be any material that is chemically and electrochemically resistant to corrosion.
  • the bulk density (electrode density) of the produced electrode it is important to adjust the bulk density (electrode density) of the produced electrode to 0.45 g / cm 3 or less.
  • Patent Document 1 it is known to increase the electrode density (0.6 g / cm 3 or more) from the viewpoint of improvement in capacitance and reduction in internal resistance.
  • the electrode density is examined from the viewpoint of voltage, and the point that the withstand voltage is improved in the direction of lowering the density is a matter found for the first time in the present invention.
  • 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.
  • Non-aqueous electrolyte solution used in the present invention is a non-aqueous electrolyte solution having a withstand voltage of 2.5 V or more, preferably a fluorine-based electrolyte solution.
  • the nonaqueous electrolytic solution having a withstand voltage of 2.5 V or more includes a nonaqueous solvent (IIA) and an electrolyte salt (IIB).
  • Non-aqueous solvent As the non-aqueous solvent (IIA), any fluorine-based solvent (IIA-1) or non-fluorinated solvent (IIA) can be used as long as the withstand voltage of the electrolytic solution can be 2.5 V or higher. -2).
  • a fluorinated solvent containing a fluorinated cyclic carbonate described in Patent Document 2 is excellent in high electric resistance and wide electrolyte solubility. This is preferable.
  • 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-1) has particularly excellent properties such as a high dielectric constant and a high withstand voltage, and also has good solubility of electrolyte salt and reduction of internal resistance. From the point that the characteristics as an electric double layer capacitor in the present invention are improved, At least one selected from the group consisting of is preferred.
  • Etc. can also be used as the fluorine-containing cyclic carbonate.
  • the electrical properties in the present invention are particularly excellent in that they have excellent characteristics such as a high dielectric constant and a high withstand voltage, as well as the solubility of the electrolyte salt, the reduction in internal resistance, and the low-temperature characteristics. From the point that the characteristics as a multilayer capacitor 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.
  • 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
  • Rf c2 For example, —CF 2 CHFCF 3 , —C 2 F 4 CHF 2 , —C 2 H 4 CF 3 , —CH 2 CHFCF 3 , and —C 2 H 4 C 2 F 5 are preferable.
  • 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 sulfolane derivative examples include fluorine-containing sulfolane derivatives described in JP-A-2003-132994, and among them, Is preferred.
  • the fluorinated solvent (IIA-1) the fluorinated cyclic carbonate represented by the formula (1) can be used alone, or another non-fluorinated solvent or fluorinated solvent can be used as a cosolvent.
  • a solvent for dissolving an electrolyte salt as a co-solvent a solvent for dissolving a fluorine-containing electrolyte salt is preferable from the viewpoint of good oxidation resistance and viscosity, and a fluorine-containing chain carbonate, a fluorine-containing chain ester, and a fluorine-containing chain ether. Is more preferable.
  • the fluorine-based solvent (IIA-1) when operated at a high voltage of 3.5 V or more includes a fluorine-containing cyclic carbonate represented by the formula (1), a fluorine-containing chain carbonate, a fluorine-containing chain ester, and Those consisting of at least one selected from the group consisting of fluorine-containing chain ethers are preferred. 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.
  • Non-fluorinated solvent As the non-fluorinated solvent (IIA-2), non-fluorinated cyclic carbonate, non-fluorinated chain carbonate, non-fluorinated chain ester, non-fluorinated chain ether, non-fluorine Lactones, non-fluorine sulfolane derivatives, other solvents for dissolving non-fluorine electrolyte salts, and the like.
  • 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.
  • Etc. can also be used.
  • 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, PF 6 - is 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 and the like, and Et 4 NBF 4 , Et 4 NPF 6 , Et 4 NSbF 6 , Et 4 NAsF 6 and the like are particularly 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 BF 4 ⁇ or 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 ⁇ ). Is preferred.
  • 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.
  • the amount of electrolyte salt (IIB) blended varies depending on the required current density, application, type of electrolyte salt, etc., but 0.1 mol / liter or more and 2.5 mol / liter or less with respect to the non-aqueous solvent (IIA). Further, it is preferably 0.8 mol / liter or more and 1.8 mol / liter or less, more preferably 1.0 mol / liter or more and 1.6 mol / liter or less.
  • the electrolytic solution used in the present invention is prepared by dissolving an electrolyte salt (IIB) in a non-aqueous solvent (IIA).
  • 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 electrolyte solution can simultaneously improve flame retardancy, low temperature characteristics, solubility of electrolyte salts and compatibility with hydrocarbon solvents, and stable characteristics can be obtained at a withstand voltage of 3.5 V or more. It is excellent as an electrolyte for electric double layer capacitors.
  • the upper limit of the withstand voltage is preferably as high as possible, and is appropriately set depending on the type and application of the non-aqueous electrolyte to be used.
  • the electrode (I) is usually wound through a separator or a current collector to constitute a wound element.
  • Conventional separators and current collectors can be used as they are.
  • the electric double layer capacitor is assembled by placing the non-aqueous electrolyte (II) and the winding element in a case made of aluminum or the like, and sealing and sealing with a rubber sealing body.
  • a laminate type electric double layer capacitor or a coin type electric double layer capacitor can be obtained by a known method.
  • the measurement method and evaluation method employed in the examples are as follows.
  • Electrode density (unit: g / cm 3 ) The external dimensions and mass are measured, and the bulk density (g / cm 3 ) is calculated from these values.
  • Electrolytic solution was applied to a three-electrode voltage measuring cell (working electrode, counter electrode: platinum (where the area ratio of the counter electrode and working electrode is 5: 1), reference electrode: Ag, HS cell manufactured by Hosen Co., Ltd.) Then, the potential is pulled at 3 mV / sec with a potentiostat, and the decomposition current is measured. The maximum potential at which the decomposition current no longer increases is defined as the withstand voltage of the electrolyte.
  • Capacitance, internal resistance, and withstand voltage of the capacitor Increase the charging voltage to the applied voltage (2.5V) while charging the laminate cell with a constant current with an electronic power supply. After maintaining the constant voltage state for 5 minutes and confirming that the charging current is sufficiently lowered and saturated, constant current discharge is performed and the cell voltage difference ( ⁇ V) and the current value (I) are measured.
  • the constant current value for charging and discharging is 10 mA / F, and 35 mA.
  • the cell voltage and current are measured by 0.5 second sampling.
  • the current value (I) flowing through the cell is calculated by connecting a 1 ⁇ fixed resistor in series to the cell and measuring the voltage across this end. This current value is used when measuring the internal resistance of the cell.
  • the capacitance of the capacitor (unit: F) and the internal resistance (unit: ⁇ ) of the capacitor are calculated as follows.
  • each of the cells in the same manner with 8 types of specified applied voltages (3.0V, 3.3V, 3.5V, 3.7V, 3.9V, 4.1V, 4.3V) Calculate the internal resistance value. Since the internal resistance value of the cell is constant regardless of the applied voltage unless the cell deteriorates, the maximum applied voltage value at which no increase in the internal resistance value of the cell is observed with the increase in the applied voltage is Of withstand voltage.
  • Example 1 (Production of electrodes) Activated carbon particles (specific surface area 2100 m 2 / g. Average particle size 11 ⁇ m. CEP21 manufactured by Nippon Oil Corporation. Activated carbon 1) and 100 parts by mass of ketjen black (EC600JD manufactured by Lion Corporation) as a conductive material, 3 parts by mass of acetylene black (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.) was dry mixed with a stirrer. It was transferred to a kneader and 2 parts by mass of polyacrylic acid (Aron A-10H manufactured by Toagosei Co., Ltd.) and 50 parts by mass of water were added.
  • ketjen black E600JD manufactured by Lion Corporation
  • this slurry was applied onto an etched aluminum current collector (thickness 20 ⁇ m) previously coated with a conductive paste (T602 manufactured by Nippon Graphite Co., Ltd.) with a film thickness of 20 ⁇ m, and dried at 110 ° C. Later, press treatment was performed to produce a roll electrode having an activated carbon layer thickness of 80 ⁇ m (electrode density 0.40 g / cm 3 ).
  • Electrolyte using spirobipyrrolidinium tetra phosphate as an electrolyte salt (manufactured by Hoechst (Ltd.)), CF 3 as an electrolyte solvent - ethylene carbonate (CF 3 -EC) and fluorine-containing ether (HCF 2 CF 2 CH 2 OCF 2 CF 2 H.
  • a fluorine-based electrolytic solution having an electrolyte salt concentration of 1 mol / liter was prepared by mixing 1: 1 fluorine-containing ether 1). It was 5.0V when the withstand voltage of this fluorine-type electrolyte solution was measured.
  • Example 2 A slurry for the same electrode as in Example 1 was prepared, and 17.5 parts by mass of water was added to 100 parts by weight of the slurry as a viscosity adjustment immediately before application (the stability of this slurry evaluated separately was ⁇ ). ) Using this slurry, an electrode having a thickness of 80 ⁇ m was immediately prepared in the same manner as in Example 1. The electrode density of this electrode was 0.38 g / cm 3 . When this electrode was subjected to a bending resistance test and examined for mechanical durability, the electrode was not cracked (evaluation: ⁇ ).
  • a laminate type electric double layer capacitor was produced using a fluorine-based electrolyte prepared in the same manner as in Example 1 except that this electrode was used, and withstand voltage (V), capacitance at 2.5 V (F) , And the internal resistance ( ⁇ ) at each voltage was measured. The results are shown in Table 1.
  • Example 3 A slurry for the same electrode as in Example 1 was prepared, and 20 parts by mass of water was added to 100 parts by weight of the slurry as a viscosity adjustment immediately before application (the stability of this slurry evaluated separately was good). . Using this slurry, an electrode having a thickness of 80 ⁇ m was immediately prepared in the same manner as in Example 1. The electrode density of this electrode was 0.36 g / cm 3 . When this electrode was subjected to a bending resistance test and examined for mechanical durability, the electrode was not cracked (evaluation: ⁇ ).
  • Example 4 A slurry for the electrode as in Example 1 was prepared, and as a viscosity adjustment just before coating, 11.3 parts by mass of water was added to 100 parts by weight of the slurry (the stability of this slurry evaluated separately was ⁇ ). ) Using this slurry, an electrode having a thickness of 80 ⁇ m was immediately prepared in the same manner as in Example 1. The electrode density of this electrode was 0.43 g / cm 3 . When this electrode was subjected to a bending resistance test and examined for mechanical durability, the electrode was not cracked (evaluation: ⁇ ).
  • Comparative Example 1 The same slurry for electrodes as in Example 1 was prepared, and the solid content concentration was further set to 30% by mass (the stability of this slurry was good). A comparative electrode having a thickness of 80 ⁇ m was produced using this slurry. The electrode density of this electrode was 0.53 g / cm 3 . When this comparative electrode was subjected to a bending resistance test and examined for mechanical durability, the electrode was not cracked (evaluation: ⁇ ).
  • a laminate type electric double layer capacitor was produced using a fluorine-based electrolytic solution prepared in the same manner as in Example 1 except that this comparative electrode was used, and withstand voltage (V), capacitance at 2.5V. (F) and internal resistance ( ⁇ ) at each voltage were measured. The results are shown in Table 1.
  • Comparative Example 2 A slurry for the electrode as in Example 1 was prepared, and 7.5 parts by mass of water was added to 100 parts by weight of the slurry as a viscosity adjustment immediately before application (the stability of this slurry evaluated separately was ⁇ ). ) Using this slurry, an electrode having a thickness of 80 ⁇ m was immediately prepared in the same manner as in Example 1. The electrode density of this electrode was 0.46 g / cm 3 . When this electrode was subjected to a bending resistance test and examined for mechanical durability, the electrode was not cracked (evaluation: ⁇ ).
  • Example 5 PTFE binder (D210C manufactured by Daikin Industries, Ltd .; binder 2) 10 parts by weight and 80 parts by weight of water were added as a binder, and the mixture was used for a predetermined time. An electrode having a thickness of 80 ⁇ m was immediately prepared in the same manner as in Example 1 using this slurry. The electrode density of this electrode was 0.40 g / cm 3 . When this electrode was subjected to a bending resistance test and examined for mechanical durability, the electrode was not cracked (evaluation: ⁇ ).
  • a laminate type electric double layer capacitor was produced using a fluorine-based electrolyte prepared in the same manner as in Example 1 except that this electrode was used, and withstand voltage (V), capacitance at 2.5 V (F) was measured. The results are shown in Table 2.
  • Example 6 A slurry for the electrode was prepared in the same manner as in Example 1 except that YP50F (non-graphitizable carbon manufactured by Kuraray Chemical Co., Ltd., activated carbon 2) was used as the activated carbon, and this slurry was immediately used as in Example 1. Thus, an electrode having a thickness of 80 ⁇ m was produced. The electrode density of this electrode was 0.40 g / cm 3 . When this electrode was subjected to a bending resistance test and examined for mechanical durability, the electrode was not cracked (evaluation: ⁇ ).
  • YP50F non-graphitizable carbon manufactured by Kuraray Chemical Co., Ltd., activated carbon 2
  • a laminate type electric double layer capacitor was produced using a fluorine-based electrolyte prepared in the same manner as in Example 1 except that this electrode and the electrolyte were used, and withstand voltage (V), capacitance at 2.5V. (F) was measured. The results are shown in Table 2.
  • Comparative Example 3 A laminated electric double layer capacitor was produced in the same manner as in Example 6 except that the electrode of Comparative Example 1 was used as the electrode, and the withstand voltage (V) and the electrostatic capacity (F) at 2.5 V were measured. The results are shown in Table 2.
  • Example 7 Using the same electrode as in Example 1, the electrolyte used was spirobipyrrolidinium tetraphosphate (SBP-BF 6 ) (manufactured by Nippon Carlit Co., Ltd.) as the electrolyte salt, and CF 3 -ethylene carbonate as the electrolyte solvent.
  • SBP-BF 6 spirobipyrrolidinium tetraphosphate
  • CF 3 -ethylene carbonate as the electrolyte solvent.
  • a mixture of fluorine-containing ether (HCF 2 CF 2 CH 2 OCF 2 CFHCF 3 .Fluorine-containing ether 2) in a ratio of 1: 1 was used, and a fluorine-based electrolytic solution having an electrolyte salt concentration of 1 mol / liter was used. It was 5.0V when the withstand voltage of this fluorine-type electrolyte solution was measured.
  • a laminate type electric double layer capacitor was produced in the same manner as in Example 1 except that this electrode and the electrolytic solution were used, and the withstand voltage (V) and the electrostatic capacity (F) at 2.5 V were measured. The results are shown in Table 3.
  • Example 8 Using the same electrode as in Example 1, the electrolyte used was triethylmethylammonium BF 4 as the electrolyte salt, and PC (propylene carbonate) and fluorine-containing ether (HCF 2 CF 2 CH 2 OCF 2 CF 2 H) were used as the electrolyte solvent. A mixture of 1: 1 was used, and a fluorine-based electrolytic solution having an electrolyte salt concentration of 1 mol / liter was used. It was 5.0V when the withstand voltage of this fluorine-type electrolyte solution was measured.
  • PC propylene carbonate
  • fluorine-containing ether HCF 2 CF 2 CH 2 OCF 2 CF 2 H
  • a laminate type electric double layer capacitor was produced in the same manner as in Example 1 except that this electrode and the electrolytic solution were used, and the withstand voltage (V) and the electrostatic capacity (F) at 2.5 V were measured. The results are shown in Table 3.
  • Comparative Example 4 A laminated electric double layer capacitor was produced in the same manner as in Example 1 except that the same electrode as in Comparative Example 1 was used and the same fluorine-based electrolytic solution as in Example 8 was used as the electrolytic solution. The capacitance (F) at 0.5 V was measured. The results are shown in Table 3.
  • Example 9 Using the same electrode as in Example 1, the electrolyte used was tetraethylammonium BF 4 as the electrolyte salt, and PC (propylene carbonate) and fluorine-containing carbonate (CF 3 CH 2 OCOOCH 2 CF 3 ) were used as the electrolyte solvent at a ratio of 1: 1.
  • a mixed electrolyte was used, and a fluorine electrolyte solution having an electrolyte salt concentration of 1 mol / liter was used. It was 5.0V when the withstand voltage of this fluorine-type electrolyte solution was measured.
  • a laminate type electric double layer capacitor was produced in the same manner as in Example 1 except that this electrode and the electrolytic solution were used, and the withstand voltage (V) and the electrostatic capacity (F) at 2.5 V were measured. The results are shown in Table 3.
  • Comparative Example 5 A laminated electric double layer capacitor was produced in the same manner as in Example 1 except that the same electrode as in Comparative Example 1 was used and the same fluorine-based electrolytic solution as in Example 9 was used as the electrolytic solution. The capacitance (F) at 0.5 V was measured. The results are shown in Table 3.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

La présente invention concerne un condensateur électrique double couche, qui présente une capacité électrostatique élevée, une faible résistance interne et une tension de tenue élevée. Ce condensateur électrique double couche est caractérisé en ce qu'il est équipé d'une électrode qui contient du charbon activé et un matériau liant, ainsi qu'une solution électrolytique non aqueuse, et en ce que (I) la densité de l'électrode est de 0,45 g/cm3 maximum et que (II) la solution électrolytique non aqueuse affiche une tension de tenue de 2,5 V minimum.
PCT/JP2009/070463 2008-12-08 2009-12-07 Condensateur électrique double couche WO2010067772A1 (fr)

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JP2008-312475 2008-12-08
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002104817A (ja) * 2000-07-25 2002-04-10 Kuraray Co Ltd 活性炭、その製造方法、分極性電極及び電気二重層キャパシタ
JP2003282369A (ja) * 2002-03-20 2003-10-03 Osaka Gas Co Ltd 電気二重層キャパシタ用炭素材及びその製造方法
WO2008084846A1 (fr) * 2007-01-12 2008-07-17 Daikin Industries, Ltd. Condensateur électrique à deux couches

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002104817A (ja) * 2000-07-25 2002-04-10 Kuraray Co Ltd 活性炭、その製造方法、分極性電極及び電気二重層キャパシタ
JP2003282369A (ja) * 2002-03-20 2003-10-03 Osaka Gas Co Ltd 電気二重層キャパシタ用炭素材及びその製造方法
WO2008084846A1 (fr) * 2007-01-12 2008-07-17 Daikin Industries, Ltd. Condensateur électrique à deux couches

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