WO2000057439A1 - Composition d'electrolyte pour condensateur electrique double couche, electrolyte polymere solide, composition pour electrode polarisable, electrode polarisable, et condensateur electrique double couche - Google Patents
Composition d'electrolyte pour condensateur electrique double couche, electrolyte polymere solide, composition pour electrode polarisable, electrode polarisable, et condensateur electrique double couche Download PDFInfo
- Publication number
- WO2000057439A1 WO2000057439A1 PCT/JP2000/001732 JP0001732W WO0057439A1 WO 2000057439 A1 WO2000057439 A1 WO 2000057439A1 JP 0001732 W JP0001732 W JP 0001732W WO 0057439 A1 WO0057439 A1 WO 0057439A1
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- WO
- WIPO (PCT)
- Prior art keywords
- electric double
- double layer
- compound
- electrolyte
- polarizable electrode
- Prior art date
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- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- HQPMKSGTIOYHJT-UHFFFAOYSA-N ethane-1,2-diol;propane-1,2-diol Chemical compound OCCO.CC(O)CO HQPMKSGTIOYHJT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
-
- 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
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
- Electrolyte composition for electric double layer capacity solid polymer electrolyte, composition for polarizable electrode, polarizable electrode, and electric double layer capacity
- the present invention relates to an electrolyte composition and a solid polymer electrolyte for an electric double layer capacity, a composition for a polarizable electrode and a polarizable electrode, which are preferably used for backup applications of various electronic devices, and the like.
- Electric double layer capacity Electric double layer capacity. Background art
- positive and negative electrodes are provided on a pair of left and right current collectors.
- positive and negative electrodes are made by adding a conductive material for improving the conductivity of the electrodes to a high-area material such as activated carbon, and collecting electricity such as aluminum foil with a binder. It has a structure carried on the body.
- a separator is interposed between the positive and negative electrodes, and the normal electrode and the separator are impregnated with an electrolytic solution.
- the film-like electric double-layer capacity has a configuration of a positive electrode electrolyte (separate layer) / negative electrode, and the positive electrode / electrolyte (separate layer) / negative electrode composite is formed.
- the positive electrode electrolyte separate layer
- the positive electrode / electrolyte separate layer
- negative electrode composite is formed.
- no rolling pressure is applied to the film capacitor, so no pressure is applied between the positive electrode electrolyte and the electrolyte Z negative electrode.
- the positive electrode and the negative electrode are easily separated from the electrolyte. Therefore, in the film-shaped electric double layer capacitor, the electrolyte (separator) disposed between the positive electrode and the negative electrode has a function of firmly bonding the positive and negative electrodes in addition to the role of the electrolyte, that is, the adhesive property. However, adhesiveness is required.
- polytetrafluoroethylene and polyfluorovinylidene are used as a binder for supporting a slurry of a carbon material such as activated carbon on a metal current collector.
- a carbon material such as activated carbon
- polytetrafluoroethylene and polyfluorovinylidene are used as a binder for supporting a slurry of a carbon material such as activated carbon on a metal current collector.
- Polyvinylpyrrolidone, carboxymethylcellulose and the like are used.
- polyvinylidene fluoride has excellent film-forming ability.
- the electrode binder must have a function of bonding a high-area material such as activated carbon, that is, adhesiveness and adhesiveness.
- the present invention has been made in view of the above circumstances, and by introducing a substituent having a large dipole moment into a polyurethane molecule, a high dielectric constant and a high ion conductive salt can be obtained. While maintaining the ability to dissolve at a high concentration, it has high adhesiveness, is suitable as a binder that firmly binds high-area materials and conductive materials, and has an interface impedance equivalent to that of an electrolyte solution.
- Polyurethane polymer compound bin-resin
- an electrolyte composition for electric double layer capacitor and a solid polymer containing this polymer compound and an ion conductive salt as main components.
- a composition for a polarizable electrode and a polarizable electrode having excellent properties such as high adhesiveness and dielectric properties which are mainly composed of an electrolyte, a poly urethane polymer compound, a high-area material, and a conductive material; and Electric double layer composed of these For the purpose that you provide Yapashi evening.
- the ion-conductive metal salt has a considerably high concentration in the ion-conductive solid polymer electrolyte and a low dielectric constant polymer mat.
- the association of ions is likely to occur, and the decrease in conductivity due to the association of ions is observed.
- a dipole is added to the polymer to improve the polarity of the matrix. Introducing a large-moment substituent causes ion association.
- the ion conductivity is improved
- Polyurethane compounds exhibit remarkable adhesion and remarkability when a large dipole moment substituent is introduced. It was found that the adhesiveness was improved.
- a boron compound in a polyurethane compound obtained by reacting an excess of an isocyanate compound with an excess of a polyol compound is obtained. It is obtained by reacting a hydroxyl group of an alcohol compound having a large dipole moment substituent with part or all of the remaining isocyanate group, and the above-mentioned polyurethane compound is reacted with NHC Polyurethane polymer compound, in which a large substituent of the above dipole moment is bonded through a bond, has high dielectric constant, ability to dissolve ion conductive salt at high concentration, and excellent adhesion.
- the electrolyte composition for the electric double layer capacitor and the solid polymer electrolyte which are the main components, have high ion conductivity and high adhesiveness, and in addition to their role as excellent electrolytes, It has the function of firmly adhering to the separator, and the composition for a polarizable electrode mainly composed of a polyurethane polymer compound, a high-area material, and a conductive material has high adhesion and dielectric properties.
- the present inventors have found that they have excellent characteristics such as performance and are optimal as a constituent material of an electric double layer capacitor, and have completed the present invention.
- the above-mentioned electrolyte composition for electric double layer capacity is cured, and has an adhesive strength of 0.8 kN / m or more according to a method in accordance with JISK 6854 (1994).
- a composition for a polarizable electrode comprising, as main components, a polyurethan polymer compound formed by bonding, a high-area material, and a conductive material;
- a polarizable electrode obtained by applying the composition for a polarizable electrode on a current collector
- the polarizable electrodes are used as the pair of polarizable electrodes, and the polarizer electrodes are used as the pair of polarizable electrodes.
- An electric double-layer capacity wherein the separation is performed by impregnating the base material with a solution containing an ion conductive salt.
- an electric double-layer capacity in which a separator is interposed between a pair of polarizable electrodes, the polarizable electrodes are used as the pair of polarizable electrodes, and the separator is used as the separator.
- An electric double layer capacity wherein a separator is prepared by applying or impregnating the electrolyte composition for electric double layer capacity to a base material for separation.
- the polarizable electrodes are used as the pair of polarizable electrodes, and the polarizer electrodes are used as the pair of polarizable electrodes.
- the electrolyte composition for electric double layer capacities of the present invention can be obtained by reacting an excess amount of an isocyanate compound with a polyvinyl compound to obtain a residue in a polyurethane compound. It is obtained by reacting a hydroxyl group of an alcohol compound having a large substituent of a dipole moment with a part or all of an isocyanate group.
- the main components are a polyurethane polymer compound having a large substituent of the dipole moment bonded via a bond, and an ion conductive salt.
- the above-mentioned polyurethane polymer compound is composed of an (A) component isolating compound, a (B) component polyol compound, and a (C) component having one or more hydroxyl groups and one or more hydroxyl groups in the molecule.
- the dipole moment is obtained by reacting the dipole moment with an alcohol compound having a large substituent.
- an alicyclic isocarbonate or an aliphatic isocarbonate can be used as long as the compound has two or more isocarbonate groups in the molecule. It can be either a cyanate or an aromatic isocyanate.
- MDI methylene diphenyl diisocyanate
- polymeric MDI polymeric MDI
- tolylene diisocyanate TDI
- resin diisocyanate Cyanate LPI
- Hydrogenated Tolylene Diisocyanate Hexamethylene Diisocyanate (HDI)
- Xylylene Diisocyanate XDI
- Hydrogenated Xylylene Diisocyanate Naphthylene Diisocyanate ( NDI)
- Bifen Nirange Insulinate, 2, 4, 6 — Trisopropirinile Resilinate (TIDI) Diphenylene tertiary silicate, trizindi thiocyanate (T ⁇ DI), isophorone diisocyanate (IPDI), 4,4 'dicyclohexylmetane thiocyanate (HMDI), teto Lamethylxylylene diisocyanate (TMXDI), 2'2,4_
- polyol compound (B) examples include high molecular weight polyols such as polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol copolymer, ethylene glycol, and the like.
- 2 Propylene glycol
- 1,3 Propylene glycol
- 1,3 Butanol
- 1,4-butanediol 1,5—Pentanediol
- 1,6 Hexanediol
- 2, 2—Dimethyl-1,3-propanediol diethylene glycol, dipropylene glycol
- 1,4 cyclohexanedimethanol
- p Xylylene diylene
- fenirjenol noramine methyl ethanolamine
- 3, 9 bis (2—hydroxy—1, 1— Dimethyl) 12,4,8,10—tetraoxaspiro [5,5] -opendecane.
- the polyfunctional polyols include trifunctional polyethylene glycol, trifunctional polypropylene glycol, and trifunctional (ethylene glycol / propylene glycol).
- Random copolymers bifunctional poly (ethylene glycol), bifunctional poly (propylene glycol), and bifunctional (ethylene glycol / propylene glycol) random copolymers.
- four, five Polyfunctional polyols of higher functionality can also be used.
- the weight average molecular weight (M w) is preferably from 200 to 100,000, more preferably from 500 to 800, more preferably It is 10000 to 600000. If the weight average molecular weight of the high molecular weight polymer is too small, the physical properties of the resulting polyurethan high molecular compound may be reduced. Drilling may be difficult.
- the composition of the high molecular polyol is such that the content of the polyethylene glycol (EII) unit is at least 20 mol%, preferably at least 30 mol%, more preferably at least 50 mol%. It is more preferably at least 80 mol%. If the content of polyethylene dalichol units is too small, the solubility of the ion conductive salt may decrease.
- EII polyethylene glycol
- one of the various polyol compounds described above can be used alone or in combination of two or more, and a combination of a bifunctional polyol and a trifunctional polyol can be used. You can also.
- the mixing ratio between the bifunctional polyol and the trifunctional polyol depends on the molecular weight of the mixture, but is preferably 1:25 by weight.
- a monohydric alcohol can be used for the reaction.
- the monohydric alcohol include methanol, ethanol, butanol, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, and the like.
- Pyrene glycol monoether, ethylene glycol 'propylene glycol copolymer monoethyl ether, and the like can also be used.
- the polyurethane polymer compound of the present invention has a large dipole moment substituent of the component (C) in addition to the components (A) and (B). The alcohol compound is reacted.
- the concentration of the ion conductive metal salt is considerably high, and in a low dielectric constant polymer matrix, ion association is likely to occur. A decrease in conductivity is observed.
- the ion is less likely to be associated and the conductivity is improved.
- the polyurethane compound when a substituent having a large dipole moment is introduced, the polyurethan compound is significantly reduced. It became clear that the adhesiveness and tackiness were improved. Therefore, it is significant to introduce a large dipole moment substituent into polyurethane.
- an alcohol compound having one or more hydroxyl groups and one or more large substituents of dipole moment in the molecule may be reacted with an isocyanate compound.
- the alcohol in an alcohol compound having one or more hydroxyl groups and one or more dipole moment large substituents in the molecule, the alcohol may have 1 to 10 carbon atoms, particularly 1 to 10 carbon atoms.
- aliphatic alcohols such as aliphatic monohydric alcohols, phenols, benzyl alcohols and cresols.
- a value when bound to a phenyl group, a methyl group or an ethyl group is preferably 1.0 D ebye or more.
- a neutral substituent is preferable to an ionic substituent, and one CN (cyano group) is particularly preferable.
- Such an alcohol compound of the component (C) has an amino group.
- N-acetylethanolamine nitrophenol with nitro group, nitrophenol, methylnitrophenol, ethylene cyanohydrin with cyano group, hydr Roxyacetonitrile, cyanophenol, cyanobenzyl alcohol and the like.
- the alcohol compound of the component (C) used in the present invention a compound in which a part of the hydrogen atoms of the alcohol is substituted with a group having a large dipole moment such as a cyano group is used.
- a group having a large dipole moment such as a cyano group
- an alcohol having a substituent in which a cyano group is bonded to a cyanobenzyl group, a cyanobenzoyl group, or an alkyl group is preferable.
- alcohols having a cyanoethyl group one CH 2 CH 2 CN) (ethylene cyanohydrin) are preferred.
- the conductivity of the resin is reduced as compared to the case without the dipole moment. And the conductivity and the adhesion and tackiness of the polyurethane compound are greatly improved.
- the substance required to exhibit this effect is an alcohol compound having one or more hydroxyl groups and one or more large dipole moment substituents in the molecule of component (C).
- the amount of the alcohol compound is important. Preferred amounts are: an isocyanate compound of component (A), a polyol compound of component (B), one or more hydroxyl groups and one or more dipole molecules in the molecule of component (C).
- the (A) component isocarbonate compound when reacting the (A) component isocarbonate compound, the (B) component polyol compound and the (C) component alcohol compound, the (A) component isocarbonate compound
- the stoichiometric ratio of [NCO] in [B] and [OH] of (B) and (C) components is important.
- the (A) component isocyanate compound is a polyol compound
- the (C) component molecule has one or more hydroxyl groups and one or more dipole moments.
- a urethanization catalyst, a defoaming agent and the like can be added in a usual amount, if necessary.
- the urethanization catalyst is not particularly limited.
- 1,4-diazabicyclo [2.2.2] octane (DABCO) triethylamine
- metal catalysts such as tin compounds such as tin octoate and dibutyl tin dilaurate, and lead compounds.
- the polymer compound of the present invention is obtained by mixing and reacting the above-mentioned predetermined amounts of the components (A) to (C) and, if necessary, a urethanization catalyst and a defoaming agent. It can be manufactured by
- the polyurethan polymer compound of the present invention is obtained by reacting the above-mentioned (A) component isocyanate compound and (B) component polyol compound in an excess of (A) component.
- the hydroxyl group of the alcohol compound of the above-mentioned component (C) reacts with the isocyanate group remaining in the resulting polyurethane compound, and the dipole moment is large.
- the substituent is bonded to the above polyurethan compound via an NHC bond. That is, it can be expressed by the following equation.
- PU represents a polyurethane compound
- A represents an alcohol residue having a large substituent in the above dipole moment.
- the alcohol of the component (C) is ethylene cyanohydrin
- the polyurethan polymer compound of the present invention has a large dipole moment substituent, it has a high dielectric constant, a high adhesive strength, and a high concentration of dissolving ion conductive salt. It is suitable for various electrochemical materials such as resin for electric double layer capacity and electrolyte for electric double layer capacity.
- the polyurethane polymer compound of the present invention has an ability to dissolve the ion conductive salt at a high concentration.
- the electrolyte composition for electric double layer capacity of the present invention contains the above-mentioned polyurethane polymer compound and an ion conductive salt as main components.
- the ion conductive salt is used for ordinary electrochemical devices.
- the amount of the above-mentioned ion conductive salt varies depending on the type of the ion conductive salt to be used, the molecular weight of the polymer compound, and the like, and cannot be specified unconditionally. 5 to 100 parts by weight, preferably 10 to 500 parts by weight, more preferably 10 to 100 parts by weight of the ion conductive salt with respect to 100 parts by weight, More preferably, it is 10 to 50 parts by weight. If the amount of the ion conductive salt is too small, the ion conductor concentration becomes too low, which may result in the conductivity being substantially too low. On the other hand, if the amount is too large, the solubility of the polymer matrix in the ion conductive salt is exceeded in many cases, and salts may be precipitated.
- a solvent capable of dissolving the ionic conductive salt is used in the electrolyte composition for electric double layer capacity of the present invention. Can be added.
- Such solvents include, for example, dibutyl ether, 1,2—dimethoxetane, 1,2—ethoxymethoxetane, methyldigram Chain ethers such as glycol, methyl ether trimethyl, methyl tetragram, methyl ethyl lime, ethyl diglyme, butyl diglyme, glycol ethers (ethyl ethyl sorbitol, ethyl carbitol, butyl cell sorb, butyl carbitol, etc.); Heterocyclic ethers such as trahydrofuran, 2—methyltetrahydrofuran, 1,3—dioxolane, 4,4-dimethyl-1,3—dioxane, etc.
- Amide solvents such as N-methylformamide, N, N — Dimethylformamide, N — Methylacetamide, N — Methylpyrrolidinone, etc., solvent for solvents (getyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene) And a solvent such as imidazolidinone (1,3-dimethyl-2-imidazolidinone).
- solvents may be used alone.
- two or more kinds can be used as a mixture.
- a carbonate-based solvent such as propylene carbonate, which is a non-aqueous solvent, is particularly preferred.
- the amount of the solvent to be added is preferably 1 to 90% by weight, more preferably 25 to 75% by weight, based on the total weight of the electrolyte composition for electric double layer capacity. If the added amount of the solvent is too large, the adhesiveness of the polyurethane polymer compound may be inhibited.
- a solvent for dilution may be used for the purpose of decreasing the viscosity for forming a thin film.
- the conditions of this solvent are as follows: first, it does not react with the isocyanate compound; second, it dissolves the isocyanate compound and the polyol compound; and third, it has a boiling point of 12 A solvent that has a relatively low boiling point of 0 ° C or less. If so, it can be used without any particular restrictions. For example, tetrahydrofuran, acetate, methylethylketone, toluene, 1,4-dioxane, ethylene glycol dimethyl ether, and the like can be used.
- the electrolyte composition for electric double layer capacity of the present invention has a high adhesive strength and a high ion conductivity.
- an electrolytic composition for an electric double layer capacity containing 5 to 100 parts by weight of an ion conductive salt with respect to 100 parts by weight of a polyurethane high molecular compound was cast on a stainless steel plate. After, the San de I Tutsi structure superposed another stainless steel plate, 8 0 ° C for 4 hours left to measure the conductivity of those cured with if, 3 X 1 0 4 in the complex conductivity measurement It has high conductivity of about SZ cm.
- the method for thinning (casting) the solid electrolyte composition for electric double layer capacity is not particularly limited.
- roller coating such as application overnight rolls, screen coating, etc. It can be applied to a uniform thickness by using a method such as a doc-over-blade method, spin coating, barco-overcoat, etc.
- the electrolyte composition for electric double layer capacity of the present invention is preferably at room temperature to 120 ° C. for 0 to 7 hours, more preferably at 60 to 100 ° C. for 1 to 10 hours. By heating for 4 hours, it hardens and becomes a solid polymer electrolyte (separate overnight) for electric double layer capacity having elasticity.
- the solid polymer electrolyte for electric double layer capacity of the present invention has high ion conductivity, and in addition to playing an excellent role as an electrolyte, has a high adhesive strength.
- the solid polymer electrolyte can be interposed between the pair of polarizable electrodes to perform the function of firmly bonding the bipolar electrodes.
- the solid polymer electrolyte for electric double layer capacity of the present invention is the solid polymer electrolyte for electric double layer capacity of the present invention.
- Adhesive strength when measured by a method based on the standard of the peeling adhesive strength test method of the adhesive in accordance with JISK 6854 (1994) is preferable. It exhibits a high adhesive strength of at least 0.8 kN / m, more preferably at least lkN / m, and even more preferably at least 1.5 kN / m.
- composition for a polarizable electrode of the present invention comprises a polyurethane polymer compound, a high-area material, and a conductive material as main components.
- the same polyurethane polymer compound as the above-mentioned electrolyte composition for electric double layer capacities can be used.
- a specific surface area of 5 0 0 m 2 Z g or more preferable to rather is 1 0 0 0 m 2 Z g or more, rather than to preferred Ri good 1 5 0 0-3 0 0 0
- activated carbon obtained by activating a carbon material by a steam activation method, a molten KOH activation method, or the like is particularly preferable.
- the activated carbon include coconut-based activated carbon, phenol-based activated carbon, petroleum coke-based activated carbon, and polyacene.One of these can be used alone, or two or more can be used in combination. Can be used. Among them, phenol-based activated carbon, petroleum coke-based activated carbon, and polyacene are preferred for realizing large capacitance.
- the compounding amount of the high area material is 100 to 250 parts by weight, preferably 150 to 200 parts by weight, based on 100 parts by weight of the polyurethane polymer compound. 0 parts by weight. If the added amount of the high-area material is too large, the adhesive strength of the composition for a polarizable electrode is reduced, and the adhesiveness to a current collector may be poor. On the other hand, if the amount is too small, the resistance of the polarizable electrode may increase, and the electric capacity of the produced polarizable electrode may decrease.
- the conductive material is not particularly limited as long as it can impart conductivity to the composition.
- carbon black, Ketjen black, acetylene black, carbon paste, natural graphite, artificial graphite examples include metal powders such as metal fibers, titanium oxide, and ruthenium oxide.
- metal powders such as metal fibers, titanium oxide, and ruthenium oxide.
- Ketchen black and acetylene black which are a type of carbon black, are preferred.
- the average particle size of the conductive material powder is 10 to 100 nm, preferably 20 to 40 nm.
- the amount of the conductive material is from 50 to 500 parts by weight, preferably from 100 to 300 parts by weight, based on 100 parts by weight of the polyurethane polymer compound. If the amount of the conductive material is too large, the ratio of the high-area material may decrease, and the capacitance may decrease. On the other hand, if the amount is too small, the effect of imparting conductivity may be insufficient.
- a diluting solvent can be added to the composition for a polarizable electrode of the present invention, in addition to the above-mentioned polyurethane polymer compound, high-area material, and conductive material.
- the diluting solvent include acetonitrile, tetrahydrofuran, aceton, methylethylketone, 1,4-dioxane, and ethylene glycol dimethyl ether.
- the addition amount of the diluting solvent is preferably 80 to 150 parts by weight with respect to 100 parts by weight of the whole composition for a polarizable electrode.
- the polarizable electrode of the present invention is obtained by applying the composition for a polarizable electrode on a current collector.
- the current collector is preferably made of metal.
- Aluminum and stainless steel are preferred as the metal current collector because they have high corrosion resistance.
- aluminum is preferred because it is light and has low electrical resistance.
- the shape of the current collector may be any shape such as a foil shape, an expanded metal shape, a sintered fiber sheet shape, and a plate-shaped metal foam.
- foils having a thickness of 20 to 100 zm are preferred because they can be easily wound or laminated and are relatively inexpensive.
- a metal foil is used for the current collector, if the surface is roughened by a chemical, electrochemical, or physical method, the adhesion between the polarizing electrode and the metal current collector is improved, and It is preferable because the resistance can be reduced.
- the polarizable electrode of the present invention may be obtained by coating a composition for a polarizable electrode on a current collector by, for example, roller coating such as an application roll, screen coating, a doctor blade method, or the like. It can be formed by applying a uniform thickness using a means such as spin coating, chip coating, and the like. Thereafter, the polarizable electrode of the present invention in a semi-solid state is obtained by being left at 60 to 100 ° for 1 to 6 hours.
- the polarizable electrode of the present invention has an adhesive strength of 0.8 kN Zm or more, more preferably lk N / m or more, in a method based on JISK 6854 (1994). More preferably, it shows a high adhesive strength of 1.5 kN / m or more.
- the electric double layer capacitor of the present invention has a separator interposed between a pair of polarizable electrodes.
- the pair of polarizable electrodes it is preferable to use the above-described polarizable electrode of the present invention and to use the pair of polarizable electrodes having the same configuration.
- a separation base obtained by impregnating a base material with a solution containing an ion-conductive salt is used.
- the separation base material those commonly used as separation base materials for electric double layer capacity can be used.
- Such separation base materials include, for example, polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, porous PTFE film, craft paper, rayon fiber and sisal fiber mixed sheet. Paper, Manila hemp sheet, glass fiber sheet, cellulosic electrolytic paper, paper made of rayon fiber, mixed paper of cellulose and glass fiber, and a combination of these in multiple layers.
- the ion conductive salt and the solvent capable of dissolving the ion conductive salt include the ion conductive salt exemplified in the electrolyte composition for electric double layer capacity of the present invention. The same solvent as that capable of dissolving the ion conductive salt can be used.
- the ion conductive salt concentration in the ion conductive salt-containing solution is 0.5 to 2.5 mol ZL.
- the electric double layer is formed. Capacitive evening is obtained.
- separator a separator obtained by applying or impregnating the electrolyte composition for an electric double layer capacitor of the present invention on a separator substrate is used.
- the separation base material is as described above.
- the separator composition obtained by applying the electrolyte composition for electric double layer capacity of the present invention to a base material for separation, or a separation solution obtained by impregnating the composition in the pores of separation layer. can be used. These separators are interposed between a pair of polarizable electrodes of the present invention, applied with a predetermined pressure, left at 60 to 100 ° C for 1 to 8 hours, and cured. The electric double layer capacity is obtained.
- a gel separator in which an electrolyte composition for an electric double layer capacitor is mixed with a solvent capable of dissolving an ion conductive salt.
- a solvent capable of dissolving the ionic conductive salt the same solvent as the solvent exemplified in the electrolyte composition for an electric double layer capacitor can be used.
- a solid polymer electrolyte for an electric double layer capacitor obtained by curing the above-mentioned electrolyte composition for an electric double layer capacitor of the present invention is used as the separator.
- the electrolyte composition for electric double layer capacity of the present invention is applied onto the surface of the polarizable electrode of the present invention by roller coating such as application coating, screen coating, and doc mixing. Apply a uniform thickness using a method such as spinning, spin coating, or barco, and cast using a knife applicator.
- an electric double layer capacity After applying pressure so as to have a predetermined thickness, By leaving it to stand for 8 hours and curing, an electric double layer capacity can be obtained. It is also possible to use a gel separator in which an electrolyte composition for electric double layer capacity and a solvent capable of dissolving the ion conductive salt are mixed. This solvent is the same as described above.
- the binder resin made of the polyurethan polymer compound of the present invention as the binder resin of the polarizable electrode constituting the electric double layer capacitor of the present invention, The powdery high-area material and the conductive material can be firmly bonded. Further, when the electrolyte composition for electric double layer capacity and the solid polymer electrolyte (separate layer) of the present invention are used as the separator to be interposed between the polarizable electrodes, the polarizable electrode and the separator are separated. And the binder resin and the separator (solid polymer electrolyte) have the same composition, so the interfacial resistance between the polarizable electrode and the solid polymer electrolyte is reduced. As a result, a high-quality electric double layer capacity having excellent performance can be obtained.
- solution I One or more hydroxyl groups and one or more dipole moments in the molecule of the (A) component isolating compound, the (B) component polyol compound, and the (C) component
- Non-aqueous solvent propylene carbonate in which (C 2 H 5 ) 4 NBF 4 was dissolved in 1 mol ZL was added and mixed (hereinafter referred to as solution II).
- the electric double layer capacity of the present invention obtained in this manner has the following structure: [aluminum current collector / polarizable electrode / separator electrode z polarizable electrode z aluminum current collector]. It is recognized that the electrode and the separator are firmly coupled, can be charged and discharged, and function effectively as an electric double layer capacity.
- the shape of the electric double layer capacity according to the present invention is preferably a film shape, but is not limited thereto, and a pair of long electrode bodies may be formed into a long shape.
- the element is formed by winding the element through a separator, and the element is impregnated with a non-aqueous electrolytic solution and accommodated in a cylindrical case having a bottom.
- a plurality of elements are formed by alternately stacking a plurality of layers through a separator to form an element, and the element is impregnated with a non-aqueous electrolyte and used in various shapes such as a square shape housed in a bottomed square case. be able to.
- the electric double-layer capacity of the present invention can be miniaturized, has a high electric capacity, and has a long life, so that it can be used for personal computers, portable terminals, and other memory backup power supplies. It can be suitably used for various purposes such as a power supply for instantaneous power failures such as a capacitor, a solar power generation energy storage system used in combination with a solar cell, and a load leveling power supply combined with a battery.
- the mixture was mixed with 1.0 part of drain.
- solution I a polyurethane polymer compound
- This II solution was cast using a doctor overnight knife and left at 80 ° C for 6 hours to obtain a solid polymer electrolyte for electric double layer capacity (cured composite material). ) created.
- the cured product obtained had an absorption of urethane bond R — 0 — C ⁇ N— in the infrared absorption spectrum of 174 to 169 cm cm 1 , and an absorption of cyano group of 2 230 to 2130 cm- 1 was confirmed, and one CH 2 CH 2 CN group formed an NHCOO bond in the polyol compound and the polyurethane compound obtained from the isocyanate compound.
- the product was a three-dimensional crosslinked product because it was not dissolved in a solvent.
- the cured composite in the form of a film of 200 m was sandwiched between two copper plates, and the measurement was performed by an alternating current impedance method.
- the evaluation was made based on the standard of the test method for the peel adhesion strength of the adhesive of JISK 6854. Specifically, a copper plate having a thickness of 0.6 mm, a width of 25.5 ⁇ 0.2 mm, and a length of 300 mm, which was surface-treated with abrasive paper, was used as the adherend. An electrolyte composition for an electric double layer capacity was applied as an adherent layer of the adherend, left at 80 ° C. for 6 hours, and cured and adhered to obtain a T-type peel test specimen. Both ends of the test piece were attached to a gripper of a tester capable of being fixed, and the measurement was performed.
- the moving speed of the crosshead was set at 100 OmZmin, and the movement was continued until the remaining portion of the bonded portion was about 1 Omm.
- the measurement results were processed by the optimal linear method, and the peeling adhesive strength was determined from the obtained peeling load according to JIS Z8401.
- Example 1 the amount of ethylene cyanohydrin was 0.57 parts, and polymeric MDI (MR-200, manufactured by NPU) was used in order to keep [NCO] / [OH] ⁇ 1.
- a solid polymer electrolyte for an electric double layer capacitor (cured composite) was prepared in the same manner as in Example 1, except that 2.8 parts were used.
- the obtained cured composite was a three-dimensional crosslinked product, and as a result of analysis, it was confirmed that a urethane bond and the presence of a cyano group were present.
- Example 3 The conductivity and the adhesive strength of the obtained cured composite were measured in the same manner as in Example 1 above. The cured composite was allowed to stand at 100 ° C. for 5 hours, and the rate of weight loss due to evaporation was measured. Table 2 shows the results. [Example 3]
- Example 1 0.229 parts of ethylene cyanohydrin was used, and Polymeric MDI (MR—200, manufactured by NPU) was used to keep [NC [] / [OH] ⁇ 1.
- a solid polymer electrolyte for electric double layer capacity (cured composite) was prepared in the same manner as in Example 1 except that the amount was changed to 2.25 parts.
- the obtained cured composite was a three-dimensional crosslinked product, and as a result of analysis, it was confirmed that a urethane bond and the presence of a cyano group were present.
- the conductivity and the adhesive strength of the obtained cured composite were measured in the same manner as in Example 1 above.
- the cured composite was allowed to stand at 100 ° C. for 5 hours, and the weight loss due to evaporation was measured. Table 2 shows the results.
- Example 1 A solid polymer electrolyte for electric double layer capacity (Example 1) was prepared in the same manner as in Example 1 except that 1.69 parts of cyanophenol were used in place of ethylene cyanohydrin. The cured composite obtained was a three-dimensional crosslinked product. As a result of analysis, the presence of urethane bonds and cyano groups was confirmed.
- the conductivity and the adhesive strength of the obtained cured composite were measured in the same manner as in Example 1 above.
- the cured composite was allowed to stand at 100 ° C. for 5 hours, and the weight loss due to evaporation was measured. Table 2 shows the results.
- Example 1 A solid polymer electrolyte for an electric double layer capacitor (Example 1) was prepared in the same manner as in Example 1 except that 1.13 parts of ethanol were used instead of ethylene cyanohydrin. Composite cured product) was prepared.
- the obtained cured product of the composite is a three-dimensional cross-linked product.
- the presence of a tan bond and a cyano group was confirmed.
- the conductivity and the adhesive strength of the obtained cured composite were measured in the same manner as in Example 1 above.
- the cured composite was allowed to stand at 100 ° C. for 5 hours, and the rate of weight loss due to evaporation was measured. Table 2 shows the results.
- the obtained cured composite was a three-dimensional crosslinked product, and as a result of analysis, it was confirmed that a urethane bond and the presence of a cyano group were present.
- the conductivity and the adhesive strength of the obtained cured composite were measured in the same manner as in Example 1 above.
- the cured composite was allowed to stand at 100 ° C. for 5 hours, and the rate of weight loss due to evaporation was measured. Table 2 shows the results.
- An electric double layer was produced in the same manner as in Example 1 except that 1.2 parts of polyethylene glycol 400 was used in place of 1,4-butanediol of the bifunctional polyol.
- a solid polymer electrolyte (cured composite) for capacitors was created.
- the obtained cured composite was a three-dimensional crosslinked product, and as a result of analysis, it was confirmed that a urethane bond and the presence of a cyano group were present.
- the conductivity and the adhesive strength of the obtained cured composite were measured in the same manner as in Example 1 above.
- the cured composite was allowed to stand at 100 ° C. for 5 hours, and the rate of weight loss due to evaporation was measured. Table of results See Figure 2.
- Example 8 Electrolyte composition for electric double layer capacity containing non-aqueous solvent and solid polymer electrolyte for electric double layer capacity
- 3.66 parts of volumetric MDI (MR-200, manufactured by NPU) was added to the mixture, and the mixture was stirred and vacuum degassed.
- solution I a polyurethane polymer compound
- the obtained polyurethane polymer was mixed with tetraethylammonium tetrafluoroborate (C 2 H) so that the concentration of the polyurethane component / non-aqueous solvent was 1 Z 1 (weight ratio). 5) 4 NBF 4 1 mol / L dissolved nonaqueous solvent pro propylene carbonate Natick sheet 1 1.4 was dissolved in 9 parts, Po Li c — down polymer compound-supporting electrolyte complex (electric double layer capacitor Electrolyte composition) (hereinafter referred to as solution II).
- composition was cast using a doctor-night knife applicator and left at 80 ° C for 6 hours to obtain a solid polymer electrolyte for an electric double layer capacitor.
- Composite cured product was prepared.
- the obtained cured composite was a three-dimensional crosslinked product, and as a result of analysis, it was confirmed that a urethane bond and the presence of a cyano group were present.
- Example 8 tetraethylammonium tetrafluorobo Rate (C 2 H 5 ) 4
- a solid polymer electrolyte (cured composite) for electric double layer capacity was prepared in the same manner as in Example 8, except that the weight ratio was adjusted to 3 (weight ratio).
- the obtained cured composite was a three-dimensional crosslinked product, and as a result of analysis, it was confirmed that a urethane bond and the presence of a cyano group were present.
- a solid polymer electrolyte for an electric double layer capacitor (composite cured) was prepared in the same manner as in Example 1 except that 5.61 parts were used. Thing) was created.
- the obtained cured product of the composite was a three-dimensional crosslinked product. As a result of analysis, the presence of urethane bonds was confirmed.
- the conductivity and the adhesive strength of the obtained cured composite were measured in the same manner as in Example 1 above.
- the cured composite was allowed to stand at 100 ° C. for 5 hours, and the weight loss rate due to evaporation was measured. Table 2 shows the results.
- the obtained composition was left at 80 ° C. for 6 hours to prepare a solid polymer electrolyte for electric double layer capacity.
- Trifunctional (ethylene glycol / propylene glycol) random copolymer Sanix FA-103
- PEG 400 Polyethylene glycol 400
- ADVANTAGE OF THE INVENTION while maintaining high dielectric constant and the ability to dissolve an ion conductive salt in a high concentration, it is possible to obtain a polyadhesive film having high adhesiveness and capable of obtaining an interface impedance equivalent to that of an electrolyte solution.
- Example 10 Composition for polarizable electrode and polarizable electrode
- composition for a polarizable electrode was cast on an aluminum current collector using a doctor knife, and then released at 80 ° C for 2 hours. Then, the acetonitrile was evaporated to produce a polarizable electrode in a semi-solid state.
- a film-like electric double-layer capacity was obtained by applying pressure through a separator-impregnated base material (PTFE porous film) impregnated.
- the obtained film-like electric double layer capacity has a configuration of [aluminum current collector Z-polarizable electrode / separator electrode Z-polarizable electrode aluminum current collector], and can be charged and discharged. It is recognized that it functions effectively as double layer capacity.
- Example 1 The II solution of Example 1 was applied or impregnated on a separator base material (a porous PTFE film) to obtain a separator.
- a separator base material a porous PTFE film
- This separator was interposed between a pair of polarizable electrodes prepared in Example 10, and after applying pressure, it was left at about 80 ° C. for 6 hours to be cured.
- the solution II of Example 1 which was disposed between the pair of polarizable electrodes of Example 10 via the separator was thermally polymerized to obtain a film-like electric double layer capacity. .
- the obtained film-like electric double-layer capacitor has a configuration of [aluminum current collector Z-polarizing electrode Z separator] Z-polarizing electrode Z-aluminum current collector] and is effectively used as an electric double-layer capacitor. It works.
- a film-like electric double layer capacity was prepared in the same manner as in Example 12 except that the pair of polarizable electrodes prepared in Example 10 and the I I solution of Example 8 were used as the I I solution.
- the obtained film-like electric double layer capacity is It has been recognized that the structure has a function of an electric double-layer electrode and an aluminum current collector].
- Example 10 On the surface of the polarizable electrode obtained in Example 10, the solution II of Example 1 was arranged slightly overly, and another polarizable electrode of the same configuration was superimposed on top of this. Then, pressure was applied so that the gap between the two polarizable electrodes was 25 m, and the mixture was left to cure at about 80 ° C for 6 hours.
- Example 10 As a result, the liquid II of Example 1 disposed between the pair of polarizable electrodes of Example 10 was thermally polymerized to form a solid polymer electrolyte layer, and the film-like electric double layer capacity was reduced. was gotten.
- the obtained film-like electric double layer capacity has a configuration of [aluminum current collector / polarizable electrode Z solid polymer electrolyte layer / polarizable electrode / aluminum current collector]. It is recognized that the evening is tightly coupled, charge / discharge is possible, and effectively functions as an electric double layer capacity.
- a film-like electric double layer capacity was prepared in the same manner as in Example 14 except that the pair of polarizable electrodes prepared in Example 10 and the I I solution of Example 8 were used as the I I solution.
- the obtained film-like electric double layer capacity has a configuration of [aluminum current collector / polarizable electrode / solid polymer electrolyte layer Z-polarizable electrode / aluminum current collector]. Is effective. ADVANTAGE OF THE INVENTION According to this invention, it has high adhesiveness which has a polyurethane polymer compound, a high-area material, and a conductive material as main components, and has the outstanding characteristic which can firmly couple a high-area material etc.
- polarizable electrode having polarization and polarization The polarizable electrode and the electric double layer capacity composed of the same have high ion conductivity and a high dielectric constant, and a pair of polarizable electrodes and a separator (electrolyte) can be firmly adhered to each other. This is the most suitable for multi-layer capacity.
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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CA002333037A CA2333037A1 (en) | 1999-03-23 | 2000-03-22 | Electrolyte composition and solid polymer electrolyte for electric double-layer capacitors, polarizable electrode-forming composition, polarizable electrode, and electric double-layer capacitors |
EP00911268A EP1134758A4 (en) | 1999-03-23 | 2000-03-22 | ELECTROLYTE COMPOSITION FOR DOUBLE-LAYER ELECTRICAL CAPACITOR, SOLID POLYMER ELECTROLYTE, COMPOSITION FOR POLARIZABLE ELECTRODE, POLARIZABLE ELECTRODE, AND DOUBLE-LAYER ELECTRICAL CAPACITOR |
US09/701,034 US6433996B1 (en) | 1999-03-23 | 2000-03-22 | Electrolyte composition for electric double layer capacitor, solid polymer electrolyte, composition for polarizable electrode, polarizable electrode, and electric double layer capacitor |
MYPI20002628A MY136007A (en) | 1999-03-23 | 2000-06-09 | Electrolyte compositions for electric double layer capacitor, solid polymer electrolyte, composition for polarizable electrode, polarizable electrode, and electric double layer capacitor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP11/78085 | 1999-03-23 | ||
JP7808599 | 1999-03-23 |
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WO2000057439A1 true WO2000057439A1 (fr) | 2000-09-28 |
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PCT/JP2000/001732 WO2000057439A1 (fr) | 1999-03-23 | 2000-03-22 | Composition d'electrolyte pour condensateur electrique double couche, electrolyte polymere solide, composition pour electrode polarisable, electrode polarisable, et condensateur electrique double couche |
PCT/JP2000/001731 WO2000056797A1 (fr) | 1999-03-23 | 2000-03-22 | Compose polymere, resine liante, composition pour electrolyte polymere conducteur d'ions, et cellule secondaire |
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PCT/JP2000/001731 WO2000056797A1 (fr) | 1999-03-23 | 2000-03-22 | Compose polymere, resine liante, composition pour electrolyte polymere conducteur d'ions, et cellule secondaire |
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US (2) | US6576372B1 (ja) |
EP (2) | EP1134758A4 (ja) |
KR (2) | KR100540903B1 (ja) |
CN (2) | CN1302309A (ja) |
CA (2) | CA2333037A1 (ja) |
MY (1) | MY136007A (ja) |
WO (2) | WO2000057439A1 (ja) |
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EP1189243A2 (en) * | 2000-09-19 | 2002-03-20 | Nisshinbo Industries, Inc. | Ion-conductive composition, gel electrolyte, non-aqueous electrolyte battery, and electrical double-layer capacitor |
JP2002128514A (ja) * | 2000-10-16 | 2002-05-09 | Nisshinbo Ind Inc | 炭素質材料、電気二重層キャパシタ用分極性電極及び電気二重層キャパシタ |
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US6704192B2 (en) * | 1999-02-19 | 2004-03-09 | Amtek Research International Llc | Electrically conductive, freestanding microporous sheet for use in an ultracapacitor |
US20020122985A1 (en) * | 2001-01-17 | 2002-09-05 | Takaya Sato | Battery active material powder mixture, electrode composition for batteries, secondary cell electrode, secondary cell, carbonaceous material powder mixture for electrical double-layer capacitors, polarizable electrode composition, polarizable electrode, and electrical double-layer capacitor |
US7342068B2 (en) * | 2003-11-18 | 2008-03-11 | Air Products And Chemicals, Inc. | Aqueous polyurethane dispersion and method for making and using same |
JP4624666B2 (ja) * | 2003-12-26 | 2011-02-02 | タキロン株式会社 | イオン導電性をもつ導電性粘着材 |
JP4492177B2 (ja) * | 2004-03-29 | 2010-06-30 | 日油株式会社 | 高分子電解質二次電池用電極および高分子電解質二次電池 |
US7173805B2 (en) * | 2004-07-20 | 2007-02-06 | Hewlett-Packard Development Company, L.P. | Polymer material |
US20060020100A1 (en) * | 2004-07-20 | 2006-01-26 | Shirley Lee | Conductive agents for polyurethane |
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- 2000-03-22 CN CNB008006180A patent/CN1190811C/zh not_active Expired - Fee Related
- 2000-03-22 EP EP00911268A patent/EP1134758A4/en not_active Withdrawn
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- 2000-03-22 EP EP00911267A patent/EP1090939A1/en not_active Withdrawn
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EP1189243A2 (en) * | 2000-09-19 | 2002-03-20 | Nisshinbo Industries, Inc. | Ion-conductive composition, gel electrolyte, non-aqueous electrolyte battery, and electrical double-layer capacitor |
EP1189243A3 (en) * | 2000-09-19 | 2003-11-26 | Nisshinbo Industries, Inc. | Ion-conductive composition, gel electrolyte, non-aqueous electrolyte battery, and electrical double-layer capacitor |
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Also Published As
Publication number | Publication date |
---|---|
EP1090939A1 (en) | 2001-04-11 |
CN1190811C (zh) | 2005-02-23 |
CA2332768A1 (en) | 2000-09-28 |
WO2000056797A1 (fr) | 2000-09-28 |
EP1134758A1 (en) | 2001-09-19 |
US6433996B1 (en) | 2002-08-13 |
CN1302444A (zh) | 2001-07-04 |
CN1302309A (zh) | 2001-07-04 |
KR20010025099A (ko) | 2001-03-26 |
CA2333037A1 (en) | 2000-09-28 |
KR100540903B1 (ko) | 2006-01-16 |
EP1134758A4 (en) | 2005-11-30 |
MY136007A (en) | 2008-07-31 |
KR20010043782A (ko) | 2001-05-25 |
US6576372B1 (en) | 2003-06-10 |
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