WO2006098213A1 - Dispositif electrochimique - Google Patents

Dispositif electrochimique Download PDF

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Publication number
WO2006098213A1
WO2006098213A1 PCT/JP2006/304586 JP2006304586W WO2006098213A1 WO 2006098213 A1 WO2006098213 A1 WO 2006098213A1 JP 2006304586 W JP2006304586 W JP 2006304586W WO 2006098213 A1 WO2006098213 A1 WO 2006098213A1
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Prior art keywords
conductive polymer
ionic liquid
electrode
thiophene
electrochemical element
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PCT/JP2006/304586
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English (en)
Japanese (ja)
Inventor
Masamitsu Tachibana
Hideo Yamagishi
Mutsuaki Murakami
Hiroyuki Furutani
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Kaneka Corporation
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Priority to JP2007508091A priority Critical patent/JPWO2006098213A1/ja
Publication of WO2006098213A1 publication Critical patent/WO2006098213A1/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
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • 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
    • H01G11/02—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 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
    • 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
    • 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
    • H01G11/64—Liquid electrolytes characterised by additives
    • 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
    • H01M10/056—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
    • 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
    • H01M10/0566—Liquid materials
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrochemical device, and more particularly to a redox capacitor using a bipolar conductive polymer doping / de-doping reaction.
  • An electrochemical element is an element using an electrochemical reaction, and includes elements used for energy storage such as a battery, a capacitor, and a fuel cell. In such devices, it has long been considered to use a conductive polymer doping and dedoping reaction. However, doping and dedoping reactions of conductive polymers have a problem of lack of repeated stability and do not occur during repeated reactions. Electrochemical devices based on these principles are a major problem in practical use. There is.
  • An electric double layer capacitor is an electrochemical element for electrical storage that utilizes an electric double layer capacitance generated at the interface between an electrode and an electrolyte when a voltage is applied.
  • the mechanism of storage by this electric double layer capacity is characterized by being able to charge / discharge faster than secondary batteries with electrochemical reaction and having excellent repeated life characteristics.
  • the electric double layer capacitor has the disadvantage that its energy density is much lower than that of the secondary battery. Since the electric double layer capacity is proportional to the surface area of the electrode, activated carbon having a large surface area is generally used as the electrode. However, even when using an activated carbon electrode with such a large surface area, the energy density of an electric double layer capacitor remains at around 5 WhZkg, and its capacity density is less than that of a secondary battery.
  • a capacitor using a pseudo capacitance by a conductive polymer has been proposed.
  • the pseudocapacitance is stored with an electron transfer process (Faraday process) at the electrode interface.
  • Faraday process electron transfer process
  • the electric double layer is formed at the interface even in the process in which the pseudo capacity is developed, the electric double layer capacity and the pseudo capacity are developed in parallel, resulting in a large capacity.
  • Such pseudocapacitance is reduced when the conductive polymer is used. It is manifested by a dox reaction, that is, a dope de-dope reaction.
  • Patent Document 1 discloses a capacitor composed of a conductive polymer film.
  • a capacitor using a pseudo-capacitance is an element that can exhibit breakthrough characteristics, but has not been put into practical use due to two major technical problems. .
  • molten salts that are liquid at room temperature have recently been developed and attracting attention. These are referred to as ionic liquids and include quaternary salt cations such as imidazolium pyridinium and appropriate key ions (Br-, A1C1-, BF-, PF-, etc.)
  • Ionic liquids have features such as non-volatility, nonflammability, chemical stability, and high ionic conductivity, and are attracting attention as reusable green solvents used in chemical reactions such as various syntheses and catalytic reactions. Ionic liquids have a large potential window, excellent voltage resistance, and high ion concentration. In addition, since it is flame retardant and does not volatilize, it has excellent safety without worrying about evaporation. For this reason, application of ionic liquids as electrolytes for electric double layer capacitors is being studied.
  • Patent Document 1 Japanese Patent Laid-Open No. 6-104141
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-109875
  • Non-Patent Document 1 Andy Rudge et al., Journal of Power Sources 47, 1994, 89-107 Disclosure of Invention
  • the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a novel electrochemical device having improved repeated stability of doping and dedoping reactions. It is.
  • the electrochemical element of the present invention is characterized by having a bipolar conductive polymer and an electrolyte containing an ionic liquid.
  • the reason why the doping reaction does not occur gradually during repeated doping and dedoping reactions in the electrolyte is that the dedoped dopant diffuses into the electrolyte, and the conductive polymer during doping This is because there is no effective dopant in the vicinity of. Therefore, we first examined the combination of conductive polymer and ion liquid. If the ion component and Z or cation component of the ionic liquid are selected as components that can also be conductive polymer dopants, the dopant should always be present in the vicinity of the conductive polymer.
  • the ionic liquid, the ion component and the Z or cation component constituting the ionic liquid are incorporated as a dopant of the conductive polymer while repeating the doping and dedoping reactions, and the ionic liquid
  • the ionic liquid and the Z or force thione component constituting the ionic liquid and a part of the dopant of the conductive polymer are considered to form an ionic liquid 'conductive polymer composite.
  • 'Conductive polymer composites are considered to contribute to the development of excellent doping stability of repeated undoping reactions.
  • the present inventors have found that a particularly high performance electrochemical device can be realized by using a bipolar polymer among the conductive polymers, and have completed the present invention. That is, the present invention is as follows.
  • the electrochemical device of the present invention is characterized by having a bipolar conductive polymer and an electrolyte containing an ionic liquid.
  • the electrolyte is preferably a mixture of an ionic liquid and an organic solvent.
  • the bipolar conductive polymer further contains an ionic liquid.
  • the ionic liquid used in the present invention is BF-on, PF-on or sulfonic acid.
  • ionic liquids containing Yuon 1-Ethyl 3-methyl imidazolium tetrafluoroborate, 1-Butyl 3-methyl imidazole tetrafluoroborate, 1-Ethyl 3-methyl imidazolium At least one selected from xafluorophosphate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazolium mutosylate, 1-butyl 3-methylimidazolium tosylate More preferred.
  • the bipolar conductive polymer used in the present invention has an electric conductivity of 1000 times or more in the doped state and the undoped state, and the conductivity in the doped state is not less than 0. OlSZcm. Is preferred.
  • the bipolar conductive polymer used in the present invention is preferably a polythiophene derivative, such as poly 3- (4 fluorophenyl) thiophene, poly 3- (4-tert-butylphenol) thiophene, Poly 3— (4 trifluoromethyl phenol) thiophene, Poly 3 mono (2, 4 difluorophenol) thiophene, Poly 3— (2, 3, 4, 5, 6 Pentafluoro oral phenol) thiophene More preferably, it is at least one selected.
  • a polythiophene derivative such as poly 3- (4 fluorophenyl) thiophene, poly 3- (4-tert-butylphenol) thiophene, Poly 3— (4 trifluoromethyl phenol) thiophene, Poly 3 mono (2, 4 difluorophenol) thiophene, Poly 3— (2, 3, 4, 5, 6 Pentafluoro oral phenol) thiophene More preferably, it is at least one selected.
  • the electrochemical device of the present invention includes two electrodes facing each other and an electrolyte containing an ionic liquid sandwiched between the electrodes, and at least the surface of the electrode has a conductive high polarity.
  • the molecule is present so as to contact the electrolyte.
  • the electrochemical element of the present invention is preferably a redox capacitor used as a polar device.
  • FIG. 1 is a diagram schematically showing a configuration of a redox capacitor 1 which is a preferred example of an electrochemical element of the present invention.
  • FIG. 2 is a diagram schematically showing changes in voltage and current during charging / discharging of a system using a bipolar conductive polymer used in the present invention.
  • FIG. 3 is a diagram schematically showing cells used in Examples and Comparative Examples of the present invention.
  • FIG. 4 is a graph showing cyclic voltammetry measured in Comparative Example 1.
  • the bipolar conductive polymer in the present invention is a conductive polymer capable of both P-doping and N-doping (a-on-cation both-doping type conductive polymer).
  • Fig. 2 schematically shows the state of charge and discharge in a system in which a bipolar conductive polymer is used for two electrodes, with current on the vertical axis and voltage on the horizontal axis. The arrows in Fig. 2 indicate the direction of change in voltage and current during discharge.
  • one of the conductive polymers is P-doped (a-
  • the other conductive polymer is N-doped (force thione doped).
  • the voltage of the system after charging is V. Discharge
  • one conductive polymer is de-doped with ions, the other conductive polymer is de-doped with cations, and a doping charge Q is released.
  • both conductive polymers return to the state where they are not doped with cation and cation.
  • a bipolar polymer among conductive polymers it is possible to realize a particularly high-performance electrochemical element in characteristics such as discharge voltage, stored charge, and energy density. it can.
  • bipolar conductive polymer examples include, but are not limited to, various polythiophene derivatives.
  • Suitable as a polythiophene derivative that is a bipolar conductive polymer used in the present invention examples include poly-1- (4-fluorophenyl) thiophene, poly-3- (4-trifluoromethylphenol) thiophene, poly-3- (2,4-difluorophenyl) thiophene, poly-3- ( 2, 3, 4, 5, 6 Pentafluorophenyl) thiophene, at least one selected.
  • polythiophene derivatives having 1 to 4 fluorine atoms per monomer unit are preferable because the N-doped polymer is moderately stabilized.
  • poly-1- (4-fluorophenyl) thiophene, poly-3- (4-t-butylphenol) thiophene, poly-3- (4 trifluoromethylphenol) thiophene, poly-3- (2 , 4-difluorophenyl) thiophene is preferably used.
  • the bipolar conductive polymer used in the present invention can be doped and dedoped with a large amount of dopants, which is preferable from the viewpoint of increasing the capacitance of the electrochemical device.
  • a conductive polymer whose electrical conductivity change due to doping and dedoping is 1000 times or more.
  • the polythiophene derivatives exemplified above can be used without any problem.
  • the change in electrical conductivity due to the above-described doping and dedoping can be known, for example, as follows. That is, SnO glass etc. by electrolytic polymerization
  • a conductive polymer film is formed on the conductive substrate 2 and the produced conductive substrate with the conductive polymer film is used together with a reference electrode (for example, RE5 reference electrode manufactured by BAS Co., Ltd.) and a counter electrode (for example, a platinum plate) as a dopant. Soaked in an electrolyte solution containing ions (for example, propylene carbonate solution of ImolZL tetrachloroammotetrafluoroborate). In this electrolyte solution, a conductive substrate with a conductive polymer film is formed. Doping of molecules Performs sufficient doping of the conductive polymer film by maintaining the potential at a potential for a certain period of time.
  • ions for example, propylene carbonate solution of ImolZL tetrachloroammotetrafluoroborate
  • the conductive substrate with the conductive polymer film is taken out of the solution, and the conductive polymer film is peeled off from the conductive substrate, washed with methanol, and dried.
  • the electrical conductivity of the obtained conductive polymer film in the doped state is measured by a general electrical conductivity measurement method such as the 4-terminal method.
  • the conductive polymer film is electrolytically polymerized in the same manner as above, and this is kept at a potential at which de-doping occurs in the electrolyte for a certain period of time, thereby producing a de-doped conductive polymer film.
  • the electrical conductivity of the conductive polymer film in the doped state is measured.
  • the conductive polymer used in the present invention has a high electrical conductivity, and the viewpoint power to lower the internal resistance of the capacitor is also preferable.
  • a conductive polymer exhibiting a conductivity of 0.01 S / cm or more (more preferably 1. OSZ cm or more) in a doped state V but for example, the polythiophene derivatives exemplified above are problematic. It can be used without.
  • the conductivity in the doped state can be measured using, for example, the method described above.
  • the bipolar conductive polymer dopant preferably used in the present invention includes the conductivity and thermal stability of the bipolar conductive polymer, the capacity of doping and dedoping, the stability, and the speed. Selected in consideration of the effect on
  • the dopants preferably used in the bipolar conductive polymer of the present invention include p-toluenesulfonate ion, benzenesulfonate, anthraquinone 2-sulphonate, triisopropinorenaphthalene sulphonate, Examples thereof include polyvinyl sulfonate ions, dodecyl benzene sulfonate ions, alkyl sulfonate ions, n-propyl phosphate ions, perchlorate ions, and tetrafluoroborate ions.
  • the smaller the dopant, the smaller the doping There is a tendency to have excellent performance, and p-toluenesulfonic acid,
  • the bipolar conductive polymer in the present invention can be easily prepared into a thin and uniform conductive polymer film, and the film thickness can be controlled. Therefore, the electropolymerization in the presence of an organic solvent is possible. It is preferable that it is obtained by.
  • a bipolar conductive polymer can be deposited on the anode by a method in which a monomer is dissolved in a solvent together with a supporting electrolyte and anodized to perform dehydrogenation polymerization.
  • the oxidation-reduction potential of a polymer is lower than that of a monomer, so that the acid of the polymer skeleton further progresses during the polymerization process, and as a result, the support electrolyte, ion, is incorporated into the polymer as a dopant. It is.
  • Electrolytic polymerization has the advantage that a conductive polymer can be obtained by such a mechanism without having to add a dopant later. Further, as will be described later, it is preferable to use a carbon electrode for electrolytic polymerization and to deposit a conductive polymer on the surface thereof, because such an electrode can be used as it is as a polarizing electrode for a redox capacitor or the like.
  • Examples of supporting electrolytes in which a cation component and a Z or cation component are incorporated into a polymer as a dopant include sodium alkylsulfonate, sodium p-toluenesulfonate, sodium dodecylbenzenesulfonate, triisopropylnaphthalene.
  • Examples include tetra n-butyl ammonium, boron tetrafluoride tetraethyl ammonium, and boron tetrafluoride tetra n-butyl ammonium.
  • ionic liquids and key components are common, such as sodium p-toluenesulfonate, tetraethylammonium tetrafluoride, tetra-n-butylammonium tetrafluoride. are preferred.
  • the bipolar conductive polymer in the present invention may be polymerized in an ionic liquid.
  • a bipolar conductive polymer (described later) containing an ionic liquid can be produced in advance.
  • the electrolyte used in the electrochemical device of the present invention includes an ionic liquid.
  • ionic liquid refers to a liquid that is liquid at room temperature even though only ionic forces are formed, and is composed of a combination of a cation such as imidazolium and an appropriate ion.
  • a cation such as imidazolium and an appropriate ion.
  • the electrolyte contains an ionic liquid, so that durability and safety are improved compared to the case of using an electrolyte composed of only an ordinary organic solvent. An excellent electrochemical device can be realized.
  • the ionic liquid is a liquid that only has ions and has a high ion concentration
  • an electrochemical element using an electrolyte containing the ionic liquid has an advantage of high doping and dedoping capacity and responsiveness.
  • the ionic liquid has a wide potential window (high withstand voltage)
  • Examples of the cation constituting the ionic liquid preferably used in the present invention include an imidazolium cation, a pyridinium cation, a pyrrolidinium cation, an ammonium cation, and a triazine derivative cation. Force V, not limited to these.
  • the imidazolium cation is preferably used from the viewpoint of ease of use.
  • the key components that make up the ionic liquid are Br-, A1C1-, PF-, NO-, R NO-
  • A represents a substituent containing an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an ether group, an ester group, an acyl group or the like, and may contain fluorine.
  • R COO— —OOCR CO, which is a caron containing carboxylate (one COO)
  • the substituent which contains a formula hydrocarbon group, an aromatic hydrocarbon group, an ether group, an ester group, an acyl group, etc. is shown, and may contain fluorine. ) Is preferably used in the present invention.
  • R is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, ether
  • a substituent containing a group, an ester group, an acyl group or the like is shown, and may contain fluorine. ), Benzenesulfonic acid, toluenesulfonic acid and the like are preferably used in the present invention.
  • the ionic liquid in the present invention is excellent in the repeated stability of doping and undoping, and therefore, among the above, BF-on, PF-on or sulfonic acid-on is used.
  • U which is preferably an ionic liquid containing.
  • ionic liquids preferably used in the present invention include 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluororeborate, 1-ethinoleo. At least selected from 3-methinoreimidoxalium hexaphleoleophosphate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-ethyl-3-ethyl imidazolium tosylate, 1-butyl 3-methylimidazolium tosylate One is mentioned.
  • 1-ethyl-3-methylimidazole tetrafluoroborate and 1-butyl-3-methylimidazolium are used because of the large accumulated charge due to doping and undoping and excellent repeat stability of doping and undoping. It is preferable to use mutetrafluoroborate as the ionic liquid.
  • the ionic liquid is contained in a ratio of 1: 3 to 1: 10000 with respect to the bipolar conductive polymer.
  • the ratio of 1: 5 to 1: 100 is preferable. More preferably, it is contained. If the ionic liquid is less than 1: 10000 with respect to the bipolar conductive polymer, the proportion of the ionic liquid is too small to contribute to the improvement of the doping and dedoping performance. Moreover, if the ionic liquid exceeds 1: 3 with respect to the bipolar conductive polymer, there is a problem that the strength of the conductive polymer film is weakened.
  • the ionic liquid preferably used in the present invention can be synthesized by combining the above-mentioned ions and cations using a known method.
  • Specific examples of the synthesis method include a key exchange method, an acid ester method, and a neutralization method.
  • the electrolyte used in the present invention may be composed only of an ionic liquid as long as it contains an ionic liquid, and may be a mixture of an ionic liquid and an organic solvent. However, by using a mixture of an ionic liquid and an organic solvent as an electrolyte, a high ion concentration and a low viscosity can be realized with an appropriate balance. Doping capacity and response speed can be increased, which is preferable.
  • Examples of the organic solvent used in the mixture include acetonitrile, propylene power, and the like.
  • Organic solvents that have been widely used in the art, such as carbonate, ethylene carbonate, and ⁇ -butyllatatone, can be used without particular limitation. Above all, when it mixes with various ionic liquids at an arbitrary ratio and the viscosity of the liquid mixture decreases! For this reason, it is preferable to use acetonitrile.
  • the mixing ratio is not particularly limited, but as described above, among organic solvents such as acetonitrile, propylene carbonate, ethylene carbonate, and y-butyllatatone.
  • organic solvent: ionic liquid 1: 3 to 10: 1 (volume ratio) is preferred 1: 3 to 3: 1 is more preferred . If the volume ratio of the ionic liquid to the organic solvent is less than 1:10, the ion concentration tends to be low, which tends to be unfavorable for doping and dedoping, and the volume ratio of the ionic liquid to the organic solvent. If the ratio exceeds 3: 1, the viscosity of the mixed solution tends to increase and the electrical conductivity tends to decrease.
  • the electrochemical device of the present invention preferably further comprises a bipolar conductive polymer force S ionic liquid.
  • the bipolar conductive polymer containing the ionic liquid may be produced by impregnating the conductive polymer with the ionic liquid later, or polymerization of the conductive polymer. It may be produced by coexisting an ionic liquid from the process.
  • the ionic liquid contained in the bipolar conductive polymer those described above can be used without particular limitation.
  • the cationic component constituting the ionic liquid may be a component that can be a dopant for a bipolar conductive polymer or a component that cannot be a dopant for a conductive polymer. .
  • the cation component or the anion component constituting the ionic liquid is a component that can serve as a dopant for a bipolar conductive polymer. Even when a dedoping reaction of the bipolar conductive polymer occurs, It is realized that the ion component and the Z or cation component, which can be effective dopants for the conductive polymer, are always present in the vicinity of the conductive polymer. It becomes possible to show. Therefore, it is important to dope 'de-doping reaction in ionic liquid, and to make the ion component that constitutes the ionic liquid as a component that can be a dopant of a bipolar conductive polymer. This will have a significant effect on improving the repeated stability of the dedoping reaction.
  • the ionic component and the Z or cation component of the ionic liquid constituting the bipolar conductive polymer dopant and Part of the ionic liquid conductive polymer composite, which is a common component, is formed. That is, at the start of the doping and dedoping reaction, the bipolar conductive polymer dopant and the ionic component and the Z or cation component of the ionic liquid are not necessarily the same, but repeatedly.
  • an electropolymerized film containing an electroconductive polymer having a bipolar polarity electropolymerized in an organic solvent containing an ionic liquid, an electrode composite comprising the electrode, and an electrolyte containing the ionic liquid It is good also as an electrochemical element which combined.
  • the doping and dedoping reactions should be carried out, and at that time, the ionic component and the Z or force thione component constituting the ionic liquid should be set as components capable of becoming a bipolar conductive polymer dopant. This significantly improves the repeated stability of the doping and dedoping reactions.
  • electrochemical element in the present specification refers to all elements that repeatedly use conductive polymer doping and dedoping reactions, and includes capacitors such as redox capacitors, batteries, electrochromic elements, Includes sensors and the like.
  • the electrochemical device of the present invention is preferably realized by a redox capacitor (type III redox capacitor)!
  • the electrochemical device of the present invention includes, for example, two opposing electrodes and an electrolyte containing an ionic liquid sandwiched between the electrodes, and at least the surface of the electrode has a bipolar conductive property. It is preferable to realize the structure in which the conductive polymer exists so as to be in contact with the electrolyte.
  • FIG. 1 is a diagram schematically showing a configuration of a redox capacitor 1 which is a preferred example of the electrochemical device of the present invention.
  • the redox capacitor is a capacitor obtained by expanding the capacitance of the electric double layer capacitor by using a pseudo capacitance.
  • the redox capacitor of the present invention uses all or part of oxidation / reduction of an electrode material, charge / discharge in an electric double layer, and desorption of ions on the electrode surface for storage and release of electric energy. It is a type of electrochemical capacitor including metal oxide electrode systems, reversible redox solution systems, and underpotential chanore systems.
  • an electrochemical capacitor has been developed that has a capacity density of 120 WhZkg at the active material level, an output density of about 20 kwZkg or more, and can be charged and discharged at high speed within a few seconds.
  • the redox capacitor 1 of the example shown in FIG. 1 includes, for example, two plate-like electrodes 2 and 3 arranged with a separator 4 interposed therebetween, and each of the electrode elements 2 and 3 is an electrode element. It has a structure where 5 and 6 are in contact.
  • the laminated structure composed of the electrode 2, the separator 4, and the electrode 3 is fixed between the electrode elements 5 and 6 by the gasket 7 so that the electrode elements 5 and 6 do not contact each other.
  • the material for forming the electrodes 2 and 3 is not particularly limited as long as it can be used for a redox capacitor.
  • an electrode formed only of a bipolar conductive polymer, a composite electrode of a carbon material and a bipolar conductive polymer, a composite electrode of a metal material and a bipolar conductive polymer, a metal material And a composite material electrode of carbon material and a bipolar conductive polymer can be used.
  • the composite material electrode of the carbon material and the bipolar conductive polymer is formed by using, for example, an organic solvent such as ethanol ethanol and methyl pyrrolidone and the bipolar conductive polymer as the electrode material and the carbon material. Further, a binder can be added to form a dispersion, which can be applied to the surface of the metal current collector and then dried. As the binder, fluorine resin such as polytetrafluoroethylene and polyvinylidene fluoride is preferably used. The amount of binder used with respect to the electrode material is preferably about 5 to 20% by weight.
  • Metal current collector As the body, metals such as aluminum, nickel, stainless steel, titanium, and tantalum are preferably used, and these metals may be gold or platinum plated, or may be a polymer film formed with a metal layer. .
  • the metal current collector is more preferably used in the form of a rolled foil, a punching foil, an etched foil, an expanded metal foil or the like.
  • the polarizing electrode is not a current collector but in the form of a sheet, the conductive polymer Z-carbon composite material is mixed with the above binder, and a lubricant is added to form a paste, which is then extruded. These can be rolled with a rolling roll to form an electrode sheet.
  • carbon may be dispersed by dispersing a carbon material in a polymerization solution of a bipolar conductive polymer, followed by chemical polymerization, and coating the surface of the carbon material with a bipolar conductive polymer.
  • a composite electrode of a material and a bipolar conductive polymer can be produced. An electrode is produced in the same manner as described above using the carbon material coated with the bipolar conductive polymer thus produced.
  • the composite material electrode of the carbon material and the ambipolar conductive polymer can also be produced as follows. First, a carbon material and a binder are added to an organic solvent such as ethanol, methanol, or methylpyrrolidone to form a dispersion, which is applied to the surface of a metal current collector and then dried to produce a carbon electrode. Next, electrolytic polymerization is performed using this as an electrode to form a conductive polymer thin film on the surface of the carbon electrode, and the surface of the carbon material is coated with a thin conductive polymer. An electrode produced by this method is a useful method for reducing impedance because the conductive polymer layer can be made extremely thin.
  • an organic solvent such as ethanol, methanol, or methylpyrrolidone
  • the carbon material used for the composite material electrode of the carbon material and the bipolar conductive polymer is not particularly limited as long as it is a carbon material used for electrode formation in this field. It is preferable to contain activated carbon powder and / or graphite powder. This is because the addition of activated carbon powder or graphite powder can reduce electrode resistance and increase surface area. Accordingly, carbon blacks such as acetylene black and furnace black having a large surface area, activated carbon particles having a relatively large pore size, carbon fibers having a relatively small particle size, graphite fibers, and carbon nanotubes are particularly preferred as the carbon material. It is mentioned as a thing. Carbon materials have a specific surface area (analysis of nitrogen adsorption isotherm data at liquid nitrogen temperature). It is preferable to use a material having a BET specific surface area value of 20 m 2 Zg or more.
  • the laminated structure of the electrode 2, the separator 4, and the electrode 3 shown in FIG. 1 is impregnated with an electrolyte containing the ionic liquid described above (preferably a mixture of the ionic liquid and the organic solvent).
  • an electrolyte containing the ionic liquid described above preferably a mixture of the ionic liquid and the organic solvent.
  • the separator 4 those conventionally used for capacitors can be used without any particular limitation, and a porous one is preferably used.
  • the electrode elements 5 and 6 and the gasket 7 can be used without any particular limitation as long as they are conventionally used for capacitors.
  • As the gasket 7, an electrically insulating material is used.
  • the method of charging / discharging the electrochemical device of the present invention is the same as that of a normal electric double layer capacitor, and can be performed by applying a voltage between a pair of electrodes or passing a current.
  • the electrochemical device of the present invention is preferably realized as a redox capacitor used as a polar device that distinguishes between a positive electrode and a negative electrode, since the cycle life can be extended. In general, this is the direction of repeating only union or deionization of either a cation or a cation in a bipolar conductive polymer. This is because there is little deterioration of the dedoping property.
  • the electrochemical device of the present invention is preferably used in an appropriate voltage range so as not to be overcharged from the viewpoint of extending the cycle life. This is because when the dopant is excessively doped, the bipolar conductive polymer is strongly oxidized or reduced, so that the bipolar conductive polymer itself deteriorates and functions as an electrode that repeats doping and dedoping. This is because the performance decreases.
  • both polarities are formed on SnO glass by electrolytic polymerization.
  • the electropolymerization solution was 4-fluorophenylthiophene 0.1M as a monomer and boron tetrafluoride tetraethylammonium (Tetraethylammonium tetrafluoroborate HTEA'BF) as a supporting salt.
  • a propylene carbonate (PC) solution containing 1M was used. here
  • the TEA 'BF 1M propylene carbonate solution used was purchased from Sanwa Oil.
  • the SnO glass plate which is the working electrode, has a SnO coating on one side
  • BAS RE-5 reference electrode (AgZAg + reference electrode
  • the solution in the reference electrode is 0.1 M of tetrachloramine perchlorate (Bu N'CIO), silver nitrate.
  • the electrolytic polymerization solution is accommodated in a container, and these are electrolyzed in a state in which the working electrode is arranged with an interval of lcm between the reference electrode and the counter electrode. It was immersed in the polymerization solution. The working electrode was soaked only in the region of lcm from the end side in the electrolytic polymerization solution (that is, the area of the working electrode immersed in the electrolytic polymerization solution was 3 X lcm). In this state, the potential of the working electrode is maintained at +1.2 V for 120 seconds with respect to the reference electrode for 120 seconds.
  • a film of 3- (4 fluorophenyl) thiophene was formed.
  • the poly-3- (4-fluorophenol) thiophene film is P-doped (in this case, BF-ion doped)
  • the potential of the S ⁇ glass (working electrode) partially formed with a poly-3- (4 fluorophenyl) thiophene film was maintained at 0.0 V with respect to the RE-5 reference electrode for 240 seconds.
  • the reference electrode, working electrode and counter electrode were immersed in this solution in the same manner as described above (the working electrode was immersed only in the region where the edge force was 1 cm), and cyclic voltammetry (CV) measurement was performed.
  • CV cyclic voltammetry
  • a potential sweep was started from the natural potential of the dedope film of poly 3- (4 fluorophenyl) thiophene toward the positive side.
  • Figure 4 shows the obtained CV.
  • the width of the potential sweep was 2. lV to + 0.8V relative to the RE-5 reference electrode, and the potential sweep (sweep) speed was 25 mVZs.
  • the horizontal axis represents the potential of the working electrode with the reference electrode potential as the standard of OV
  • the horizontal axis OV in the graph represents + 490mV (+ 0. 4 9V).
  • the upward peak on the right side of Fig. 4 is P-doped (BF- dopin
  • the downward peak on the left (the peak of the current in the direction where the absolute value of the current increases in one direction in the region below the horizontal axis of 1.5 V) is N-doped (doping of tetraethylamine-mucation)
  • the left upward peak (current peak in the direction where the absolute value of the current increases in the + direction in the region of 0 V or more on the horizontal axis) is N-dedoped (dedoped with tetraethylammonium cation) Equivalent to.

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Abstract

L’invention concerne un dispositif électrochimique comprenant un polymère conductif bipolaire et un électrolyte contenant un liquide ionique. L’électrolyte s’obtient de préférence en mélangeant au moins une substance choisie parmi l’acétonitrile, le carbonate de propylène, le carbonate d’éthylène et la Ϝ-butyl lactone avec un liquide ionique, dans un rapport volumique compris entre 1:3 et 10:1. Une telle constitution permet d’obtenir un dispositif électrochimique présentant une répétabilité améliorée pour le dopage/dédopage de réactions.
PCT/JP2006/304586 2005-03-17 2006-03-09 Dispositif electrochimique WO2006098213A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
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JP2016225412A (ja) * 2015-05-28 2016-12-28 Jsr株式会社 蓄電デバイス
US20210130198A1 (en) * 2016-12-28 2021-05-06 Lg Electronics Inc. Water treatment apparatus filter and water treatment apparatus including same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001338846A (ja) * 2000-05-30 2001-12-07 Matsushita Electric Ind Co Ltd 電気化学キャパシタ
JP2003243028A (ja) * 2002-02-14 2003-08-29 Central Glass Co Ltd 電気化学ディバイス
JP2004527902A (ja) * 2000-12-23 2004-09-09 ルー，ウエン イオン性液体を内蔵する長寿命共役ポリマー電気化学デバイス

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CA2215849A1 (fr) * 1997-09-11 1999-03-11 Christophe Michot Nouveau solvant et composition electrolytique a haute conductivite ayant une stabilite a large plage

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001338846A (ja) * 2000-05-30 2001-12-07 Matsushita Electric Ind Co Ltd 電気化学キャパシタ
JP2004527902A (ja) * 2000-12-23 2004-09-09 ルー，ウエン イオン性液体を内蔵する長寿命共役ポリマー電気化学デバイス
JP2003243028A (ja) * 2002-02-14 2003-08-29 Central Glass Co Ltd 電気化学ディバイス

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016225412A (ja) * 2015-05-28 2016-12-28 Jsr株式会社 蓄電デバイス
US20210130198A1 (en) * 2016-12-28 2021-05-06 Lg Electronics Inc. Water treatment apparatus filter and water treatment apparatus including same

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