EP1889270A1 - Procedes de production d'electrode pour pile electrochimique et de cette pile avec l'electrode - Google Patents

Procedes de production d'electrode pour pile electrochimique et de cette pile avec l'electrode

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Publication number
EP1889270A1
EP1889270A1 EP05751144A EP05751144A EP1889270A1 EP 1889270 A1 EP1889270 A1 EP 1889270A1 EP 05751144 A EP05751144 A EP 05751144A EP 05751144 A EP05751144 A EP 05751144A EP 1889270 A1 EP1889270 A1 EP 1889270A1
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EP
European Patent Office
Prior art keywords
polymerization
electrode
producing
monomers
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05751144A
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German (de)
English (en)
Other versions
EP1889270A4 (fr
Inventor
Hidenori c/o NIPPON CHEMI-CON CORPORATION UCHI
Kenji c/o NIPPON CHEMI-CON CORPORATION TAMAMITSU
Shunzo c/o NIPPON CHEMI-CON CORPORATION SUEMATSU
Satoru c/o NIPPON CHEMI-CON CORPORATION TSUMEDA
Alexander M. Timonov
Sergey A Logvinov
Nikolay Shkolnik
Sam Kogan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Chemi Con Corp
Gen3 Partners Inc
Original Assignee
Nippon Chemi Con Corp
Gen3 Partners Inc
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Publication date
Application filed by Nippon Chemi Con Corp, Gen3 Partners Inc filed Critical Nippon Chemi Con Corp
Publication of EP1889270A1 publication Critical patent/EP1889270A1/fr
Publication of EP1889270A4 publication Critical patent/EP1889270A4/fr
Withdrawn legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive 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
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • 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
    • 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
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0464—Electro organic synthesis
    • H01M4/0466—Electrochemical polymerisation
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • 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
    • 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
    • H01M4/602—Polymers
    • 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
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain 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
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a method for producing an electrode for electrochemical element and a method for producing an electrochemical element with the electrode, and for more detail, relates to a method for producing an electrode for an electrochemical element and a method for producing an electrochemical element with the electrode in which energy density is improved and which is excellent in output characteristics.
  • an electric automobile and hybrid car have been expected instead of a gasoline-powered vehicle and diesel-powered vehicle which are engine-driven.
  • an electrochemical device having high energy density and high output density properties are used as a power source for driving a motor.
  • a secondary battery and a double electric layer capacitor are listed as this electrochemical device.
  • the secondary battery a lead battery, nickel/cadmium battery, nickel hydride battery, or proton battery and so on are listed. These secondary battery uses acidic or alkaline aqueous electrolyte solution which are high in ionic conductivity, thereby to have excellent output characteristics that large electric current is obtained when charging and discharging, however electrolysis voltage of water is 1.23V, therefore higher voltage may not be obtained. As a power source of the electric automobile, a high voltage of approximately 200V is required, therefore many batteries by just that much must be connected in series, resulting in disadvantage for downsizing and trimming weight of the power source.
  • a lithium ion secondary battery using organic electrolyte solution As a secondary battery of high voltage type, a lithium ion secondary battery using organic electrolyte solution is known.
  • This lithium ion secondary battery uses an organic solvent with high decomposition voltage as an electrolytic solvent, therefore when the lithium ion showing the lowest potential is an electric charge relating to charge/discharge reaction, potential of 3V or more is shown.
  • the lithium ion secondary battery brings a battery using carbon as a negative electrode occluding and releasing the lithium ion and lithium cobalt oxide (LiCoO 2 ) as a positive electrode into mainstream.
  • An electrolyte solution dissolving lithium salt such as hexafluorophosphate lithium (LiPF 6 ) into a solvent such as ethylene carbonate and propylene carbonate is used.
  • this lithium ion secondary battery is high in voltage and high in energy density to be excellent as a power source, however charge reaction is occlusion and release of the lithium ion of the electrode, therefore the secondary battery has a problem to be inferior in output characteristics, which is a disadvantage for the power source for the electric automobile requiring large instantaneous current.
  • there is an approach using derivative of polythiophene as a positive electrode for improving the charge/discharge property at a high voltage Japanese Laid-Open Patent Publication No.2003-297362.
  • An double electric layer capacitor uses a polarizable electrode such as activated carbon as positive and negative eletrodes, and uses a solution dissolving quaternary ammonium salt of boron tetrafluoride or phosphorus hexafuoride into an organic solvent such as propylene carbonate.
  • the double electric layer capacitor regards an double electric layer generating at the boundary surface between the surface of the electrode and the electrolyte solution as an electric capacitance, and there is no reaction involving ions such as a battery, thus the charge/discharge property is high and deterioration in capacity due to charge/discharge cycle is reduced.
  • an electrochemical capacitor using conductive polymer such as polyaniline, polypyrrole, polyacene, and polythiophene derivatives performs charge and discharge by p-doping or n-doping of anion or cation in non-aqueous electrolyte solution onto the conductive polymer.
  • the potential of this doping is low at a side of negative electrode and high at a side of positive electrode, therefore high voltage property is obtained (Japanese Laid-Open Patent Publication No.2000-315527).
  • an energy storage device such as a battery or super capacitor, that includes at least two electrodes, at least one of the electrodes includes an electrically conducting substrate having a layer of energy accumulating redox polymer complex compound of transition metal having at least two different degrees of oxidation, which polymer complex compound is formed of stacked transition metal complex monomers.
  • the stacked transition metal complex monomers have a planar structure with the deviation from the plane of no greater than 0.1 nm and a branched system of conjugated pi-bonds
  • the polymer complex compound of transition metal can be formed as a polymer metal complex with substituted tetra-dentate Schiff s base, and the layer thickness of redox polymer is within the range 1 nm-20 micrometer (International Patent Publication No.WO03/065536).
  • the above polymer complex compound may be used for both positive and negative electrodes since it's central metal could be reversibly oxidized-reduced.
  • the capacitor using these electrodes as the both electrodes allows to have a high operating voltage of 3V and a high energy density of 300Jg "1 , and a method for producing it by which this energy density is obtained is also described (International Patent Publication No. WO 04/030123). Summary of the Invention
  • an object of the present invention is to provide a method for producing an electrode for an electrochemical element and a method for producing an electrochemical element with the electrode having a high energy density and excellent output characteristics.
  • the present invention has had discussions on a method for producing electrode to solve the above problems. Consequently, the present invention provides a method for forming a thin and uniform electrode film more effectively through a method for producing an electrode for an electrochemical element, characterized by absorbing monomers for polymerization on a surface of a conductive porous material having a specific surface area of 100 to 300Om ⁇ "1 and having an average pore diameter in the range of 0.4 to lOOnm, performing electrolysis polymerization by applying pulse voltage using said conductive porous material as an electrode in electrolyte solution to stack said monomers for polymerization, and forming a conductive polymer layer on the surface of the conductive porous material.
  • the present invention makes it possible to produce an electrochemical element with the said electrode for the electrochemical element in the series of the steps through the electrolysis polymerization by applying pulse voltage from the external port of the electrochemical element after assembling the structure of the electrochemical element
  • the present invention enables more effectively thin and uniform coating of the surface of an electrode structure of a conductive porous material having a specific surface area of 100 to 300Om ⁇ "1 and having an average pore diameter in the range of 0.4 to lOOnm with polymer complex compound of transition metal, namely enables more effectively an increase of surface area compared to film thickness, consequently the electrode prepared by the present method increases ratio of doping and dedoping per unit volume against films of anion and cation, and achieves improvement of rate property and cycle property, resulting in an electrochemical device use electrode having high power properties.
  • the electrode prepared as described above is also possible to form the electrode film without blocking hole portions of porous material, therefore surface area is increased and energy density is improved. As a result, an electrochemical device use electrode which is excellent in output characteristics and high energy density can be obtained.
  • the double electric layer capacitor produced by the method of the present invention is formed as the electrode constituent of films in which polymer complex compound of transition metal is formed on the surface of the conductive porous material, such electrode can be used as a constituent element of the device such as the battery or capacitor as it is. Accordingly, it is possible to obtain in simplified and reduced steps the electrode for the electrochemical element including polymer complex compound of transition metal, which is excellent in output property and enhanced in energy density.
  • Fig 1. is a schematic view showing a stacked state of polymer metal complex (a - oxidized state, b - reduced state).
  • Fig 2. a) is a schematic view showing polymer metal complex in an oxidized state bonded on electrode surface by chemical adsorption
  • b) is a schematic view showing polymer metal complex in a reduced state bonded on the electrode surface by the chemical adsorption.
  • Fig 3. a) is a schematic view when polymer metal complex is in a neutral state, b) is a schematic view when polymer metal complex is in an oxidized state.
  • Fig. 4 is a cross sectional view of a double electric layer capacitor produced by a method of the present invention.
  • the process for adsorbing monomers for polymerization on the surface of the conductive porous material having a specific surface area in the range of 100 to 3000m 2 /g and having an average pore diameter in the range of 0.4 to 100 nm it is preferable to employ a process for adsorbing monomers for polymerization on the surface of the conductive porous material by removing solvent in the solution of monomers for polymerization after impregnating the conductive porous material with solution of monomers for polymerization.
  • the process is performed in such a way that the conductive porous material, for instance, activated carbon fabric woven in the form of cloth is impregnated with the solution of the monomers for polymerization, subsequently pulled up, and then a solvent in the solution of monomers for polymerization is removed by drying treatment, for instance. Removal of the solvent allows the monomers for polymerization to remain in the state of adhering so as not to easily desorb due to adsorptive power of the activated carbon.
  • the conductive porous material for instance, activated carbon fabric woven in the form of cloth
  • a solvent in the solution of monomers for polymerization is removed by drying treatment, for instance. Removal of the solvent allows the monomers for polymerization to remain in the state of adhering so as not to easily desorb due to adsorptive power of the activated carbon.
  • the conductive porous material used herein is preferable to be conductive porous material having a specific surface area in the range of 100 to 3000m 2 /g and having an average pore diameter in the range of 0.4 to 100 nm, specifically activated carbon, and particularly preferable to be activated carbon fabric woven in the form of cloth.
  • the conductive porous material may be molded in the form of disc, in which activated carbon powder, acetylene black, and polytetrafluorethylene as binder are blended respectively with 77: 20: 3 wt %.
  • the solution of the monomers for polymerization used herein is preferable to be a complex monomer solution of a transition metal having at least two different oxidation numbers
  • the conductive polymer formed by electrolysis polymerization is preferable to be an energy storage redox polymer layer including a polymer complex compound of a transition metal, which stores energy through the redox reaction.
  • electrolysis polymerization mode for instance, potential sweep polymerization method, constant potential polymerization method, constant current polymerization method, and potential step method as well as potential pulse method are listed.
  • potential pulse method may be used in the present invention.
  • the monomers of polymerization are adsorbed on the surface of the conductive porous material due to the effects of taking the monomers for polymerization in the pore as well as adsorbing power of substance which the conductive porous material holds.
  • polymerization reaction may develop remaining the state that the monomers of polymerization are thinly and uniformly adsorbed on the surface of the conductive porous material, thereby effecting conductive polymer.
  • Conditions of the electrolysis polymerization in the method for producing electrochemical elements according to the present invention are as follows.
  • the specific surface area of the electrode substrate preferably may be 200 to 3000m 2 g "1 , more preferably 1000 to 300QmV 1 .
  • the electrolysis polymerization on this substrate may be performed under the following condition of the electrolysis time, the downtime, the polymerization charge and the number of pulse.
  • the electrolysis time may be 0.1 to 60 second, preferably 0.5 to 10 second, more preferably 0.7 to 5 second.
  • the downtime may be 10 to 300 second, preferably 10 to 60 second, more preferably 20 to 30 second.
  • a pulse ratio which defines as a proportion of a pulse repetition time (the electrolysis time + the downtime) to the electrolysis time, is less than 1500, preferably less than 60, and less than 30.
  • down-state means that value of the electric potential becomes the value at which the polymerization of the monomer stops.
  • value of the electric potential may be -2 to +0.5 V, preferably -1 to +0.3 V, more preferably -0.5 to 0 V.
  • pulse voltage condition may be Ag/Ag+ of 0.5 to 1.0V, preferably AgZAg+ of 0.5 to 0.7V, more preferably AgZAg+ of 0.5 to 0.6V. If voltage is in this range, an enough amount of complex monomer oxide is formed through an electrochemical reaction, therefore the complex polymer compound of transition metal is formed efficiently, and further the formed complex polymer compound of transition metal is difficult to form over-oxide, consequently complex polymer compound of high-capacity density transition metal is formed.
  • polymerization is performed by immersing the above electrode into the electrolyte solution and applying pulse voltage, however not only such a double pole type but also triple pole type may be used, polymerization of which is performed by applying an constant potential to the reference electrode with using a working electrode and a counter electrode as well as the reference electrode or flowing oxidation current.
  • the number of cycle may be 100 to 10000 cycles, preferably 100 to 5000 cycles, more preferably 200 to 2000 cycles. If the number of cycle is in this range, an amount of production of the complex polymer compound of transition metal is enough, in addition, the complex polymer compound of transition metal is not produced excessively, therefore a thin film of the complex polymer compound of transition metal is maintained.
  • the electrolyte solution used for the electrolysis polymerization of the present invention is preferably non-aqueous type using organic solvent, and a salt which is soluble in organic solvent and which can ensure ions conductivity is preferably used in the supporting electrolyte solution, and both the kind and concentration are not limited.
  • an organic solvent preferably contains one or more substances selected from a group constituted of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, sulphorane, acetonitrile, and dimethoky ethane.
  • lithium salt having the lithium ion, quaternary ammonium salt or quaternary phosphonium salt having quaternary ammonium cation or quaternary phosphonium cation respectively may be listed.
  • LiPF 6 LiBF 4 , LiClO 4 , LiN(CF 3 SO 2 ) 2 , LiCF 3 SO 3 , LiC(SO 2 CF 3 ) 3 , LiAsF 6 and LiSbF 6 and so on are listed.
  • quaternary ammonium salt or quaternary phosphonium salt a salt comprising cation expressed by Rl R2 R3 R4N+ or Rl R2 R3 R4 P+ (where Rl, R2, R3, R4 are alkyl group with the number of carbon of 1 to 6), and anion consisting of PF6-, BF4-, C1O4-, N(CF3SO2)2-, C3SO3-, C(SO2CF3)3-, AsF6- or SbF6- is preferable. Specifically, PF6-, BF4-, C1O4- or N(CF3SO2)2- is used as anion.
  • the most preferable electrolyte solution utilized in the present electrolysis polymerization is propylene carbonate (PC) dissolving (C 2 Hs) 4 NBF 4 in the density unit of [mol/liter].
  • the conductive polymer layer formed by the present electrolysis polymerization is the layer of an energy storage redox polymer including a polymer complex compound of a transition metal, which stores energy through the redox reaction.
  • the polymer complex compound of transition metal may be the polymer metal complex of tetra-dentate Schiff's base, in particular, represented by the following graphical formula:
  • R is H or electron donating substituent
  • R' is H or halogen
  • n is an integer number of 2 to 200000.
  • transition metal Me Ni, Pd, Co, Cu, and Fe are listed.
  • R CH 3 O-, C 2 H 5 O-, HO-, and -CH 3 are listed.
  • a redox polymer complex compound of transition metal is configured as "unidirectional" or “stack" macromolecules.
  • Polymer metal complexes are bonded with the inter-electrode surface due to chemisorption.
  • Charge transfer in polymer metal complexes is effected due to "electron hopping" between metal centers with different states of charge. Charge transfer can be described mathematically with the aid of a diffusion model. Oxidation or reduction of polymer metal complexes, associated with the change in the states of charge of metal centers and with directed charge transfer over polymer chain, is accompanied, to maintain overall electrical neutrality of the system, by penetration into a polymer of charge-compensating counter-ions that are present in the electrolyte solution surrounding the polymer or by the egress of charge-compensating counter-ions from the polymer.
  • the existence of metal centers in different states of charge in a polymer metal complex is the reason for calling them "mixed-valence” complexes or "partially-oxidized” complexes.
  • the metal center in the exemplary polymer complex poly- may be in one of three states of charge: Ni 2+ -neutral state; Ni 3+ -oxidized state; Ni + -reduced state.
  • this polymer is in the neutral state ( Figure 3a)
  • Figure 3a When this polymer is in the neutral state ( Figure 3a), its monomer fragments are not charged and the charge of the metal center is compensated by the charge of the ligand environment.
  • the electrode of the present invention may use polymer metal complex in an oxidized state as a charged state of positive electrode and use a reduced state as a charged state of negative electrode. Therefore, the electrode of the present invention is allowed to be used for both positive and negative electrodes.
  • the present invention more effectively enables thin and uniform coating of the surface of an conductive porous material with polymer complex compound of transition metal, namely more effectively enables an increase of surface area compared to film thickness, consequently the electrode prepared by the present method increases ratio of doping and dedoping per unit volume against films of anion and cation, and achieves improvement of rate property and cycle property, resulting in an electrochemical device use electrode having high power properties.
  • a secondary battery may be prepared as following.
  • a non-aqueous electrolyte solution dissolving lithium salt as a solute is used as an electrolyte solution.
  • an electrode by a method of the present invention is used as a positive electrode, and an electrode occluding and releasing lithium such as lithium metal or carbon capable of occluding and releasing lithium is used as a negative electrode.
  • the secondary battery may also be produced by using the electrode of the present invention for the negative electrode, and using lithium metal oxide such as LiCoO 2 for the positive electrode. In any cases, output characteristics and energy density are improved.
  • acid aqueous solution having proton as an electrolyte solution is used.
  • an electrode of the present invention is used as a positive electrode and the negative electrode of the proton battery such as quinoxaline based polymer is used as a negative electrode.
  • the above proton battery is high in energy density.
  • a double electric layer capacitor may be prepared as following.
  • the above non-aqueous type may be used as an electrolyte solution.
  • this double electric layer capacitor improves in energy density.
  • an electrode having the double electric layer capacitor for a positive electrode and using the negative electrode of the present invention as a negative electrode, such as activated carbon for a negative electrode this double electric layer capacitor improves in energy density in the same way.
  • An electrochemical capacitor may be prepared as following.
  • an electrolyte solution a non-aqueous electrolyte solution dissolving lithium salt, quaternary ammonium salt or quaternary phosphonium salt as a solute is used.
  • a conductive polymer such as polythiophene having oxidation-reduction reaction responsiveness for a negative electrode
  • metal oxide such as the conductive polymer or ruthenium oxide as the positive electrode and using the negative electrode of the present invention as a negative electrode
  • energy density improves.
  • the polymer complex electrode by the method of the present invention may be used for both positive and negative electrodes, therefore the electrode of the present invention may be used for both electrodes, thereby that allows a electrochemical capacitor having high energy density to be obtained.
  • the double electric layer capacitor manufactured by the present invention is provided with a metallic casing 1 in the form of a flat vessel and cover 2, an activated carbon electrode 4, a separator 5 inserted between both activated carbon electrodes 4 and a top sealing gasket 6 for sealing surrounding area of the casing 1 and the cover 2.
  • the manufacturing process of such a double electric layer capacitor by the present invention is as follow.
  • the activated carbon fabric woven in the form of cloth is utilized as the activated carbon electrode 4.
  • the electrode 4 is impregnated with the solution of the monomers for polymerization, subsequently pulled up, and then a solvent in the solution of monomers for polymerization is removed by drying treatment, for instance. Removal of the solvent allows the monomers for polymerization to remain in the state of adhering so as not to easily desorb due to adsorptive power of the activated carbon.
  • the inside of the casing 1 is sealed by superimposing the separator 5 on the activated carbon electrode 4, fitting the cover 2 on the casing 1 and caulking the casing 1 around the top sealing gasket 6, after impregnating the activated carbon electrode 4 with electrolyte solution by pouring thereon.
  • the electrolysis polymerization of monomers for polymerization is performed by applying pulse voltage from the external electrode of the electrochemical element.
  • a conductive polymer is formed on the surface of the activated carbon electrode.
  • electric energy, which has been applied during the electrolysis polymerization is efficiently consumed for the polymerization reaction because the monomers for polymerization, which changes into a conductive polymer, remain in the state of adhering to the surface of the electrode. This enables to minimize the electric energy for forming the conductive polymer with a desired thickness, and also to reduce polymerization time.
  • the conditions regarding the conductive porous material, the solution of monomers for polymerization, the electrolysis polymerization, the electrolytic solution and the conductive polymer layer which are utilized in the manufacturing process of the electrochemical element according to the present invention are equivalent to those in the manufacturing process of the electrode for the electrochemical element described above.
  • the separator utilized in the manufacturing process of the electrochemical element according to the present invention it is preferable to employ a micro porous film or non woven fabric made of polyethylene or polypropylene in the range of 0.05 to 0.1 mm in thickness
  • a micro porous film or non woven fabric made of polyethylene or polypropylene in the range of 0.05 to 0.1 mm in thickness

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne, d'une part un procédé de production d'électrode pour pile électrochimique améliorant la densité d'énergie et le débit, et un procédé de production d'électrode correspondant. En l'occurrence, on absorbe des monomères pour polymérisation sur une surface d'un matériau poreux conducteur de superficie spécifique de 100 à 3000m2g-1 pour un diamètre moyen des pores de 0,4 à 100 nm. Pour réaliser ensuite une polymérisation par électrolyse, on applique une tension d'impulsions utilisant comme électrode dans la solution électrolyte le matériau poreux conducteur de façon à empiler les monomères à polymériser, puis on forme sur la surface du matériau poreux conducteur une couche polymère conductrice. Il se forme un film électrode fin et uniforme, à savoir l'électrode de la pile électrochimique aux excellentes caractéristiques de débit et à la densité d'énergie amélioré. L'invention concerne également un procédé de production d'une pile électrochimique par formation d'une couche polymère conductrice sur la surface du matériau poreux conducteur à l'intérieur d'un boîtier extérieur. A cet effet, on absorbe des monomères pour polymérisation sur une surface d'un matériau poreux conducteur d'une superficie spécifique de 100 à 3000m2g-1 pour un diamètre moyen des pores de 0,4 à 100 nm. En l'occurrence, pour former une pile électrochimique, on utilise le matériau poreux conducteur dans les pores duquel on fait absorber les monomères à polymériser. On place la pile électrochimique et la solution électrolyte dans un boîtier extérieur, et on réalise une polymérisation par électrolyse des monomères à polymériser dans la solution électrolyte par application d'une tension d'impulsions à partir d'une électrode externe du boîtier extérieur de façon à empiler le monomère à polymérisation. Ce procédé permet de produire une pile électrochimique avec l'électrode de l'invention par la suite d'opérations en passant par une polymérisation par électrolyse, ce qui réduit le nombre des opérations nécessaires à la production de la pile électrochimique.
EP05751144A 2005-06-10 2005-06-10 Procedes de production d'electrode pour pile electrochimique et de cette pile avec l'electrode Withdrawn EP1889270A4 (fr)

Applications Claiming Priority (1)

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PCT/JP2005/011085 WO2006131992A1 (fr) 2005-06-10 2005-06-10 Procedes de production d'electrode pour pile electrochimique et de cette pile avec l'electrode

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EP1889270A1 true EP1889270A1 (fr) 2008-02-20
EP1889270A4 EP1889270A4 (fr) 2010-05-26

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US (1) US20090026085A1 (fr)
EP (1) EP1889270A4 (fr)
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JP5583152B2 (ja) * 2012-01-25 2014-09-03 富士シリシア化学株式会社 リチウム二次電池電極用組成物、及びリチウム二次電池
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WO2019008681A1 (fr) * 2017-07-04 2019-01-10 株式会社Ｊａｓｔ研究所 Batterie secondaire et procédé de fabrication de batterie secondaire
JP7120887B2 (ja) * 2018-11-09 2022-08-17 出光興産株式会社 導電性高分子含有多孔質体の製造方法
CN111293275B (zh) * 2020-05-09 2020-09-01 北京小米移动软件有限公司 一种锂离子电池电极、电池及其活化方法

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WO2006131992A1 (fr) 2006-12-14
JP2008546210A (ja) 2008-12-18
US20090026085A1 (en) 2009-01-29

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