WO2020196747A1 - Dispositif de stockage d'énergie et procédé de fabrication de dispositif de stockage d'énergie - Google Patents

Dispositif de stockage d'énergie et procédé de fabrication de dispositif de stockage d'énergie Download PDF

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WO2020196747A1
WO2020196747A1 PCT/JP2020/013649 JP2020013649W WO2020196747A1 WO 2020196747 A1 WO2020196747 A1 WO 2020196747A1 JP 2020013649 W JP2020013649 W JP 2020013649W WO 2020196747 A1 WO2020196747 A1 WO 2020196747A1
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storage device
power storage
positive electrode
polymer
voltage
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Japanese (ja)
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矢野　雅也
弘義 武
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Nitto Denko Corp
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Nitto Denko Corp
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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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/62—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
    • H01M4/622—Binders being 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a power storage device and a method for manufacturing the power storage device.
  • Patent Document 1 describes an electrochemical device in which a positive electrode having a positive electrode material layer containing a conductive polymer and a negative electrode having a negative electrode material layer that occludes and releases lithium ions are combined.
  • a process called aging is performed in the fabrication of this electrochemical device. For example, in the embodiment of Patent Document 1, aging is performed at 25 ° C. for 24 hours while applying a charging voltage of 3.8 V between the terminals of the positive electrode and the negative electrode.
  • the present invention provides a power storage device and a method for manufacturing the power storage device, which is advantageous for increasing the discharge capacity of the power storage device at a low temperature.
  • the present invention It is a power storage device It comprises a positive electrode containing an electrochemically active polymer having an oxidant and a reducer.
  • the Raman spectrum of the polymer obtained by using a light source having an excitation wavelength of 514nm when the voltage of the electric storage device is 3.6V, the intensity at 1560 ⁇ 1660 cm -1 for the maximum value of magnitude in 1300 ⁇ 1370 cm -1 Satisfy the condition that the ratio of maximum values is 2.8 or less Provides a power storage device.
  • the present invention To provide a positive electrode containing an electrochemically active polymer having an oxidant and a reductant. A voltage exceeding 3.8 V is applied to the positive electrode. Provided is a method for manufacturing a power storage device.
  • the present invention To provide a positive electrode containing an electrochemically active polymer having an oxidant and a reductant. A voltage of 3.7 V or more is applied to the positive electrode at a temperature of 50 ° C. to 80 ° C. Provided is a method for manufacturing a power storage device.
  • the present invention To provide a positive electrode containing an electrochemically active polymer having an oxidant and a reducer and a conductive auxiliary agent having an aspect ratio of 10 or more. A voltage of 3.7 V or higher is applied to the positive electrode. Provided is a method for manufacturing a power storage device.
  • the above power storage device is advantageous for increasing the discharge capacity at low temperature.
  • the above production method is advantageous for increasing the discharge capacity of the power storage device at low temperature while using a positive electrode containing an electrochemically active polymer having an oxidant and a reducer.
  • FIG. 1 is a cross-sectional view schematically showing an example of a positive electrode used in the manufacturing method of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing an example of the power storage device according to the present invention.
  • a predetermined voltage may be applied to the positive electrode for a predetermined period of time for aging.
  • an electrochemically active polymer having an oxidant and a reductant is considered to increase its conductivity by aging.
  • the discharge capacity of the power storage device at a low temperature can be increased, the value of the power storage device can be increased. According to the studies by the present inventors, it has been found that it is difficult to increase the discharge capacity of the power storage device at a low temperature by the aging described in Patent Document 1.
  • the power storage device 5 includes a positive electrode 1.
  • the positive electrode 1 contains an electrochemically active polymer 12.
  • the polymer 12 has an oxidized body and a reduced product.
  • Raman spectra of polymer 12 obtained by using a light source having an excitation wavelength of 514nm when the voltage is 2.2V of the electric storage device 5, the intensity at 1450 ⁇ 1550 cm -1 of intensity at 1300 ⁇ 1370 cm -1 for the maximum value Mb
  • the condition that the ratio (Ma / Mb) of the maximum value Ma of is 4.0 or less is satisfied.
  • the Raman spectrum of the polymer 12 obtained using a light source with an excitation wavelength of 514 nm when the voltage of the storage device 5 is 3.6 V is from 1560 to 1560 to the maximum intensity (Md) at 1300 to 1370 cm- 1 .
  • the condition that the ratio (Mc / Md) of the maximum value (Mc) of the intensity at 1660 cm -1 is 2.8 or less is satisfied.
  • the discharge capacity of the power storage device 5 at a low temperature tends to increase. The reason is not clear, but it is considered that when the polymer 12 satisfies the above conditions, the active region of the polymer 12 becomes large. It is considered that the maximum value of the intensity at 1300 to 1370 cm -1 in the above Raman spectrum is derived from the cation radical of the polymer 12.
  • Ma / Mb is preferably 3.5 or less, more preferably 3.0 or less, still more preferably 2.5 or less, particularly preferably 2.0 or less, and particularly preferably 1.5 or less. It is as follows.
  • the lower limit of Ma / Mb is not limited to a specific value.
  • Ma / Mb is, for example, 0.1 or more, and may be 1.0 or more.
  • Mc / Md is preferably 2.6 or less, more preferably 2.4 or less, still more preferably 2.2 or less, and particularly preferably 2.0 or less.
  • the lower limit of Mc / Md is not limited to a specific value.
  • Mc / Md is, for example, 0.1 or more, 0.5 or more, or 1.0 or more.
  • the peak area at 400 to 401 eV is, for example, 15% or more of the peak area at 398 to 402 eV. Is.
  • the discharge capacity of the power storage device 5 at a low temperature tends to increase more reliably.
  • the method for manufacturing the power storage device 5 includes, for example, the following steps (Ia) and (IIa).
  • the method for manufacturing the power storage device 5 may include the following steps (IIb) instead of the step (IIa).
  • (Ia) Provided is a positive electrode 1 containing an electrochemically active polymer having an oxidized body and a reduced product.
  • (IIa) A voltage exceeding 3.8 V is applied to the positive electrode 1.
  • a voltage of 3.7 V or higher is applied to the positive electrode 1 at a temperature of 50 ° C to 80 ° C.
  • the method for manufacturing the power storage device 5 may include the following steps (Ib) instead of the steps (Ia) and the following steps (IIc) instead of the steps (IIa).
  • (Ib) Provided is a positive electrode 1 containing an electrochemically active polymer having an oxidized body and a reduced product and a conductive auxiliary agent having an aspect ratio of 10 or more.
  • (IIc) A voltage of 3.7 V or higher is applied to the positive electrode 1.
  • a voltage exceeding 3.8 V is applied to the positive electrode 1, or a voltage of 3.7 V or more is applied to the positive electrode 1 at a temperature of 50 ° C. to 80 ° C. It is considered that the dopant easily penetrates into the inside of the polymer 12, and the active region of the polymer 12 becomes large.
  • the step (IIc) by applying a voltage of 3.7 V or more to the positive electrode 1 containing the conductive auxiliary agent having an aspect ratio of 10 or more, the dopant easily penetrates into the inside of the polymer 12. , It is considered that the active region of the polymer 12 becomes large. As a result, it is considered that the discharge capacity of the power storage device 5 at a low temperature becomes particularly large.
  • the environmental temperature of the positive electrode 1 when the voltage is applied to the positive electrode 1 is not limited to a specific temperature.
  • This environmental temperature is, for example, 20 ° C. or higher, preferably 25 ° C. or higher, and more preferably 50 ° C. or higher.
  • This environmental temperature is, for example, 80 ° C. or lower.
  • step (IIa) for example, charging and discharging are repeated according to the upper limit voltage of charging determined so that a voltage exceeding 3.8 V is applied to the positive electrode 1.
  • This allows, for example, the polymer to repeat doping and dedoping at the positive electrode 1. In this case, a state in which a voltage exceeding 3.8 V is applied to the positive electrode 1 occurs intermittently.
  • the state in which the above voltage is applied to the positive electrode 1 may be maintained. This can, for example, keep the polymer 12 doped. In this case, the state in which the above voltage is applied to the positive electrode 1 may be generated continuously or intermittently.
  • the voltage applied to the positive electrode 1 is, for example, 3.9 V or more, preferably 4.0 V or more, and more preferably 4.1 V or more.
  • the voltage applied to the positive electrode 1 may be larger than 3.7V, may be 3.8V or higher, may be 3.9V or higher, and may be 4 It may be 0.0V or more, or 4.1V or more.
  • the voltage applied to the positive electrode 1 is, for example, 4.3 V or less. As a result, damage to the positive electrode 1 is unlikely to occur, and the discharge capacity of the power storage device 5 at a low temperature tends to increase more reliably.
  • the power storage device 5 obtained by this manufacturing method can exhibit a discharge capacity of 45 mAh / g or more at ⁇ 30 ° C.
  • the discharge capacity that the power storage device 5 can exert at ⁇ 30 ° C. is preferably 50 mAh / g or more, more preferably 55 mAh / g or more, and further preferably 60 mAh / g or more.
  • the time during which the voltage exceeding 3.8 V is applied to the positive electrode 1 is not limited to a specific value, but is, for example, 1 to 10 hours.
  • the time for applying the voltage of 3.7 V or more to the positive electrode 1 is not limited to a specific value, but is, for example, 1 to 10 hours.
  • the time during which a voltage of 3.7 V or higher is applied to the positive electrode 1 is not limited to a specific value, but is, for example, 1 to 48 hours.
  • the positive electrode 1 includes, for example, an active material layer 10, a current collector 20, and a conductive layer 30.
  • the active material layer 10 contains the above polymer (polymer 12).
  • the conductive layer 30 is arranged between the active material layer 10 and the current collector 20.
  • the conductive layer 30 is in contact with the active material layer 10 and the current collector 20. Due to the conductive layer 30, peeling or the like is unlikely to occur between the active material layer 10 and the current collector 20. Therefore, even if a voltage exceeding 3.8 V or a voltage of 3.7 V or more is applied to the positive electrode 1 in the steps (IIa), (IIb), or (IIc), the positive electrode 1 is not easily damaged and the power storage device. It is possible to prevent the internal resistance of 5 from increasing. As a result, the discharge capacity of the power storage device 5 at a low temperature tends to increase more reliably.
  • the conductive layer 30 is not limited to a specific mode as long as the discharge capacity of the power storage device 5 at a low temperature can be increased.
  • the conductive layer 30 contains, for example, conductive particles 32 made of a carbon material and a binder 35 in contact with the outer surface of the conductive particles 32. In this case, the conductive layer 30 easily adheres to the active material layer 10 and the current collector 20, and the voltage exceeding 3.8 V or the voltage of 3.7 V or more is generated in the steps (IIa), (IIb), or (IIc). Even if it is applied to the positive electrode 1, the positive electrode 1 is not easily damaged.
  • the contact angle of water droplets on the surface formed by the conductive layer 30 is, for example, 100 ° or less.
  • the contact angle of water droplets on the surface of the conductive layer 30 can be measured, for example, according to the static droplet method in Japanese Industrial Standards JIS R 3257: 1999 before forming the active material layer 10.
  • the measurement temperature of the contact angle of the water droplet is 25 ° C.
  • the contact angle of water droplets on the surface of the conductive layer 30 is determined by, for example, forming the active material layer 10 and then removing at least a part of the active material layer 10 by a method such as polishing or cutting to expose the conductive layer 30. It may be measured on the surface of the conductive layer 30.
  • at least a part of the current collector 20 may be removed by a method such as polishing or cutting to expose the conductive layer 30, and measurement may be performed on the surface of the exposed conductive layer 30.
  • the small contact angle of water droplets on the main surface of the conductive layer 30 is advantageous from the viewpoint of enhancing the adhesion between the conductive layer 30 and the active material layer 10.
  • the contact angle of the water droplets is preferably 90 ° or less, more preferably 80 ° or less, and even more preferably 70 ° or less.
  • the contact angle of the water droplet is, for example, 10 ° or more.
  • the peel strength P of the active material layer 10 with respect to the conductive layer 30 measured by the Surface And Interfacial Cutting Analysis System is, for example, 0.15 kN / m or more.
  • the peel strength P is determined by, for example, the following formula (1).
  • the measurement mode of SAICAS is the constant speed mode.
  • the cutting speed is 10 ⁇ m / sec.
  • FH is the horizontal cutting stress [N] when the SAICAS diamond cutting edge (manufactured by Daipla, rake angle: 10 °) is horizontally moved at the interface between the active material layer 10 and the conductive layer 30.
  • W is the blade width [m] of the cutting blade of SAICAS.
  • SAICAS is a registered trademark of Daipla Co., Ltd.
  • P FH / W (1)
  • the peel strength P is preferably 0.15 kN / m or more, more preferably 0.17 kN / m or more, and further preferably 0.23 kN / m or more.
  • the binder 35 of the conductive layer 30 is not limited to a specific binder as long as the discharge capacity of the power storage device 5 at a low temperature can be increased.
  • the binder 35 contains, for example, at least one selected from the group consisting of methyl cellulose, hydroxyethyl cellulose, polyethylene oxide, carboxymethyl cellulose, derivatives thereof, salts thereof, polyolefins, natural rubbers, synthetic rubbers, and thermoplastic elastomers.
  • the conductive layer 30 easily adheres to the active material layer 10 and the current collector 20, and the voltage exceeding 3.8 V or the voltage of 3.7 V or more is generated in the steps (IIa), (IIb), or (IIc). Even if it is applied to the positive electrode 1, the positive electrode 1 is not easily damaged.
  • the synthetic rubber or thermoplastic elastomer for example, a styrene-butadiene copolymer, an acrylonitrile-butadiene copolymer, or a methyl methacrylate-butadiene copolymer can be used.
  • the binder 35 may contain at least one selected from the group consisting of polyolefin, carboxymethyl cellulose, and styrene-butadiene copolymer. In this case, the adhesion between the conductive layer 30 and the active material layer 10 or the current collector 20 tends to increase more reliably.
  • the binder 35 preferably contains at least one of carboxymethyl cellulose and a styrene-butadiene copolymer. In this case, the adhesion between the conductive layer 30 and the active material layer 10 tends to increase. In particular, when the binder 15 of the active material layer 10 described later contains a predetermined component, the adhesion between the conductive layer 30 and the active material layer 10 tends to increase.
  • the carbon material contained in the conductive layer 30 is, for example, graphite.
  • the thickness of the conductive layer 30 has a thickness of, for example, 0.1 ⁇ m to 20 ⁇ m.
  • the conductive layer 30 may have a thickness of 0.1 ⁇ m to 10 ⁇ m, or may have a thickness of 0.1 ⁇ m to 5 ⁇ m.
  • the electrochemically active polymer 12 contained in the positive electrode 1 contains, for example, at least one of polyaniline and a polyaniline derivative. In this case, the discharge capacity of the power storage device 5 at a low temperature can be increased more reliably.
  • Polyaniline and polyaniline derivatives are collectively referred to as "polyaniline compounds".
  • the polymer 12 is typically a semi-oxidized polyaniline-based compound having an oxidized form and a reduced form.
  • Polyaniline is typically obtained by electrolytic polymerization or chemical oxidative polymerization of aniline.
  • Polyaniline derivatives are typically obtained by electrolytic or chemical oxidative polymerization of aniline derivatives.
  • the aniline derivative has, for example, at least one substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group at a position other than the 4-position of aniline.
  • substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group at a position other than the 4-position of aniline.
  • the aniline derivative is, for example, (i) o-substituted aniline such as o-methylaniline, o-ethylaniline, o-phenylaniline, o-methoxyaniline, and o-ethoxyaniline, or (ii) m-methylaniline.
  • aniline derivative M-Ethylaniline, m-methoxyaniline, m-ethoxyaniline, m-phenylaniline and the like can be m-substituted anilines.
  • only one kind of aniline derivative may be used, or two or more kinds of aniline derivatives may be used in combination.
  • Dopants such as protonic acid may be doped into polyaniline compounds in order to impart conductivity.
  • the polyaniline and the polyaniline derivative contained in the polymer 12 are dedoping. Specifically, the polyaniline and the polyaniline derivative contained in the polymer 12 are in a state in which a dopant such as a protonic acid is dedoping. In this case, the polymer 12 can be appropriately dispersed in the active material layer 10, and the energy density of the power storage device 5 can be easily increased.
  • the polymer 12 containing the dedoping polyaniline and the like disperses well in the slurry even if the dispersion medium of the slurry for forming the active material layer 10 is water.
  • the polymer 12 when assembling the power storage device 5, the polymer 12 is dedoping in the positive electrode 1. When the power storage device 5 is in a charged state, the polymer 12 is in a state of being doped in the positive electrode 1. It is conceivable to assemble the power storage device 5 by combining a positive electrode chemically doped in advance and a negative electrode that has not been charged. In this case, in the initial charge of the power storage device 5, only the chemically undoped electrochemically active polymer at the positive electrode contributes to the charge. Therefore, the initial charge capacity of the power storage device 5 becomes significantly small, which is not preferable for the power storage device 5.
  • the power storage device 5 by combining a positive electrode chemically doped in advance and a negative electrode such as a lithium pre-doped negative electrode. In this case, it is possible to discharge the power storage device 5 immediately after assembling, but the chemically doped dopant is difficult to be electrochemically doped and dedoping, resulting in a decrease in the capacity of the power storage device 5. Therefore, it is difficult to obtain the desired power storage device 5. Even if the polymer 12 in the dedoping state in the positive electrode 1 provided in the step (I) is used as the power storage device 5 by repeating the doping and dedoping of the polymer 12 in the step (II). it can.
  • the polyaniline and the polyaniline derivative contained in the electrochemically active polymer 12 contain, for example, 35 to 60% of oxides on a mass basis. In this case, the storage stability of the polymer 12 is good, and the polymer 12 can exhibit desirable properties as an active material of the positive electrode 1.
  • the chemical structures of the oxidized form Ox and the reduced form Red of polyaniline are shown in the following formula (a). In the formula (a), each of x and y is an integer of 0 or more.
  • the amount of an oxidizing agent added such as manganese dioxide is stoichiometrically adjusted with respect to polyaniline so that the content of the oxidant in the polyaniline compound is within a predetermined range (35 to 60% on a mass basis).
  • the content of the oxidant in the polyaniline-based compound contained in the electrochemically active polymer 12 can be determined from, for example, the solid 13 CNMR spectrum.
  • the content of the oxidant in the polyaniline-based compound contained in the polymer 12 is the ratio A640 / A340 of the maximum absorption A640 near 640 nm and the maximum absorption A340 near 340 nm in the electron spectrum of the spectrophotometer. It is also possible to obtain it from the oxidation degree index represented by.
  • the content of the oxidant (ratio of the oxidant) in the polyaniline compound contained in the electrochemically active polymer 12 can be determined, for example, according to the method described in paragraphs 0040 to 0051 of JP-A-2018-26341. ..
  • the electrochemically active polymer 12 forms particles having an average particle size of more than 0.5 ⁇ m, for example.
  • the average particle size of the particles formed by the polymer 12 is, for example, the maximum diameter of 50 or more particles when observing 50 or more particles of the polymer 12 using an electron microscope such as a scanning electron microscope (SEM). It can be determined by measuring. Alternatively, the average particle size of the particles formed by the polymer 12 may be determined by using a particle image analyzer that images the shape of the particles using a microscope and analyzes them by image analysis.
  • the "average particle size" refers to the median diameter (D50).
  • the median diameter is a particle size in which the number of particles having a particle size larger than that value is equal to the number of particles having a particle size smaller than that value.
  • the polymer 12 forms particles having the above-mentioned average particle size, even if a voltage of less than 3.7 V is applied to the positive electrode 1 for aging, the dopant does not easily penetrate into the particles, and the polymer 12 It is difficult to increase the active region of the active material as an active material, and it is difficult to increase the discharge capacity of the power storage device 5 at a low temperature.
  • the voltage exceeding 3.8 V or the voltage of 3.7 V or more in the steps (IIa), (IIb), or (IIc) Is applied to the positive electrode 1 so that it easily penetrates into the particles formed by the polymer 12.
  • the active region of the polymer 12 tends to be large, and the discharge capacity of the power storage device 5 at a low temperature tends to be large.
  • the average particle size of the particles formed by the polymer 12 is, for example, 20 ⁇ m or less.
  • the content of the polymer 12 in the active material layer 10 is, for example, 1% or more, preferably 5% or more, more preferably 20% or more, and further preferably 40% or more, in particular, on a mass basis. Desirably 60% or more. As a result, the energy density of the power storage device 5 tends to increase.
  • the active material layer 10 further contains, for example, a conductive auxiliary agent 14.
  • the conductive auxiliary agent 14 is typically made of a conductive material having a property that does not change depending on the voltage applied for charging / discharging the power storage device 5.
  • the conductive auxiliary agent 14 can be a conductive carbon material or a metallic material.
  • the conductive carbon material is, for example, conductive carbon black such as acetylene black and Ketjen black, or fibrous carbon material such as carbon fiber and carbon nanotube.
  • the conductive carbon material is preferably conductive carbon black.
  • the conductive auxiliary agent 14 preferably has an aspect ratio of 10 or more. As a result, the discharge capacity of the power storage device 5 at a low temperature is likely to increase.
  • An example of a conductive auxiliary agent having an aspect ratio of 10 or more is a fibrous carbon material such as carbon fiber and carbon nanotube.
  • the conductive auxiliary agent 14 may contain a conductive auxiliary agent having an aspect ratio of less than 10, and both a conductive auxiliary agent having an aspect ratio of 10 or more and a conductive auxiliary agent having an aspect ratio of less than 10 are used. It may be included.
  • An example of a conductive auxiliary agent having an aspect ratio of less than 10 is conductive carbon black.
  • the content of the conductive additive 14 in the active material layer 10 is, for example, 1 to 30%, preferably 4 to 25%, and more preferably 4 to 19% on a mass basis.
  • the polymer 12 can be activated more reliably while suppressing the content of the conductive auxiliary agent. As a result, it is easy to increase the energy density of the power storage device 5.
  • the active material layer 10 further contains, for example, a binder 15.
  • the binder 15 contains, for example, an elastomer.
  • the elastomer can be natural rubber, synthetic rubber, or thermoplastic elastomer.
  • the binder 15 is typically in contact with the outer surface of the particles formed by the polymer 12 and the outer surface of the conductive aid 14.
  • the binder 15 binds the particles formed by the polymer 12 and the conductive auxiliary agent 14. As a result, even if a voltage exceeding 3.8 V or a voltage of 3.7 V or more is applied to the positive electrode 1 in the steps (IIa), (IIb), or (IIc)) more reliably, the positive electrode 1 is damaged. Hard to receive. As shown in FIG.
  • the active material layer 10 has, for example, pores 16.
  • the pores 16 are formed so as to be continuous from one main surface of the active material layer 10 to the other main surface, for example.
  • the electrolytic solution is impregnated into the pores 16. Since the binder 15 contains an elastomer, the binder 15 is easily deformed without generating a large stress according to the dimensional change of the electrochemically active polymer particles accompanying the charging and discharging of the power storage device 5.
  • the binder 15 contains, for example, a rubber material.
  • the rubber material can be, for example, a styrene-butadiene copolymer, an acrylonitrile-butadiene copolymer, or a methyl methacrylate-butadiene copolymer.
  • the total of the polar term and the hydrogen bond term in the Hansen solubility parameter of the binder 15 is, for example, 20 MPa 1/2 or less.
  • the binder 15 and the polymer 12 have a good affinity, and the conductive additive 14 easily comes into contact with the polymer 12.
  • the adhesion between the active material layer 10 and the conductive layer 30 tends to increase.
  • the calculation for determining the Hansen solubility parameter can be performed according to the method described in Charles M. Hansen, Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007).
  • HSPiP Hansen Solubility Parameters in Practice
  • HSPiP Hansen Solubility Parameters in Practice
  • the total of the polarity term and the hydrogen bond term in the Hansen solubility parameter of the binder made of the composite material is determined by summing the product of the Hansen solubility parameter of each component constituting the binder and the mass-based composition ratio of each component. it can.
  • the sum of the polar term and the hydrogen bond term in the Hansen solubility parameter of the binder 15 is preferably 19 MPa 1/2 or less, more preferably 12 MPa 1/2 or less, and further preferably 8 MPa 1/2 or less. ..
  • the predetermined component can be, for example, a rubber material such as methyl cellulose, hydroxyethyl cellulose, polyethylene oxide, carboxymethyl cellulose, derivatives thereof, salts thereof, or styrene-butadiene copolymer.
  • the predetermined component is carboxymethyl cellulose or a styrene-butadiene copolymer.
  • the content of the binder 15 in the active material layer 10 is, for example, 1 to 30%, preferably 4 to 25%, and more preferably 4 to 18% on a mass basis.
  • the electrochemically active polymer 12 can be appropriately dispersed in the active material layer 10 while suppressing the content of the binder 15. As a result, it is easy to increase the energy density in the power storage device 5.
  • the active material layer 10 may contain an active material other than the polymer 12 if necessary.
  • the active material other than the polymer 12 is, for example, a carbon material such as activated carbon.
  • the activated carbon can be an alkaline activated carbon, a steam activated carbon, a gas activated carbon, or a zinc chloride activated carbon.
  • the active material layer 10 may further contain an additive such as a thickener, if necessary.
  • Thickeners are, for example, methyl cellulose, hydroxyethyl cellulose, polyethylene oxide, carboxymethyl cellulose, derivatives thereof, or salts thereof. Among them, carboxylmethyl cellulose, a derivative thereof, or a salt thereof is preferably used as a thickener.
  • the content of the thickener in the active material layer 10 is, for example, 1 to 20%, preferably 1 to 10%, and more preferably 1 to 8% on a mass basis.
  • the current collector 20 is a foil or mesh made of a metal material such as nickel, aluminum, and stainless steel.
  • the current collector 20 is prepared, and the conductive layer 30 is formed on the main surface of the current collector 20.
  • the conductive layer 30 is formed, for example, by coating, sputtering, vapor deposition, ion plating, or CVD using a predetermined raw material.
  • the conductive layer 30 is formed by applying a slurry prepared by dispersing the conductive particles 32 and the binder 35 in a dispersion medium to the main surface of the current collector 20 to form a coating film, and the coating film is dried. It can be formed by that.
  • a slurry prepared by dispersing the electrochemically active polymer 12, the conductive additive 14, and the binder 15 in a dispersion medium is applied to the surface of the conductive layer 30 to form a coating film, and this coating film is applied.
  • the active material layer 10 can be formed by drying. In this way, the positive electrode 1 can be manufactured. If necessary, an active material other than the electrochemically active polymer 12 and an additive such as a thickener are added to the slurry for forming the active material layer 10.
  • the power storage device 5 can be manufactured using the positive electrode 1.
  • the power storage device 5 includes an electrolyte layer 3, a negative electrode 2, and a positive electrode 1.
  • the negative electrode 2 is arranged in contact with the first main surface of the electrolyte layer 3.
  • the positive electrode 1 is arranged in contact with the second main surface of the electrolyte layer 3.
  • the active material layer 10 of the positive electrode 1 is in contact with the second main surface of the electrolyte layer 3.
  • the electrolyte layer 3 is arranged between the positive electrode 1 and the negative electrode 2. Since the power storage device 5 includes the positive electrode 1, it can exhibit good characteristics regarding rapid charging and discharging.
  • the electrolyte layer 3 is composed of an electrolyte.
  • the electrolyte layer 3 is, for example, a sheet in which a separator is impregnated with an electrolytic solution or a sheet made of a solid electrolyte.
  • the electrolyte layer 3 is a sheet made of a solid electrolyte, the electrolyte layer 3 itself may also serve as a separator.
  • the above electrolyte contains a solute and, if necessary, a solvent and various additives.
  • the solute is, for example, a combination of a metal ion such as lithium ion and a predetermined counter ion for the metal ion.
  • Counter ions include, for example, sulfonic acid ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroarsenic ion, bis (trifluoromethanesulfonyl) imide ion, bis (pentafluoroethanesulfonyl) imide ion, and bis.
  • electrolytes include LiCF 3 SO 3 , LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ), LiN (SO 2 F) 2 , And LiCl.
  • the solvent in the electrolyte is, for example, a non-aqueous solvent (organic solvent) such as a carbonate compound, a nitrile compound, an amide compound, and an ether compound.
  • organic solvent such as a carbonate compound, a nitrile compound, an amide compound, and an ether compound.
  • Specific examples of the solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, acetonitrile, propyronitrile, N, N'-dimethylacetamide, N-methyl-2-pyrrolidone, dimethoxyethane, and the like. Diethoxyethane and ⁇ -butyrolactone.
  • solvent in the electrolyte one kind of solvent may be used alone, or two or more kinds of solvents may be used in combination.
  • a solution in which a solute is dissolved in the above solvent may be referred to as an "electrolyte solution”.
  • the electrolytic solution may contain additives as needed.
  • Additives are, for example, vinylene carbonate or fluoroethylene carbonate.
  • the negative electrode 2 includes, for example, an active material layer 60 and a current collector 70.
  • the active material layer 60 contains a negative electrode active material.
  • the negative electrode active material is a substance capable of inserting and removing a metal or ions.
  • metallic lithium, a carbon material capable of inserting and removing lithium ions by a redox reaction, a transition metal oxide, silicon, and tin are preferably used.
  • the active material layer 60 is in contact with the first main surface of the electrolyte layer 3.
  • Carbon materials capable of inserting and removing lithium ions include, for example, (i) activated carbon, (ii) coke, (iii) pitch, (iv) phenolic resin, polyimide, and a calcined product of cellulose, and (v) artificial graphite. , (Vi) natural graphite, (vii) hard carbon, or (vii) soft carbon.
  • a carbon material capable of inserting and removing lithium ions is preferably used as the main component of the negative electrode.
  • the principal component means the component contained most in terms of mass.
  • the current collector 70 is a foil or mesh made of a metal material such as nickel, aluminum, stainless steel, and copper.
  • the negative electrode 2 it is also possible to use a lithium pre-doped negative electrode in which lithium ions are pre-doped into a carbon material such as graphite, hard carbon, or soft carbon.
  • a separator is typically arranged between the positive electrode 1 and the negative electrode 2.
  • the separator prevents an electrical short circuit between the positive electrode 1 and the negative electrode 2.
  • the separator is, for example, a porous sheet that is electrochemically stable and has high ion permeability, desired mechanical strength, and insulating properties.
  • the material of the separator is preferably a porous film made of a resin such as (i) paper, (ii) non-woven fabric, (iii) polypropylene, polyethylene, and polyimide.
  • a separator is arranged between the positive electrode 1 and the negative electrode 2 to obtain a laminated body.
  • This laminate is placed in a package made of an aluminum laminate film and vacuum dried.
  • the electrolytic solution is injected into the vacuum-dried package, the package is sealed, and the power storage device is assembled.
  • the process of assembling the power storage device such as injecting the electrolytic solution into the package, is preferably carried out using a glove box in an atmosphere of an inert gas such as ultra-high purity argon gas.
  • a process for imparting desired charge / discharge characteristics to the power storage device, including the step (II) is performed. In this way, the power storage device 5 is manufactured.
  • the power storage device 5 may be manufactured in a film type, a sheet type, a square type, a cylindrical type, a button type, or the like by using a package other than the package made of the aluminum laminated film.
  • Example 1 In a glass beaker containing 138 g of ion-exchanged water, 84.0 g (amount of substance of tetrafluoroboric acid: 0.402 mol) of a 42 mass% concentration tetrafluoroboric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) In addition, 10.0 g (0.107 mol) of aniline was further added while stirring with a magnetic stirrer. Immediately after adding aniline to the aqueous solution of tetrafluoroboric acid, the aniline was dispersed as oily droplets in the aqueous solution of tetrafluoroboric acid.
  • aniline was dissolved in water to obtain a uniform and transparent aqueous solution.
  • the aqueous solution thus obtained was cooled to -4 ° C. or lower using a constant temperature bath.
  • 11.63 g (0.134 mol) of manganese dioxide powder manufactured by Wako Pure Chemical Industries, Ltd., reagent first grade
  • the aqueous solution immediately turned black-green. After that, when stirring was continued for a while, a black-green solid began to be formed.
  • the above-doped conductive polyaniline powder was placed in a 2 mol / L sodium hydroxide aqueous solution, stirred in a 3 L separable flask for 30 minutes, and the dopant tetrafluoroboric acid was dedoped by a neutralization reaction.
  • the dedoped polyaniline was washed with water until the filtrate became neutral, then stirred and washed in acetone, and filtered under reduced pressure using a Büchner funnel and a suction bottle to obtain a dedoped polyaniline powder on No. 2 filter paper. .. This was vacuum dried at room temperature for 10 hours to obtain a brown oxidatively dedoped polyaniline powder.
  • the average particle size (D50) of the polyaniline powder was 3 ⁇ m.
  • the average particle size of the polyaniline powder was calculated using Morphologi G3 manufactured by Malvern.
  • a slurry for forming a conductive layer was prepared by mixing and stirring 18 parts by mass of carbon black as conductive particles and 15 parts by mass of an aqueous dispersion containing polyolefin (PO) as a binder.
  • the concentration of polyolefin in the polyolefin dispersion was 20% by mass.
  • An aluminum foil having a thickness of 20 ⁇ m was prepared as a current collector.
  • a slurry for forming a conductive layer was applied to one main surface of an aluminum foil to form a coating film.
  • This coating film was dried in an environment of 120 ° C. for 10 minutes to form a conductive layer.
  • the thickness of the conductive layer was 1 ⁇ m.
  • a desktop automatic coating device manufactured by Tester Sangyo Co., Ltd.
  • a slurry for forming an active material layer is applied onto the conductive layer at a coating speed of 10 mm / sec by a doctor blade type applicator with a micrometer. To form a coating film.
  • this coating film was left at room temperature (25 ° C.) for 45 minutes and then dried on a hot plate at a temperature of 100 ° C. to form an active material layer.
  • the positive electrode according to Example 1 was produced.
  • the thickness of the active material layer was 54.4 ⁇ m.
  • a separator manufactured by Nippon Kodoshi Kogyo Co., Ltd., product name: TF40-
  • TF40- graphite negative electrode sheet with a current collector tab attached. 50
  • an electrode having a metal lithium foil attached to a stainless steel mesh to which a current collector tab was attached was placed on the separator.
  • the metallic lithium foil was brought into contact with the separator.
  • This laminate was placed inside a bag-shaped package made of an aluminum laminate film.
  • this laminated cell is taken out from the glove box, and inside a constant temperature bath kept at 25 ° C., in a potential range of 2.0 V to 0.01 V, it corresponds to 0.2 C with respect to the capacity of the graphite negative electrode sheet.
  • Charging and discharging were carried out for 3 cycles with the current value to be applied, and finally, a reaction of inserting lithium ions into graphite up to a capacity of 75% of the capacity of the graphite negative electrode sheet was carried out. In this way, a laminated cell containing a lithium-predoped negative electrode sheet was produced.
  • the laminate cell containing the lithium pre-doped negative electrode sheet was reinserted into the glove box.
  • the sealed portion of the laminate cell was cut off, and the lithium-predoped negative electrode sheet was taken out.
  • these were stacked so that the separator was located between the positive electrode according to Example 1 and the negative electrode sheet predoped with lithium.
  • a non-woven fabric manufactured by Nippon Kodoshi Kogyo Co., Ltd., product name: TF40-50
  • a current collector tab was attached to the positive electrode.
  • the laminate of the positive electrode, the separator, and the negative electrode sheet was placed inside a bag-shaped package made of an aluminum laminate film.
  • the three sides of the pair of square aluminum laminate films were sealed, and the other sides were separated from each other to form an opening.
  • a LiPF 6 carbonate solution having a concentration of 1.2 M (mol / dm 3 ) was injected into the package as an electrolytic solution.
  • This carbonate solution contained ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) as carbonates.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • the sealed package is taken out of the glove box, and at the positive electrode, between the current collector tab of the positive electrode and the current collector tab of the negative electrode sheet so that the doping and dedoping of polyaniline are repeated for 10 cycles.
  • a maximum voltage of 3.9 V was applied and the aging treatment was performed at 25 ° C.
  • the cumulative time when a voltage exceeding 3.8 V was applied was 8 hours. In this way, the lithium ion capacitor according to Example 1 was obtained.
  • Example 2 A lithium ion capacitor according to Example 2 was produced in the same manner as in Example 1 except that the maximum voltage in the aging treatment was adjusted to 4.0 V. The thickness of the active material layer was 54.8 ⁇ m.
  • Example 3 A lithium ion capacitor according to Example 3 was produced in the same manner as in Example 1 except that the maximum voltage in the aging treatment was adjusted to 4.1 V. The thickness of the active material layer was 54.4 ⁇ m.
  • Example 4 A lithium ion capacitor according to Example 4 was produced in the same manner as in Example 1 except that the maximum voltage in the aging treatment was adjusted to 4.2 V. The thickness of the active material layer was 52.6 ⁇ m.
  • a lithium ion capacitor according to Reference Example 1 was produced in the same manner as in Example 1 except that the maximum voltage in the aging treatment was adjusted to 3.8 V.
  • the thickness of the active material layer was 36.0 ⁇ m.
  • Example 5 A lithium ion capacitor according to Example 5 was obtained in the same manner as in Example 1 except for the following points.
  • the conductive auxiliary agent CNT paste LB217-54 manufactured by Cnano, which contains 5% by mass of carbon nanotube (CNT) powder, was used instead of the conductive carbon black (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.) powder.
  • the amounts of polyaniline powder, conductive aid, binder, and sodium carboxymethyl cellulose were adjusted as follows.
  • a maximum voltage of 3.8 V is applied between the current collector tab of the positive electrode and the current collector tab of the negative electrode sheet for 24 hours so that the polyaniline-doped state of the positive electrode is maintained.
  • Example 6 A lithium ion capacitor according to Example 6 was obtained in the same manner as in Example 5 except that the aging treatment was changed as follows. In the aging treatment, a maximum voltage of 3.8 V was applied between the current collector tab of the positive electrode and the current collector tab of the negative electrode sheet for 3 hours so that the polyaniline-doped state of the positive electrode was maintained. At this time, the environmental temperature of the positive electrode was adjusted to 60 ° C.
  • Example 7 A lithium ion capacitor according to Example 7 was obtained in the same manner as in Example 5 except that the aging treatment was changed as follows. In the aging treatment, a maximum voltage of 4.0 V was applied between the current collector tab of the positive electrode and the current collector tab of the negative electrode sheet for 3 hours so that the polyaniline-doped state of the positive electrode was maintained. At this time, the environmental temperature of the positive electrode was adjusted to 60 ° C.
  • ⁇ Reference example 2> A brown oxidatively dedoped polyaniline powder was obtained in the same manner as in Example 1. Next, this polyaniline powder was placed in a methanol solution of phenylhydrazine, and the solution was stirred for 30 minutes for reduction treatment. As a result, the polyaniline powder changed from brown to gray. The polyaniline powder was then washed with methanol and then with acetone. Next, the polyaniline powder was separated by filtration, and the separated polyaniline powder was vacuum dried at room temperature for 10 hours to obtain a reduction-dedoped polyaniline powder. The average particle size (D50) of this polyaniline powder was 3 ⁇ m. The average particle size of the polyaniline powder was calculated using Morphologi G3 manufactured by Malvern. When the oxidation degree index of this polyaniline powder was determined, the oxidation degree index was 0.05.
  • a lithium ion capacitor according to Reference Example 2 was obtained in the same manner as in Example 6 except that the polyaniline powder in the reduction dedoping state was used instead of the polyaniline powder in the oxidation dedoping state.
  • ⁇ Reference example 4> A lithium ion capacitor according to Reference Example 4 was obtained in the same manner as in Example 5 except that the aging treatment was changed as follows. In the aging treatment, a maximum voltage of 3.6 V was applied between the current collector tab of the positive electrode and the current collector tab of the negative electrode sheet for 3 hours. At this time, the environmental temperature of the positive electrode was adjusted to 60 ° C.
  • the aspect ratio of the CNT powder and the carbon black powder For the aspect ratio of the CNT powder and the carbon black powder, 30 or more CNT powders or 30 arbitrarily selected by fixing each powder on the support film and observing each sample prepared in this manner with an electron microscope. It was determined by calculating the aspect ratio of each powder from the images of one or more carbon black powders and calculating the arithmetic average.
  • the carbon nanotube (CNT) powder contained carbon nanotubes having an aspect ratio of 50 or more.
  • the conductive carbon black powder contained carbon black having an aspect ratio of less than 10.
  • the lithium ion capacitors according to Examples 1 to 7 and Reference Examples 1 to 3 correspond to 10 C in a voltage range of 3.8 V or 3.6 V to 2.2 V inside a constant temperature bath kept at -30 ° C.
  • the CCCV was charged with a current value and held at 3.8 V or 3.6 V for 10 minutes. After that, the results of CC discharge at a current value corresponding to 10C are shown in Tables 1 and 3.
  • the value was CCCV charged and held at 3.8V or 3.6V for 10 minutes. After that, the results of CC discharge with a current value corresponding to 1C are shown in Tables 2 and 3.
  • XPS measurement The positive electrode was taken out after the discharge voltage of the power storage device became 2.2 V by CC discharge of the lithium ion capacitors according to Examples 5 to 7 and Reference Examples 2 to 5 inside the constant temperature bath kept at 25 ° C.
  • SAICAS DN-20 manufactured by Daipra Wintes
  • diagonal cutting is performed from the surface of the taken out positive electrode to expose the polyaniline inside the positive electrode and prepare a sample for photoelectron spectroscopy (ESCA) measurement. did.
  • the ESCA measurement of this sample was performed using a photoelectron spectrometer Quantum 2000 manufactured by ULVAC-PHI Co., Ltd. equipped with an X-ray source by Al K ⁇ .
  • the peaks at 398 to 399 eV, the peaks at 399 to 400 eV, the peaks at 400 to 401 eV, and the peaks at 401 to 402 eV are N1, N2, N3, and N4, respectively.
  • the waveforms were separated and the area ratios were calculated.
  • Table 3 shows the ratio of the peak area corresponding to N3 to the peak area of N1, N2, N3, and N4.
  • the power storage devices according to Examples 1 to 4 were able to exhibit a higher discharge capacity than the power storage devices according to Reference Example 1.
  • the power storage devices according to Examples 1 to 4 were able to exhibit a higher discharge capacity at a low temperature than the power storage devices according to Reference Example 1. It was suggested that the discharge capacity increases at the low temperature of the power storage device by applying the maximum voltage exceeding 3.8 V to the positive electrode in the aging process.
  • the power storage devices according to Examples 5 to 7 were able to exhibit a higher discharge capacity than the power storage devices according to Reference Examples 2 to 5.
  • the power storage devices according to Examples 5 to 7 were able to exhibit a higher discharge capacity at a low temperature than the power storage devices according to Reference Examples 2 to 5.
  • the discharge capacity is increased at a low temperature of the power storage device.
  • the ratio Ma / Mb of the maximum value of the intensity in the Raman spectrum of polyaniline is 4.0 or less, and Mc / Md is 2.8 or less. It was suggested that this is advantageous in increasing the discharge capacity of the power storage device at low temperature. From the comparison between the examples and the reference examples, it is found that the area of the peak corresponding to N3 in the XPS spectrum of polyaniline is 15% or more of the area of the peak corresponding to N1, N2, N3, and N4. It was suggested that it is advantageous in increasing the discharge capacity at low temperature.

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Abstract

L'invention concerne un dispositif de stockage d'énergie (5) comprenant une électrode positive (1). L'électrode positive (1) comprend un polymère électrochimiquement actif (12). Le polymère (12) contient un oxydant et un réducteur. Le spectre Raman du polymère (12) obtenu à l'aide d'une source lumineuse dont la longueur d'onde d'excitation vaut 514 nm lorsque la tension du dispositif de stockage d'énergie (5) vaut 2,2 V vérifie la condition selon laquelle le rapport du maximum local de l'intensité de 1 450 à 1 550 cm-1 au maximum local de l'intensité de 1 300 à 1 370 cm-1 vaut 4,0 au plus. Le spectre Raman du polymère (12) obtenu à l'aide d'une source lumineuse dont la longueur d'onde d'excitation vaut 514 nm lorsque la tension du dispositif de stockage d'énergie (5) vaut 3,6 V vérifie la condition selon laquelle le rapport du maximum local de l'intensité de 1 560 à 1 660 cm-1 au maximum local de l'intensité de 1 300 à 1 370 cm-1 vaut 2,8 au plus.
PCT/JP2020/013649 2019-03-26 2020-03-26 Dispositif de stockage d'énergie et procédé de fabrication de dispositif de stockage d'énergie Ceased WO2020196747A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017090231A1 (fr) * 2015-11-27 2017-06-01 パナソニックＩｐマネジメント株式会社 Dispositif électrochimique et procédé permettant de fabriquer ce dernier
WO2018021513A1 (fr) * 2016-07-29 2018-02-01 日東電工株式会社 Électrode positive pour dispositif de stockage d'énergie, et dispositif de stockage d'énergie
WO2018143048A1 (fr) * 2017-01-31 2018-08-09 パナソニックＩｐマネジメント株式会社 Électrode positive destinée à un dispositif électrochimique et dispositif électrochimique, et procédé de fabrication associé

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017090231A1 (fr) * 2015-11-27 2017-06-01 パナソニックＩｐマネジメント株式会社 Dispositif électrochimique et procédé permettant de fabriquer ce dernier
WO2018021513A1 (fr) * 2016-07-29 2018-02-01 日東電工株式会社 Électrode positive pour dispositif de stockage d'énergie, et dispositif de stockage d'énergie
WO2018143048A1 (fr) * 2017-01-31 2018-08-09 パナソニックＩｐマネジメント株式会社 Électrode positive destinée à un dispositif électrochimique et dispositif électrochimique, et procédé de fabrication associé

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