WO2019208735A1 - 蓄電デバイス用正極及び蓄電デバイス - Google Patents
蓄電デバイス用正極及び蓄電デバイス Download PDFInfo
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- WO2019208735A1 WO2019208735A1 PCT/JP2019/017796 JP2019017796W WO2019208735A1 WO 2019208735 A1 WO2019208735 A1 WO 2019208735A1 JP 2019017796 W JP2019017796 W JP 2019017796W WO 2019208735 A1 WO2019208735 A1 WO 2019208735A1
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- positive electrode
- storage device
- conductive layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- 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
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- 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
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- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to an electrode for an electricity storage device and an electricity storage device.
- micro-hybrid that attracts regenerative energy associated with vehicle braking as electric energy has attracted attention.
- rapid charging and discharging of power storage devices such as electric double layer capacitors and lithium ion capacitors is necessary.
- an electrochemically active polymer such as polyaniline as an active material for such an electricity storage device.
- Patent Document 1 describes a positive electrode for an electricity storage device for an electricity storage device having excellent rapid charge / discharge characteristics.
- This positive electrode contains an active material containing at least one of polyaniline and a polyaniline derivative, a conductive additive, and a binder.
- the ratio of the oxidized form of polyaniline in the active material is 45% by mass or more of the whole polyaniline active material.
- the binder the sum of the polar term and the hydrogen bond term of the Hansen solubility parameter is 20 MPa 1/2 or less.
- a positive electrode is produced by applying a slurry on a current collector layer such as an aluminum foil.
- Patent Document 1 The technique described in Patent Document 1 has room for improvement with respect to characteristics related to rapid charge and discharge of an electricity storage device. Therefore, the present invention provides a positive electrode for an electricity storage device that is advantageous for improving the characteristics related to rapid charge / discharge of the electricity storage device. Moreover, this invention provides the electrical storage device provided with such a positive electrode.
- the present invention An active material layer containing electrochemically active polymer particles having an average particle size of more than 0.5 ⁇ m and not more than 20 ⁇ m and a conductive additive; A current collector, A conductive layer disposed between the active material layer and the current collector and in contact with the active material layer and the current collector, Provided is a positive electrode for an electricity storage device.
- the present invention also provides: An electrolyte layer; A negative electrode disposed in contact with the first main surface of the electrolyte layer; The positive electrode for an electricity storage device, which is disposed in contact with the second main surface of the electrolyte layer, An electricity storage device is provided.
- the above positive electrode for an electricity storage device is advantageous for improving the characteristics relating to rapid charge / discharge of the electricity storage device. Moreover, said electrical storage device can exhibit a favorable characteristic regarding rapid charging / discharging.
- FIG. 1 is a cross-sectional view schematically showing an example of a positive electrode for an electricity storage device according to the present invention.
- FIG. 2 is a cross-sectional view schematically showing an example of the electricity storage device according to the present invention.
- the present inventors have devised an electrode for an electricity storage device according to the present invention based on the following new findings obtained in the process of developing a positive electrode advantageous for improving characteristics related to rapid charge / discharge of an electricity storage device. .
- activated carbon is used as an active material in the positive electrode of an electricity storage device such as a lithium ion capacitor.
- Activated carbon has a very large specific surface area, and charging and discharging are performed by physical adsorption and desorption of ions on the surface of the activated carbon in an electricity storage device including a positive electrode including activated carbon. In such an electricity storage device, reactions for charging and discharging are very fast, and rapid charging / discharging is possible.
- the present inventors obtained a combination of positive electrodes in which an active material layer containing an electrochemically active polymer such as polyaniline as an active material was brought into direct contact with a current collector such as an aluminum foil.
- AC impedance measurement was performed using a symmetric cell.
- the impedance of the positive electrode increases in a high frequency region (for example, a region around 100 kHz). This phenomenon does not occur in a positive electrode including activated carbon as an active material, and is a phenomenon peculiar to a positive electrode including an electrochemically active polymer as an active material. It is difficult to say that the positive electrode having such characteristics is desirable in order to improve characteristics relating to rapid charge / discharge of the electricity storage device.
- the present inventors have studied day and night on the structure of the positive electrode in which the impedance is difficult to increase in the high frequency region.
- a positive electrode in which impedance is difficult to increase in a high frequency region is obtained by interposing a predetermined conductive layer between an active material layer containing electrochemically active polymer particles and a conductive additive and a current collector. It was found that it can be obtained. Moreover, it has been found that an electricity storage device produced using such a positive electrode can exhibit good characteristics with respect to rapid charge / discharge.
- the inventors of the present invention have found that the average particle diameter of the electrochemically active polymer particles in the active material layer is in a predetermined range, so that the active material layer is appropriately formed, and characteristics relating to rapid charge / discharge of the electricity storage device It has been newly found that a positive electrode advantageous for improving the resistance can be produced.
- the positive electrode 1 for an electricity storage device includes an active material layer 10, a current collector 20, and a conductive layer 30.
- the active material layer 10 contains electrochemically active polymer particles 12 and a conductive additive 14.
- the electrochemically active polymer particles 12 have an average particle size greater than 0.5 ⁇ m and not greater than 20 ⁇ m.
- the average particle diameter of the electrochemically active polymer particles 12 is, for example, when 50 or more electrochemically active polymer particles 12 are observed using an electron microscope such as a scanning electron microscope (SEM). It can be determined by measuring the maximum diameter of 50 or more electrochemically active polymer particles 12.
- the average particle diameter of the electrochemically active polymer particles 12 may be determined using a particle image analyzer that captures the shape of the particles using a microscope and analyzes the images by image analysis.
- average particle diameter refers to the median diameter (D50).
- the median diameter is a particle size such that 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 conductive layer 30 is disposed between the active material layer 10 and the current collector 20 and is in contact with the active material layer 10 and the current collector 20.
- the impedance of the positive electrode 1 is unlikely to increase in a high frequency region. This is considered to be advantageous for improving the characteristics related to rapid charge / discharge of the electricity storage device.
- the average particle diameter of the electrochemically active polymer particles 12 is more than 0.5 ⁇ m and not more than 20 ⁇ m, the electrochemically active polymer particles 12 can be appropriately dispersed in the active material layer 10, and rapid charging of the electricity storage device can be achieved. This is advantageous for improving the characteristics relating to the discharge.
- the average particle size of the electrochemically active polymer particles 12 is more than 0.5 ⁇ m and not more than 20 ⁇ m, compared with the case where the electrochemically active polymer particles having a smaller average particle size are used.
- the addition amount of the conductive aid for activating the electrochemically active polymer particles 12 may be small. Thereby, the energy density of an electrical storage device can be raised.
- the average particle diameter of the electrochemically active polymer particles 12 is more than 0.5 ⁇ m and 20 ⁇ m or less, for example, even when the slurry for forming an active material layer is prepared using water as a dispersion medium, The active polymer particles 12 can be appropriately dispersed. For this reason, it is advantageous in improving the characteristics relating to rapid charge / discharge of the electricity storage device.
- the synthesized electrochemically active polymer particles are classified to prepare polymer particles having different average particle diameters, and each polymer particle is dispersed in water to produce a slurry. did.
- the coatability of each slurry was evaluated. As a result, the slurry containing polymer particles having an average particle size of 0.5 ⁇ m could not be applied properly. On the other hand, a slurry containing polymer particles having an average particle size exceeding 0.5 ⁇ m could be properly applied.
- water has a small environmental load, and the average particle size of the electrochemically active polymer particles 12 is more than 0.5 ⁇ m and 20 ⁇ m or less, which is advantageous from the viewpoint of reducing the environmental load.
- the average particle diameter of the electrochemically active polymer particles 12 may be 0.7 ⁇ m or more, 1.0 ⁇ m or more, 3.0 ⁇ m or more, or 6.0 ⁇ m or more. It may be 10 ⁇ m or more.
- the conductive layer 30 has a thickness of 0.1 ⁇ m to 20 ⁇ m, for example. Thereby, the characteristic regarding the quick charge / discharge of an electrical storage device can be improved more reliably, avoiding that the thickness of the positive electrode 1 becomes large.
- the conductive layer 30 desirably has a thickness of 0.1 ⁇ m to 10 ⁇ m, and more desirably has a thickness of 0.1 ⁇ m to 5 ⁇ m.
- the thickness of the conductive layer 30 is measured.
- the average value of the thickness of the conductive layer 30 determined by this measurement is not limited to a specific value.
- the average value of the thickness of the conductive layer 30 determined by this measurement is, for example, 0.5 to 3.0 ⁇ m.
- the average value of the thickness of the conductive layer 30 is an arithmetic average.
- the power storage device manufactured using the positive electrode 1 for power storage devices tends to exhibit high durability. If the average thickness of the conductive layer 30 is in the above range, it is considered that the polymer 12 can be prevented from coming into direct contact with the current collector 20. For this reason, it is considered that the current collector 20 can be prevented from being deteriorated by the contact between the polymer 12 and the current collector 20, and the positive electrode 1 for an electricity storage device is likely to exhibit high durability.
- the dimensional change of the polymer 12 accompanying charging / discharging of an electrical storage device is large.
- the conductive layer 30 is unlikely to be peeled off from the active material layer 10 and the current collector 20 in spite of a large dimensional change of the polymer 12 accompanying charging / discharging of the electricity storage device. it is conceivable that.
- the thickness of the conductive layer 30 can be measured, for example, by observing a cross section of the conductive layer 30 using a scanning electron microscope (SEM). The measurement of the thickness of the conductive layer 30 may be performed before the active material layer 10 is formed in the manufacture of the positive electrode 1 or may be performed after the active material layer 10 is formed.
- the average value of the thickness of the conductive layer 30 may be 0.5 ⁇ m or more, or 1.0 ⁇ m or more. As a result, the power storage device can easily exhibit high durability more reliably.
- the average value of the thickness of the conductive layer 30 may be 3.0 ⁇ m or less, or may be 1.5 ⁇ m or less. Thereby, it can suppress that the thickness of the positive electrode 1 becomes large.
- the minimum value of the thickness of the conductive layer 30 measured at the above 10 positions is, for example, 0.1 ⁇ m or more. Thereby, it can suppress more reliably that the polymer 12 contacts the collector 20 directly, and an electrical storage device tends to exhibit high durability.
- the minimum value of the thickness of the conductive layer 30 measured at the above 10 positions may be 0.2 ⁇ m or more, 0.3 ⁇ m or more, or 0.5 ⁇ m or more. As a result, the power storage device can easily exhibit high durability more reliably.
- 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 sessile drop method in Japanese Industrial Standard JIS R 3257: 1999 before the active material layer 10 is formed.
- 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, exposing the conductive layer 30 by removing at least part of the active material layer 10 by a method such as polishing or cutting after the active material layer 10 is formed. Measurement may be performed on the surface of the conductive layer 30. In addition, at least a part of the current collector 20 may be removed by polishing or cutting to expose the conductive layer 30, and measurement may be performed on the exposed surface of the 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 improving the adhesion between the conductive layer 30 and the active material layer 10.
- the contact angle of the water droplet is desirably 90 ° or less, more desirably 80 ° or less, and further desirably 70 ° or less.
- the contact angle of this 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 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 SAICAS measurement mode is a constant speed mode. The cutting speed is 10 ⁇ m / second.
- FH is the horizontal cutting stress [N] when a SAICAS diamond cutting blade (Daipla, rake angle: 10 °) is moved horizontally at the interface between the active material layer 10 and the conductive layer 30.
- W is the blade width [m] of the SAICAS cutting blade.
- SAICAS is a registered trademark of Daipla Corporation.
- P FH / W (1)
- the peel strength P is desirably 0.15 kN / m or more, more desirably 0.17 kN / m or more, and further desirably 0.23 kN / m or more.
- the conductive layer 30 contains, for example, conductive particles 32 and a binder 35.
- the conductive particles 32 are made of a carbon material. This carbon material is, for example, graphite.
- the binder 35 is in contact with the outer surface of the conductive particles 32.
- the conductive particles 32 are bound by the binder 35. A part of the outer surface of the conductive particle 32 is in contact with the active material layer 10, and another part of the outer surface of the conductive particle 32 is in contact with the current collector 20.
- Electrochemically active polymer particles show a large dimensional change with charge / discharge of the electricity storage device compared to activated carbon. For this reason, when the active material layer containing the electrochemically active polymer particles as an active material and the current collector are in direct contact, the electrochemically active polymer particles accompanying charge / discharge of the electricity storage device It is considered that a large dimensional change affects the active material layer, the current collector, and the interface. This may adversely affect the characteristics related to rapid charge / discharge of the electricity storage device. On the other hand, since the conductive layer 30 contains the conductive particles 32 and the binder 35, it is considered that the influence of the large dimensional change of the electrochemically active polymer particles accompanying charging / discharging of the electricity storage device can be easily mitigated. For this reason, it is thought that the positive electrode 1 tends to improve the characteristic regarding the rapid charge / discharge of an electrical storage device.
- the binder 35 is not particularly limited as long as it can contact the outer surface of the conductive particles 32 and bind the conductive particles 32.
- the binder 35 is a polymer such as carboxymethyl cellulose, for example.
- the binder 35 includes at least one selected from the group consisting of, for example, methyl cellulose, hydroxyethyl cellulose, polyethylene oxide, carboxymethyl cellulose, derivatives thereof, salts thereof, polyolefin, natural rubber, synthetic rubber, and thermoplastic elastomer.
- the adhesion between the conductive layer 30 and the active material layer 10 or the current collector 20 is likely to increase.
- 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 includes, for example, 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 is more likely to increase more reliably.
- the binder 35 desirably contains at least one of carboxymethyl cellulose and a styrene-butadiene copolymer.
- the adhesion between the conductive layer 30 and the active material layer 10 tends to increase.
- the binder 15 of the active material layer 10 described later includes a predetermined component, the adhesion between the conductive layer 30 and the active material layer 10 is likely to increase.
- the content of the binder 35 in the conductive layer 30 is not limited to a specific value.
- the content of the binder 35 in the conductive layer 30 is, for example, 3% or more on a mass basis.
- the electrical storage device manufactured using the positive electrode 1 for electrical storage devices tends to exhibit high durability. If the content of the binder 35 in the conductive layer 30 is in the above range, it is considered that the polymer 12 can be prevented from directly contacting the current collector 20. For this reason, it is considered that the current collector 20 can be prevented from being deteriorated by the contact between the polymer 12 and the current collector 20, and the positive electrode 1 for an electricity storage device is likely to exhibit high durability.
- the dimensional change of the polymer 12 accompanying charging / discharging of the electricity storage device is large.
- the content of the binder 35 in the conductive layer 30 is in the above range, the conductive layer 30 peels from the active material layer 10 and the current collector 20 in spite of a large dimensional change of the polymer 12 due to charging / discharging of the electricity storage device. It is considered difficult.
- the content of the binder 35 in the conductive layer 30 may be 4% or more on a mass basis. As a result, the power storage device can easily exhibit high durability more reliably.
- the content of the binder 35 in the conductive layer 30 is, for example, 10% or less on a mass basis. Thereby, the density of the conductive particles 32 in the conductive layer 30 increases, and the internal resistance of the positive electrode 1 tends to decrease.
- the content of the binder 35 in the conductive layer 30 may be 10% or less or 6% or less on a mass basis.
- the content of the electrochemically active polymer particles 12 in the active material layer 10 is, for example, 1% or more, desirably 5% or more, more desirably 20% or more, and even more desirably, on a mass basis. It is 40% or more, and particularly preferably 60% or more. Thereby, the energy density in an electrical storage device tends to increase.
- the electrochemically active polymer particles 12 include, for example, at least one of polyaniline and polyaniline derivatives. In this case, it is possible to improve characteristics relating to rapid charge / discharge of the electricity storage device more reliably. In addition, the energy density of the electricity storage device tends to increase. Polyaniline and polyaniline derivatives are sometimes collectively referred to as “polyaniline compounds”.
- Polyaniline is typically obtained by electrolytic polymerization or chemical oxidation polymerization of aniline.
- Polyaniline derivatives are typically obtained by electropolymerization 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 the aniline. Have.
- Aniline derivatives include, for example, (i) o-substituted anilines such as o-methylaniline, o-ethylaniline, o-phenylaniline, o-methoxyaniline, and o-ethoxyaniline, or (ii) m-methylaniline.
- M-substituted anilines such as m-ethylaniline, m-methoxyaniline, m-ethoxyaniline, m-phenylaniline and the like.
- aniline derivative only one kind of aniline derivative may be used, or two or more kinds of aniline derivatives may be used in combination.
- the polyaniline compound may be doped with a dopant such as protonic acid.
- the polyaniline and the polyaniline derivative contained in the electrochemically active polymer particles 12 are desirably dedope when the positive electrode 1 is manufactured.
- the polyaniline and the polyaniline derivative contained in the electrochemically active polymer particles 12 are in a state in which a dopant such as protonic acid is dedopeed.
- the electrochemically active polymer particles 12 can be appropriately dispersed in the active material layer 10, and the energy density of the electricity storage device can be easily increased.
- the electrochemically active polymer particles 12 including dedopeed polyaniline and the like are well dispersed in the slurry even if the dispersion medium of the slurry for forming the active material layer 10 is water. It is. On the other hand, it may be difficult to satisfactorily disperse the doped polyaniline particles using water as a dispersion medium.
- the positive electrode 1 is undoped during assembly of the electricity storage device.
- the electrochemically active polymer 12 in the positive electrode 1 is in a doped state. It is conceivable to assemble an electricity storage device by combining a positive electrode chemically doped in advance and an uncharged negative electrode. In this case, only the electrochemically active polymer which is not chemically doped in the positive electrode contributes to the charging in the initial charging of the electricity storage device. For this reason, the initial charge capacity of the electricity storage device is significantly reduced, which is not preferable for the electricity storage device.
- an electricity storage device by combining a positive electrode chemically doped in advance and a negative electrode such as a lithium pre-doped negative electrode.
- a positive electrode chemically doped in advance discharge immediately after the assembly of the electricity storage device is possible, but the chemically doped dopant is less likely to be electrochemically doped and dedoped, resulting in a decrease in the capacity of the electricity storage device. For this reason, it is difficult to obtain a desired power storage device.
- an electrochemically active polymer in a state of being dedoped at the time of manufacturing the positive electrode or at the time of assembling the power storage device is electrochemically doped from the time when charging is started after the assembly of the power storage device. Then, it can be used as an electrical storage device by repeating doping and dedoping of an electrochemically active polymer.
- the polyaniline and polyaniline derivative contained in the electrochemically active polymer particle 12 include, for example, 35 to 60% of an oxidant based on mass. In this case, the preservability of the electrochemically active polymer particles 12 is good, and the electrochemically active polymer particles 12 can exhibit desirable characteristics as the positive electrode active material.
- the chemical structure of the oxidized form Ox and the reduced form Red of polyaniline is shown in the following formula (a). In the formula (a), each of x and y is an integer of 0 or more.
- the addition amount of a reducing agent such as phenylhydrazine is stoichiometrically adjusted with respect to polyaniline so that the content of the oxidant in the polyaniline compound falls within a predetermined range (35 to 60% on a mass basis).
- a reducing agent such as phenylhydrazine
- the An example of the reduction reaction of polyaniline using phenylhydrazine is shown in the following formula (b).
- the content of the oxidant in the polyaniline compound forming the electrochemically active polymer particle 12 can be determined from, for example, a solid state 13 CNMR spectrum.
- the content of the oxidant in the polyaniline-based compound that forms the electrochemically active polymer particle 12 is determined by the absorbance A640 at the absorption maximum near 640 nm and the absorbance A340 at the absorption maximum near 340 nm in the electronic spectrum of the spectrophotometer. It is also possible to obtain from the oxidation degree index represented by the ratio A640 / A340.
- the content of oxidant (ratio of oxidant) in the polyaniline compound forming the electrochemically active polymer particles 12 can be determined, for example, according to the method described in paragraphs 0040 to 0051 of JP-A-2018-26341. .
- the conductive auxiliary agent 14 included in the active material layer 10 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.
- the conductive auxiliary agent 14 can be a conductive carbon material or a metal 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 desirably conductive carbon black.
- the content of the conductive additive 14 in the active material layer 10 is, for example, 1 to 30%, desirably 4 to 25%, and more desirably 4 to 19% on a mass basis.
- the electrochemically active polymer particles 12 can be activated more reliably while suppressing the content of the conductive additive. As a result, it is easy to increase the energy density of the electricity storage device.
- the active material layer 10 further contains, for example, a binder 15.
- the binder 15 includes, for example, an elastomer.
- the elastomer can be natural rubber, synthetic rubber, or thermoplastic elastomer.
- the binder 15 typically contacts the outer surface of the electrochemically active polymer particles 12 and the outer surface of the conductive aid 14.
- the binder 15 binds the electrochemically active polymer particles 12 and the conductive aid 14.
- the binder 15 binds the electrochemically active polymer particles 12 and the conductive aid 14.
- the active material layer 10 has, for example, holes 16.
- the holes 16 are formed so as to continue from one main surface of the active material layer 10 to the other main surface.
- the electrolyte 16 is impregnated with the electrolyte 16.
- the binder 15 contains an elastomer, the binder 15 is easily deformed without generating a large stress in accordance with a dimensional change of the electrochemically active polymer particles accompanying charging / discharging of the electricity storage device. Thereby, it is thought that the characteristic regarding the rapid charge / discharge of an electrical storage device is easy to improve.
- the binder 15 includes, 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 affinity between the binder 15 and the polymer particles 12 is good, and the conductive additive 14 is likely to come into contact with the polymer particles 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).
- Hansen Solubility Parameters in Practice HSPiP
- HSPiP Hansen Solubility Parameters in Practice
- the sum of the polar term and the hydrogen bond term in the Hansen solubility parameter of the composite binder is determined by summing up the product of the Hansen solubility parameter of each component constituting the binder and the mass-based component ratio of each component. it can.
- the total of the polar term and the hydrogen bond term in the Hansen solubility parameter of the binder 15 is desirably 19 MPa 1/2 or less, more desirably 12 MPa 1/2 or less, and further desirably 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 a 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%, desirably 4 to 25%, and more desirably 4 to 18% on a mass basis.
- the electrochemically active polymer particles 12 can be appropriately dispersed in the active material layer 10 while suppressing the content of the binder 15.
- the active material layer 10 may contain an active material other than the electrochemically active polymer particles 12 as necessary.
- the active material other than the electrochemically active polymer particles 12 is, for example, a carbon material such as activated carbon.
- the activated carbon can be alkali activated carbon, water vapor activated activated carbon, gas activated activated carbon, or zinc chloride activated activated carbon.
- the active material layer 10 may further contain additives such as a thickener as necessary.
- the thickener is, for example, methyl cellulose, hydroxyethyl cellulose, polyethylene oxide, carboxymethyl cellulose, derivatives thereof, or salts thereof. Of these, carboxymethylcellulose, its derivatives, or salts thereof are desirably used as thickeners.
- the content of the thickener in the active material layer 10 is, for example, 1 to 20%, desirably 1 to 10%, more desirably 1 to 8% on a mass basis.
- the current collector 20 is, for example, 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 by, for example, coating, sputtering, vapor deposition, ion plating, or CVD using a predetermined raw material.
- the conductive layer 30 is formed by coating the main surface of the current collector 20 with a slurry prepared by dispersing the conductive particles 32 and the binder 35 in a dispersion medium, and drying the coating film. Can be formed.
- a slurry prepared by dispersing the electrochemically active polymer particles 12, the conductive auxiliary agent 14, and the binder 15 in a dispersion medium is applied to the surface of the conductive layer 30 to form a coating film.
- the active material layer 10 can be formed by drying. In this way, the positive electrode 1 can be produced. Note that additives such as an active material other than the electrochemically active polymer particles 12 and a thickener are added to the slurry for forming the active material layer 10 as necessary.
- the electricity storage device 5 can be manufactured using the positive electrode 1.
- the electricity storage device 5 includes an electrolyte layer 3, a negative electrode 2, and a positive electrode 1.
- the negative electrode 2 is disposed in contact with the first main surface of the electrolyte layer 3.
- the positive electrode 1 is disposed 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 disposed between the positive electrode 1 and the negative electrode 2. Since the electricity storage device 5 includes the positive electrode 1, it can exhibit good characteristics with respect to rapid charge / discharge.
- the electrolyte layer 3 is composed of an electrolyte.
- the electrolyte layer 3 is a sheet made of a solid electrolyte or a sheet in which a separator is impregnated with an electrolytic solution, for example.
- the electrolyte layer 3 is a sheet made of a solid electrolyte, the electrolyte layer 3 itself may also serve as a separator.
- the electrolyte includes a solute, and optionally a solvent and various additives.
- a solute for example, a metal ion such as lithium ion and a predetermined counter ion for the metal ion are combined.
- the counter ion is, for example, a sulfonate ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, a hexafluoroarsenic ion, a bis (trifluoromethanesulfonyl) imide ion, a bis (pentafluoroethanesulfonyl) imide ion, or Halogen ion.
- electrolyte examples 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 a nonaqueous 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.
- the solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, acetonitrile, propyronitrile, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, dimethoxyethane, Diethoxyethane and ⁇ -butyrolactone.
- the solvent in the electrolyte one type of solvent may be used alone, or two or more types of solvents may be used in combination.
- dissolved the solute in said solvent may be called "electrolytic solution.”
- the electrolyte may contain an additive as necessary.
- the additive is, 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 includes a negative electrode active material.
- the negative electrode active material is a material capable of inserting and removing metals or ions.
- metallic lithium, a carbon material capable of inserting and removing lithium ions by an oxidation-reduction reaction, a transition metal oxide, silicon, and tin are desirably used.
- the active material layer 60 is in contact with the first main surface of the electrolyte layer 3.
- Examples of the carbon material capable of inserting and removing lithium ions include (i) activated carbon, (ii) coke, (iii) pitch, (iv) a fired body of phenol resin, polyimide, and 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 used as a main component of the negative electrode.
- a main component means the component contained most by mass reference
- 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 a lithium material is doped in advance in a carbon material such as graphite, hard carbon, or soft carbon.
- a separator is typically disposed 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 desirably a porous film made of a resin such as (i) paper, (ii) non-woven fabric, (iii) polypropylene, polyethylene, and polyimide.
- a separator is disposed between the positive electrode 1 and the negative electrode 2 to obtain a laminate.
- This laminate is placed in a package made of an aluminum laminate film and vacuum dried.
- an electrolytic solution is injected into the vacuum-dried package and the package is sealed, so that the power storage device 5 can be manufactured.
- the manufacturing process of the electricity storage device 5 such as injection of the electrolytic solution into the package is desirably performed in an inert gas atmosphere such as ultra-high purity argon gas using a glove box.
- the electricity storage device 5 may be formed into a shape such as a film shape, a sheet shape, a square shape, a cylindrical shape, and a button shape using a package other than a package made of an aluminum laminate film.
- Example 1 In a glass beaker containing 138 g of ion-exchanged water, 84.0 g of tetrafluoroboric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade) with a concentration of 42% by mass (substance amount of tetrafluoroboric acid: 0.402 mol) was added. In addition, 10.0 g (0.107 mol) of aniline was further added while stirring with a magnetic stirrer. Immediately after the aniline was added to the tetrafluoroboric acid aqueous solution, the aniline was dispersed as oily droplets in the tetrafluoroboric acid aqueous solution.
- the mixture containing the reaction product was further stirred for 100 minutes while cooling. Then, using a Buchner funnel and a suction bottle, the obtained solid was No. It filtered under reduced pressure with 2 filter papers (made by Toyo Filter Paper Co., Ltd.) to obtain a powder.
- the powder was stirred and washed in an aqueous solution of about 2 mol / L tetrafluoroboric acid using a magnetic stirrer. Next, this powder was stirred and washed several times with acetone and filtered under reduced pressure. The obtained powder was vacuum-dried at room temperature (25 ° C.) for 10 hours to obtain 12.5 g of conductive polyaniline having tetrafluoroboric acid as a dopant.
- the conductive polyaniline was a bright green powder.
- the conductive polyaniline powder in the above doped state was placed in a 2 mol / L sodium hydroxide aqueous solution and 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 Buchner 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 polyaniline powder according to Example 1 in a brown oxidative dedope state.
- the average particle diameter (D50) of the polyaniline powder according to Example 1 was 3 ⁇ m.
- the average particle size of the polyaniline powder was calculated using Morphologi G3 manufactured by Malvern.
- the oxidation degree index of this polyaniline powder was determined to be 0.86. Moreover, the ratio of the polyaniline oxidized form in the whole polyaniline calculated
- the copolymerization ratio of styrene: butadiene [1,4 body]: butadiene [1,2 body] was 61: 31: 8.
- the solid concentration in the slurry for forming an active material layer was 30% by mass.
- a conductive layer forming slurry according to Example 1 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.
- bar coater No. 3 the slurry for forming the conductive layer was applied to one main surface of the 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 according to Example 1.
- the thickness of the conductive layer according to Example 1 was 1 ⁇ m.
- the coating thickness is adjusted to 185 ⁇ m with a doctor blade type applicator with a micrometer, and the coating speed is 10 mm / second on the conductive layer.
- An active material layer forming slurry was applied to form a coating film.
- this coating film was allowed to stand at room temperature (25 ° C.) for 45 minutes, and then dried on a hot plate having a temperature of 100 ° C. to form an active material layer. In this way, a positive electrode according to Example 1 was produced.
- the thickness of the active material layer was 73 ⁇ m.
- this laminate cell is taken out from the glove box, and is equivalent to 0.2 C with respect to the capacity of the graphite negative electrode sheet in a potential range of 2.0 V to 0.01 V in a thermostat kept at 25 ° C. 3 cycles of charge and discharge were performed at the current value, and finally, a reaction for inserting lithium ions into the graphite was performed up to a capacity of 75% with respect to the capacity of the graphite negative electrode sheet. In this way, a laminate cell including a negative electrode sheet pre-doped with lithium was produced.
- the laminate cell including the negative electrode sheet pre-doped with lithium was put into the glove box again.
- the sealing part of the laminate cell was cut out, and the negative electrode sheet pre-doped with lithium was taken out.
- these were stacked so that the separator was positioned between the positive electrode according to Example 1 and the negative electrode sheet pre-doped with lithium.
- a non-woven fabric product name: TF40-50, manufactured by Nippon Kogyo Paper Industries Co., Ltd.
- a current collector tab was attached to the positive electrode.
- the laminate of the positive electrode, the separator, and the negative electrode sheet was put into a bag-shaped package made of an aluminum laminate film.
- Example 2 A positive electrode according to Example 2 was produced in the same manner as in Example 1 except that the coating conditions of the slurry for forming the conductive layer on the aluminum foil were changed so that the thickness of the conductive layer was 3 ⁇ m.
- a lithium ion capacitor according to Example 2 was produced in the same manner as in Example 1 except that the positive electrode according to Example 2 was used instead of the positive electrode according to Example 1.
- Example 3 A positive electrode according to Example 3 was produced in the same manner as in Example 1 except that the application conditions of the slurry for forming the conductive layer on the aluminum foil were changed so that the thickness of the conductive layer was 18 ⁇ m.
- a lithium ion capacitor according to Example 3 was produced in the same manner as in Example 1 except that the positive electrode according to Example 3 was used instead of the positive electrode according to Example 1.
- a conductive layer forming slurry according to Example 4 was prepared by mixing and stirring 18 parts by mass of carbon black as conductive particles, 2 parts by mass of carboxymethyl cellulose (CMC) as a binder, and 80 parts by mass of pure water.
- a positive electrode according to Example 4 was produced in the same manner as in Example 1, except that the slurry for forming a conductive layer according to Example 4 was used instead of the slurry for forming a conductive layer according to Example 1.
- the application conditions of the conductive layer forming slurry on the aluminum foil were adjusted so that the thickness of the conductive layer in the positive electrode according to Example 4 was 1 ⁇ m.
- a lithium ion capacitor according to Example 4 was produced in the same manner as in Example 1 except that the positive electrode according to Example 4 was used instead of the positive electrode according to Example 1.
- Example 5 A positive electrode according to Example 5 was produced in the same manner as in Example 4 except that the coating condition of the slurry for forming the conductive layer on the aluminum foil was changed so that the thickness of the conductive layer was 3 ⁇ m.
- a lithium ion capacitor according to Example 5 was produced in the same manner as in Example 1 except that the positive electrode according to Example 5 was used instead of the positive electrode according to Example 1.
- Example 6 A positive electrode according to Example 6 was produced in the same manner as in Example 4 except that the coating condition of the slurry for forming the conductive layer on the aluminum foil was changed so that the thickness of the conductive layer was 18 ⁇ m.
- a lithium ion capacitor according to Example 6 was produced in the same manner as in Example 1 except that the positive electrode according to Example 6 was used instead of the positive electrode according to Example 1.
- Example 7 20 parts by mass of carbon black as conductive particles, 2 parts by mass of styrene-butadiene copolymer (SBR) as a binder, and 78 parts by mass of pure water are mixed and agitated to form a slurry for forming a conductive layer according to Example 7.
- SBR styrene-butadiene copolymer
- the copolymerization ratio of styrene: butadiene was 42:58.
- a positive electrode according to Example 7 was produced in the same manner as in Example 1 except that the slurry for forming a conductive layer according to Example 7 was used instead of the slurry for forming a conductive layer according to Example 1.
- Example 7 The application conditions of the slurry for forming the conductive layer on the aluminum foil were adjusted so that the thickness of the conductive layer in the positive electrode according to Example 7 was 1 ⁇ m.
- a lithium ion capacitor according to Example 7 was produced in the same manner as in Example 1 except that the positive electrode according to Example 7 was used instead of the positive electrode according to Example 1.
- ⁇ Comparative Example 1> Using a tabletop automatic coating device (manufactured by Tester Sangyo Co., Ltd.), the coating thickness is adjusted to 190 ⁇ m using a doctor blade type applicator with a micrometer, and the coating speed is 10 mm / sec. The material layer forming slurry was applied to form a coating film. Next, this coating film was allowed to stand at room temperature (25 ° C.) for 45 minutes, and then dried on a hot plate having a temperature of 100 ° C. to form an active material layer. In this way, a positive electrode according to Comparative Example 1 was produced. The thickness of the active material layer was 71 ⁇ m.
- a lithium ion capacitor according to Comparative Example 1 was produced in the same manner as in Example 1 except that the positive electrode according to Comparative Example 1 was used instead of the positive electrode according to Example 1.
- the lithium ion capacitor according to the example and the comparative example is taken out from the glove box, and is charged for 10 cycles at a current value corresponding to 1 C in a temperature range of 3.8 V to 2.2 V in a thermostat kept at 25 ° C.
- the discharge was performed, and the discharge capacity [mAh / g] at the 10th cycle was defined as the initial capacity Ai [mAh / g] of the lithium ion capacitors according to the example and the comparative example.
- the results are shown in Table 1.
- the initial capacity density did not change greatly, but the lithium ion capacitors according to the examples had higher output than the lithium ion capacitors according to the comparative examples.
- the maintenance rate was shown. This has shown that the lithium ion capacitor which concerns on an Example has a favorable characteristic regarding rapid charging / discharging.
- Example 8> In the same manner as in Example 1, a polyaniline powder in an oxidatively dedoped state according to Example 8 was obtained. Using Morphologi G3 manufactured by Malvern, the average particle size (D50), the 10% particle size (D10), and the 90% particle size (D90) of the polyaniline powder according to Example 8 are calculated. did. The results are shown in Table 2.
- a lithium ion capacitor according to Example 8 was produced in the same manner as in Example 1 except that the positive electrode according to Example 8 was used instead of the positive electrode according to Example 1.
- Example 9-11 A predetermined classification operation was performed on the polyaniline powder according to Example 8, and the polyaniline powder according to Example 9, the polyaniline powder according to Example 10, and the polyaniline powder according to Example 11 were obtained. Using Morphologi G3 manufactured by Malvern, the average particle size (D50) of the polyaniline powder according to Example 9-11, 10% particle size (D10) in the number-based particle size distribution, and 90% particle size (D90) was calculated. The results are shown in Table 2.
- Example 9 was the same as Example 1 except that the polyaniline powder according to Example 9-11 was used instead of the polyaniline powder according to Example 1 and the thickness of the conductive layer was adjusted to 0.87 ⁇ m.
- a positive electrode according to -11 was produced.
- a lithium ion capacitor according to Example 9-11 was produced in the same manner as in Example 1 except that the positive electrode according to Example 9-11 was used instead of the positive electrode according to Example 1.
- the lithium ion capacitor according to Example 8-11 was taken out of the glove box, and charged and discharged at a current value corresponding to 200 C in a voltage range of 3.8 V to 2.2 V inside a thermostat kept at 25 ° C.
- the discharge capacity A [mAh / g] was specified.
- the voltage V1 of the lithium ion capacitor immediately before the start of discharge and the voltage V2 immediately after the start of discharge were confirmed.
- Table 2 The results are shown in Table 2.
- the lithium ion capacitor according to Example 8-11 exhibited good high output performance and low temperature characteristics. Moreover, it was suggested that it is advantageous that the average particle diameter (D50) of the polyaniline powder is small from the viewpoint of high output performance and low temperature characteristics.
- Example 12 A slurry for forming a conductive layer according to Example 12 was obtained by mixing and stirring 18 parts by mass of carbon black as conductive particles, 4 parts by mass of a styrene-butadiene copolymer (SBR) as a binder, and 78 parts by mass of pure water.
- SBR styrene-butadiene copolymer
- the copolymerization ratio of styrene: butadiene was 42:58.
- the binder content in the solid content of the conductive layer forming slurry was 4% on a mass basis.
- An aluminum foil having a thickness of 20 ⁇ m was prepared as a current collector.
- the slurry for forming the conductive layer was applied to one main surface of the 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 according to Example 12, and a current collector with a conductive layer according to Example 12 was obtained.
- the coating thickness is adjusted to 185 ⁇ m with a doctor blade type applicator with a micrometer, and the active material layer is formed on the conductive layer at a coating speed of 10 mm / second.
- the forming slurry was applied to form a coating film.
- this coating film was allowed to stand at room temperature (25 ° C.) for 45 minutes, and then dried on a hot plate having a temperature of 100 ° C. to form an active material layer. In this way, a positive electrode according to Example 12 was produced.
- the thickness of the active material layer was 73 ⁇ m.
- a lithium ion capacitor according to Example 12 was produced in the same manner as in Example 1 except that the positive electrode according to Example 12 was used instead of the positive electrode according to Example 1.
- Example 13 Conductive layer formation according to Example 13 as in Example 12, except that the content of each component was changed so that the content of the binder in the solid content of the slurry for forming the conductive layer was 6% on a mass basis.
- a slurry was prepared.
- a positive electrode according to Example 13 was obtained in the same manner as Example 12 except that the slurry for forming a conductive layer according to Example 13 was used instead of the slurry for forming a conductive layer according to Example 12.
- a lithium ion capacitor according to Example 13 was obtained in the same manner as in Example 1 except that the positive electrode according to Example 13 was used instead of the positive electrode according to Example 1.
- Example 14 Conductive layer formation according to Example 14 in the same manner as in Example 12, except that the content of each component was changed so that the content of the binder in the solid content of the slurry for forming the conductive layer was 10% on a mass basis.
- a slurry was prepared.
- a positive electrode according to Example 14 was obtained in the same manner as in Example 1 except that the slurry for forming a conductive layer according to Example 14 was used instead of the slurry for forming a conductive layer according to Example 1.
- a lithium ion capacitor according to Example 14 was obtained in the same manner as Example 1, except that the positive electrode according to Example 14 was used instead of the positive electrode according to Example 1.
- Example 15 Conductive layer formation according to Example 15 except that the content of each component was changed so that the content of the binder in the solid content of the slurry for forming the conductive layer was 2% by mass. A slurry was prepared. A positive electrode according to Example 15 was obtained in the same manner as in Example 12, except that the slurry for forming a conductive layer according to Example 15 was used instead of the slurry for forming a conductive layer according to Example 12. A lithium ion capacitor according to Example 15 was obtained in the same manner as Example 1 except that the positive electrode according to Example 15 was used instead of the positive electrode according to Example 1.
- the durability of the lithium ion capacitors according to Examples 12 to 14 was superior to that of the lithium ion capacitor according to Example 15.
- the binder content in the positive electrode conductive layer according to Examples 12 to 14 was higher than the binder content in the positive electrode conductive layer according to Example 15. Accordingly, it is considered that the durability of the lithium ion capacitors according to Examples 12 to 14 was superior to that of the lithium ion capacitor according to Example 15.
- a conductive layer forming slurry was prepared by mixing and stirring 18 parts by mass of carbon black as conductive particles, 4 parts by mass of styrene-butadiene copolymer (SBR) as a binder, and 78 parts by mass of pure water.
- SBR styrene-butadiene copolymer
- the copolymerization ratio of styrene: butadiene was 42:58.
- An aluminum foil having a thickness of 20 ⁇ m was prepared as a current collector.
- the slurry for forming the conductive layer was applied to one main surface of the 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 according to Example 16, and a current collector with a conductive layer according to Example 16 was obtained.
- the coating thickness is adjusted to 185 ⁇ m with a doctor blade type applicator with a micrometer, and the active material layer is formed on the conductive layer at a coating speed of 10 mm / second.
- the forming slurry was applied to form a coating film.
- this coating film was allowed to stand at room temperature (25 ° C.) for 45 minutes, and then dried on a hot plate having a temperature of 100 ° C. to form an active material layer. In this manner, a positive electrode according to Example 16 was produced.
- the thickness of the active material layer was 73 ⁇ m.
- a lithium ion capacitor according to Example 16 was produced in the same manner as Example 1 except that the positive electrode according to Example 16 was used instead of the positive electrode according to Example 1.
- Example 17 A current collector with a conductive layer according to Example 17 was produced in the same manner as in Example 16 except that the application conditions of the slurry for forming the conductive layer on the aluminum foil were changed so that the average value of the thickness of the conductive layer was larger. did.
- a positive electrode according to Example 17 was produced in the same manner as in Example 16 except that the current collector with conductive layer according to Example 17 was used instead of the current collector with conductive layer according to Example 16.
- a lithium ion capacitor according to Example 17 was produced in the same manner as in Example 1 except that the positive electrode according to Example 17 was used instead of the positive electrode according to Example 1.
- Example 18 A current collector with a conductive layer according to Example 18 was produced in the same manner as in Example 16 except that the coating conditions of the slurry for forming the conductive layer on the aluminum foil were changed so that the thickness of the conductive layer was smaller.
- a positive electrode according to Example 18 was produced in the same manner as in Example 16 except that the current collector with conductive layer according to Example 18 was used instead of the current collector with conductive layer according to Example 16.
- a lithium ion capacitor according to Example 18 was produced in the same manner as in Example 1 except that the positive electrode according to Example 18 was used instead of the positive electrode according to Example 1.
- the lithium ion capacitors according to Examples 16 to 18 were taken out of the glove box, and charged and discharged at a current value corresponding to 200 C in a temperature range of 3.8 V to 2.2 V inside a thermostat kept at 25 ° C.
- the discharge capacity A [mAh / g] was specified.
- the voltage V1 of the lithium ion capacitor immediately before the start of discharge and the voltage V2 immediately after the start of discharge were confirmed.
- Table 4 The results are shown in Table 4.
- the lithium ion capacitors according to Examples 16 to 18 were subjected to a float test for 500 hours in a constant temperature bath maintained at 60 ° C. and maintaining a fully charged state (SOC: 100%) at an upper limit voltage of 3.8 V. The time change of the discharge capacity and the time change of the series resistance were measured.
- the high output performance and durability of the lithium ion capacitors according to Examples 16 and 17 were superior to the lithium ion capacitor according to Example 18.
- the average value of the thickness of the conductive layer in Examples 16 and 17 was larger than the average value of the thickness of the conductive layer in Example 18. Thereby, it is considered that the high output performance and durability of the lithium ion capacitor according to Examples 16 and 17 were superior to the lithium ion capacitor according to Example 18.
Abstract
Description
0.5μmを超え20μm以下の平均粒径を有する電気化学的に活性なポリマー粒子と導電助剤とを含有している活物質層と、
集電体と、
前記活物質層と前記集電体との間に配置され、前記活物質層及び前記集電体に接触している導電層と、を備えた、
蓄電デバイス用正極を提供する。
電解質層と、
前記電解質層の第一主面に接触して配置された負極と、
前記電解質層の第二主面に接触して配置された、上記の蓄電デバイス用正極と、を備えた、
蓄電デバイスを提供する。
P=FH/W (1)
イオン交換水138gを入れたガラス製ビーカーに、42質量%濃度のテトラフルオロホウ酸水溶液(和光純薬工業社製、試薬特級)84.0g(テトラフルオロホウ酸の物質量:0.402mol)を加え、磁気スターラーにて撹拌しながら、アニリン10.0g(0.107mol)をさらに加えた。テトラフルオロホウ酸水溶液にアニリンを加えた直後において、アニリンは、テトラフルオロホウ酸水溶液に油状の液滴として分散していた。その後、数分以内にアニリンは水に溶解し、均一で透明な水溶液が得られた。このようにして得られた水溶液を、恒温槽を用いて-4℃以下に冷却した。次に、酸化剤として二酸化マンガン粉末(和光純薬工業社製、試薬1級)11.63g(0.134mol)を、ビーカー内の混合物の温度が-1℃を超えないように、上記の水溶液中に少量ずつ加えた。水溶液に酸化剤を加えることによって、水溶液は直ちに黒緑色に変化した。その後、しばらく撹拌を続けると、黒緑色の固体が生成し始めた。
導電層の厚みが3μmとなるようにアルミニウム箔に対する導電層形成用スラリーの塗布条件を変更した以外は実施例1と同様にして、実施例2に係る正極を作製した。実施例1に係る正極の代わりに実施例2に係る正極を用いた以外は実施例1と同様にして、実施例2に係るリチウムイオンキャパシタを作製した。
導電層の厚みが18μmとなるようにアルミニウム箔に対する導電層形成用スラリーの塗布条件を変更した以外は実施例1と同様にして、実施例3に係る正極を作製した。実施例1に係る正極の代わりに実施例3に係る正極を用いた以外は実施例1と同様にして、実施例3に係るリチウムイオンキャパシタを作製した。
導電性粒子としてカーボンブラック18質量部と、バインダーとしてのカルボキシメチルセルロース(CMC)2質量部と、純水80質量部とを混合撹拌して、実施例4に係る導電層形成用スラリーを調製した。実施例1に係る導電層形成用スラリーの代わりに実施例4に係る導電層形成用スラリー用いた以外は、実施例1と同様にして実施例4に係る正極を作製した。実施例4に係る正極における導電層の厚みが1μmになるようにアルミニウム箔に対する導電層形成用スラリーの塗布条件を調整した。実施例1に係る正極の代わりに実施例4に係る正極を用いた以外は実施例1と同様にして、実施例4に係るリチウムイオンキャパシタを作製した。
導電層の厚みが3μmとなるようにアルミニウム箔に対する導電層形成用スラリーの塗布条件を変更した以外は実施例4と同様にして、実施例5に係る正極を作製した。実施例1に係る正極の代わりに実施例5に係る正極を用いた以外は実施例1と同様にして、実施例5に係るリチウムイオンキャパシタを作製した。
導電層の厚みが18μmとなるようにアルミニウム箔に対する導電層形成用スラリーの塗布条件を変更した以外は実施例4と同様にして、実施例6に係る正極を作製した。実施例1に係る正極の代わりに実施例6に係る正極を用いた以外は実施例1と同様にして、実施例6に係るリチウムイオンキャパシタを作製した。
導電性粒子としてカーボンブラック20質量部と、バインダーとしてのスチレン-ブタジエン共重合体(SBR)2質量部と、純水78質量部とを混合撹拌して、実施例7に係る導電層形成用スラリーを調製した。スチレン-ブタジエン共重合体において、スチレン:ブタジエンの共重合比が42:58であった。実施例1に係る導電層形成用スラリーの代わりに実施例7に係る導電層形成用スラリー用いた以外は、実施例1と同様にして実施例7に係る正極を作製した。実施例7に係る正極における導電層の厚みが1μmになるようにアルミニウム箔に対する導電層形成用スラリーの塗布条件を調整した。実施例1に係る正極の代わりに実施例7に係る正極を用いた以外は実施例1と同様にして、実施例7に係るリチウムイオンキャパシタを作製した。
卓上型自動塗工装置(テスター産業社製)を用いて、マイクロメーター付きドクターブレード式アプリケータによって、塗工厚みを190μmに調整し、塗布速度10mm/秒にて、厚み20μmのアルミニウム箔に活物質層形成用スラリーを塗布して塗膜を形成した。次に、この塗膜を、室温(25℃)で45分間放置した後、温度100℃のホットプレート上で乾燥させ、活物質層を形成した。このようにして、比較例1に係る正極を作製した。活物質層の厚みは、71μmであった。
実施例及び比較例に係るリチウムイオンキャパシタをグローブボックスから取り出し、25℃に保たれた恒温槽の内部で、3.8Vから2.2Vの電圧範囲で、1Cに相当する電流値で10サイクル充放電を行い、10サイクル目の放電容量[mAh/g]を、実施例及び比較例に係るリチウムイオンキャパシタの初期容量Ai[mAh/g]とした。結果を、表1に示す。
実施例及び比較例に係るリチウムイオンキャパシタに対し、25℃に保たれた恒温槽の内部で、3.8Vから2.2Vの電圧範囲で、100Cに相当する電流値で充放電を行い、100Cにおける放電容量Ah[mAh/g]を決定した。実施例及び比較例に係るリチウムイオンキャパシタにおける放電容量Ahの初期容量Aiに対する百分率を出力維持率[%]と定めた。結果を表1に示す。
各実施例において、活物質層形成用スラリーを塗布する前の導電層の表面に水滴を静置し、JIS R 3257:1999における静滴法に従って導電層の表面における水滴の接触角を測定した。水滴の接触角の測定温度は、25℃であった。この測定には、接触角計(協和界面科学社製、製品名:DropMaster DM-301)を用いた。加えて、比較例1において、活物質層形成用スラリーを塗布する前のアルミニウム箔表面の水滴の接触角を同様に測定した。結果を表1に示す。
SAICAS(ダイプラ社製、製品名:DN-20)において、各実施例及び比較例1に係る正極から切り取った試験片の活物質層の表面に所定のすくい角で切刃を押し当て、所定の荷重を切刃にかけながら切刃を水平方向に移動させて活物質層を切削した。その後、切刃が活物質層と導電層又はアルミニウム箔との界面に達してから、ダイヤモンド製の切刃(ダイプラ社製、すくい角:10°)を水平方向のみに移動させ、水平切削応力FHを測定した。この測定は、定速度モードで実施した。切削速度は、10μm/秒であった。この測定結果から、式(1)に従い、剥離強度Pを決定した。結果を表1に示す。なお、比較例1の剥離強度Pは、活物質層とアルミニウム箔との界面に関する値である。
実施例1と同様にして、実施例8に係る酸化脱ドープ状態のポリアニリン粉末を得た。マルバーン社製のMorphologi G3を用いて、実施例8に係るポリアニリン粉末の平均粒径(D50)、個数基準の粒子径分布における10%粒子径(D10)、及び90%粒子径(D90)を算出した。結果を表2に示す。実施例1に係るポリアニリン粉末の代わりに実施例8に係るポリアニリン粉末を用い、導電層の厚みが0.87μmになるように調整した以外は、実施例1と同様にして実施例8に係る正極を作製した。実施例1に係る正極の代わりに実施例8に係る正極を用いた以外は実施例1と同様にして、実施例8に係るリチウムイオンキャパシタを作製した。
実施例8に係るポリアニリン粉末に対し、所定の分級操作を行い、実施例9に係るポリアニリン粉末、実施例10に係るポリアニリン粉末、及び実施例11に係るポリアニリン粉末を得た。マルバーン社製のMorphologi G3を用いて、実施例9-11に係るポリアニリン粉末の平均粒径(D50)、個数基準の粒子径分布における10%粒子径(D10)、及び90%粒子径(D90)を算出した。結果を表2に示す。実施例1に係るポリアニリン粉末の代わりに実施例9-11に係るポリアニリン粉末を用い、導電層の厚みが0.87μmになるように調整した以外は、実施例1と同様にしてそれぞれ実施例9-11に係る正極を作製した。実施例1に係る正極の代わりに実施例9-11に係る正極を用いた以外は実施例1と同様にして、それぞれ実施例9-11に係るリチウムイオンキャパシタを作製した。
実施例8-11に係るリチウムイオンキャパシタをグローブボックスから取り出し、25℃に保たれた恒温槽の内部で、3.8Vから2.2Vの電圧範囲で、200Cに相当する電流値で充放電を行い、放電容量A[mAh/g]を特定した。放電開始直前のリチウムイオンキャパシタの電圧V1と、放電開始直後の電圧V2とを確認した。次に、ΔV=V1-V2の関係から決定したΔVの値を、200Cに相当する電流値の単位をアンペア(A)に換算した値Iで除して、直列抵抗の値を求めた。すなわち、直列抵抗=ΔV/Iの関係を有する。結果を表2に示す。
実施例8-11に係るリチウムイオンキャパシタを-30℃に保たれた恒温槽の内部で、3.8Vから2.2Vの電圧範囲で、10Cに相当する電流値でCCCV充電し3.8Vで10分間保持した。その後、10Cに相当する電流値でCC放電した結果を表2に示す。
導電性粒子としてカーボンブラック18質量部と、バインダーとしてのスチレン-ブタジエン共重合体(SBR)4質量部と、純水78質量部とを混合撹拌して、実施例12に係る導電層形成用スラリーを調製した。スチレン-ブタジエン共重合体において、スチレン:ブタジエンの共重合比が42:58であった。導電層形成用スラリーの固形分におけるバインダーの含有量は、質量基準で4%であった。
導電層形成用スラリーの固形分におけるバインダーの含有量が質量基準で6%になるように各成分の含有量を変更した以外は、実施例12と同様にして、実施例13に係る導電層形成用スラリーを調製した。実施例12に係る導電層形成用スラリーの代わりに実施例13に係る導電層形成用スラリーを用いた以外は、実施例12と同様にして、実施例13に係る正極を得た。実施例1に係る正極の代わりに実施例13に係る正極を用いた以外は、実施例1と同様にして、実施例13に係るリチウムイオンキャパシタを得た。
導電層形成用スラリーの固形分におけるバインダーの含有量が質量基準で10%になるように各成分の含有量を変更した以外は、実施例12と同様にして、実施例14に係る導電層形成用スラリーを調製した。実施例1に係る導電層形成用スラリーの代わりに実施例14に係る導電層形成用スラリーを用いた以外は、実施例1と同様にして、実施例14に係る正極を得た。実施例1に係る正極の代わりに実施例14に係る正極を用いた以外は、実施例1と同様にして、実施例14に係るリチウムイオンキャパシタを得た。
導電層形成用スラリーの固形分におけるバインダーの含有量が質量基準で2%になるように各成分の含有量を変更した以外は、実施例12と同様にして、実施例15に係る導電層形成用スラリーを調製した。実施例12に係る導電層形成用スラリーの代わりに実施例15に係る導電層形成用スラリーを用いた以外は、実施例12と同様にして、実施例15に係る正極を得た。実施例1に係る正極の代わりに実施例15に係る正極を用いた以外は、実施例1と同様にして、実施例15に係るリチウムイオンキャパシタを得た。
実施例12~15に係るリチウムイオンキャパシタをグローブボックスから取り出し、各リチウムイオンキャパシタに対し、60℃に保たれた恒温槽の内部で、上限電圧3.8Vで満充電状態(SOC:100%)を保ちつづけるフロート試験を500時間行い、放電容量の時間変化及び直列抵抗の時間変化を測定した。結果を表3に示す。
実施例12~15において、実施例1と同様にして、活物質層形成用スラリーを塗布する前の導電層の表面に水滴を静置し、JIS R 3257:1999における静滴法に従って導電層の表面における水滴の接触角を測定した。結果を表3に示す。
SAICAS(ダイプラ社製、製品名:DN-20)において、実施例12~15に係る正極から切り取った試験片の活物質層の表面に所定のすくい角で切刃を押し当て、所定の荷重を切刃にかけながら切刃を水平方向に移動させて活物質層を切削した。その後、切刃が活物質層と導電層又はアルミニウム箔との界面に達してから、ダイヤモンド製の切刃(ダイプラ社製、すくい角:10°)を水平方向のみに移動させ、水平切削応力FHを測定した。この測定は、定速度モードで実施した。切削速度は、10μm/秒であった。この測定結果から、式(1)に従い、剥離強度Pを決定した。結果を表3に示す。
導電性粒子としてカーボンブラック18質量部と、バインダーとしてのスチレン-ブタジエン共重合体(SBR)4質量部と、純水78質量部とを混合撹拌して、導電層形成用スラリーを調製した。スチレン-ブタジエン共重合体において、スチレン:ブタジエンの共重合比が42:58であった。
導電層の厚みの平均値がより大きくなるようにアルミニウム箔に対する導電層形成用スラリーの塗布条件を変更した以外は実施例16と同様にして、実施例17に係る導電層付集電体を作製した。実施例16に係る導電層付集電体の代わりに、実施例17に係る導電層付集電体を用いた以外は実施例16と同様にして実施例17に係る正極を作製した。実施例1に係る正極の代わりに実施例17に係る正極を用いた以外は実施例1と同様にして、実施例17に係るリチウムイオンキャパシタを作製した。
導電層の厚みがより小さくなるようにアルミニウム箔に対する導電層形成用スラリーの塗布条件を変更した以外は実施例16と同様にして、実施例18に係る導電層付集電体を作製した。実施例16に係る導電層付集電体の代わりに、実施例18に係る導電層付集電体を用いた以外は実施例16と同様にして実施例18に係る正極を作製した。実施例1に係る正極の代わりに実施例18に係る正極を用いた以外は実施例1と同様にして、実施例18に係るリチウムイオンキャパシタを作製した。
実施例16~18に係る導電層付集電体の一部を切断し、その一部を用いてSEMによる断面観察のための試料を作製した。SEM(日立ハイテクノロジーズ社製、製品名:S-4800形、電界放出形走査電子顕微鏡)を用いて、作製した試料の断面を観察し、2万倍に拡大した画像を得た。この画像から、集電体と導電層との境界に沿って2μm間隔で離れた10箇所の位置で導電層の厚みを測定した。この測定結果から、導電層の厚みの平均値を相加平均により求めた。また、10箇所の位置で測定された導電層の厚みの最小値を特定した。結果を表4に示す。
実施例16~18に係るリチウムイオンキャパシタをグローブボックスから取り出し、25℃に保たれた恒温槽の内部で、3.8Vから2.2Vの電圧範囲で、200Cに相当する電流値で充放電を行い、放電容量A[mAh/g]を特定した。放電開始直前のリチウムイオンキャパシタの電圧V1と、放電開始直後の電圧V2とを確認した。次に、ΔV=V1-V2の関係から決定したΔVの値を、200Cに相当する電流値の単位をアンペア(A)に換算した値Iで除して、直列抵抗の値を求めた。すなわち、直列抵抗=ΔV/Iの関係を有する。結果を表4に示す。
実施例16~18に係るリチウムイオンキャパシタに対し、60℃に保たれた恒温槽の内部で、上限電圧3.8Vで満充電状態(SOC:100%)を保ちつづけるフロート試験を500時間行い、放電容量の時間変化及び直列抵抗の時間変化を測定した。
実施例16~18において、実施例1と同様にして、活物質層形成用スラリーを塗布する前の導電層の表面に水滴を静置し、JIS R 3257:1999における静滴法に従って導電層の表面における水滴の接触角を測定した。
SAICAS(ダイプラ社製、製品名:DN-20)において、実施例16~18に係る正極から切り取った試験片の活物質層の表面に所定のすくい角で切刃を押し当て、所定の荷重を切刃にかけながら切刃を水平方向に移動させて活物質層を切削した。その後、切刃が活物質層と導電層又はアルミニウム箔との界面に達してから、ダイヤモンド製の切刃(ダイプラ社製、すくい角:10°)を水平方向のみに移動させ、水平切削応力FHを測定した。この測定は、定速度モードで実施した。切削速度は、10μm/秒であった。この測定結果から、式(1)に従い、剥離強度Pを決定した。結果を表4に示す。
Claims (18)
- 0.5μmを超え20μm以下の平均粒径を有する電気化学的に活性なポリマー粒子と導電助剤とを含有している活物質層と、
集電体と、
前記活物質層と前記集電体との間に配置され、前記活物質層及び前記集電体に接触している導電層と、を備えた、
蓄電デバイス用正極。 - 前記導電層は、カーボン材料でできた導電性粒子と、前記導電性粒子の外面に接触しているバインダーとを含有している、請求項1に記載の蓄電デバイス用正極。
- 前記導電層の前記バインダーは、メチルセルロース、ヒドロキシエチルセルロース、ポリエチレンオキサイド、カルボキシメチルセルロース、これらの誘導体、これらの塩、ポリオレフィン、天然ゴム、合成ゴム、及び熱可塑性エラストマーからなる群より選ばれる少なくとも1つを含む、請求項2に記載の蓄電デバイス用正極。
- 前記導電層の前記バインダーは、ポリオレフィン、カルボキシメチルセルロース、及びスチレン-ブタジエン共重合体からなる群より選ばれる少なくとも1つを含む、請求項2に記載の蓄電デバイス用正極。
- 前記導電層の前記バインダーは、カルボキシメチルセルロース及びスチレン-ブタジエン共重合体の少なくとも一方を含む、請求項2に記載の蓄電デバイス用正極。
- 前記導電層における前記バインダーの含有量は、質量基準で3%以上である、請求項2~5のいずれか1項に記載の蓄電デバイス用正極。
- 前記導電層における前記バインダーの含有量は、質量基準で10%以下である、請求項6に記載の蓄電デバイス用正極。
- 前記電気化学的に活性なポリマー粒子は、ポリアニリン及びポリアニリン誘導体の少なくとも一方を含む、請求項1~7のいずれか1項に記載の蓄電デバイス用正極。
- 前記ポリアニリン及びポリアニリン誘導体は、脱ドーピングされている、請求項8に記載の蓄電デバイス用正極。
- 前記ポリアニリン及びポリアニリン誘導体は、質量基準で35~60%の酸化体を含む、請求項8又は9に記載の蓄電デバイス用正極。
- 前記導電層は、0.1μm~20μmの厚みを有する、請求項1~10のいずれか1項に記載の蓄電デバイス用正極。
- 前記導電層がなす表面における水滴の接触角は、100°以下である、請求項1~11のいずれか1項に記載の蓄電デバイス用正極。
- Surface And Interfacial Cutting Analysis System(SAICAS)によって測定される前記活物質層の前記導電層に対する剥離強度は、0.15kN/m以上である、請求項1~12のいずれか1項に記載の蓄電デバイス用正極。
- 前記活物質層は、エラストマーを含むバインダーを含有している、請求項1~13のいずれか1項に記載の蓄電デバイス用正極。
- 前記活物質層は、ハンセン溶解度パラメータにおける極性項及び水素結合項の合計が20MPa1/2以下であるバインダーを含有している、請求項1~14のいずれか1項に記載の蓄電デバイス用正極。
- 前記導電層が接触している前記集電体の主面に垂直な当該蓄電デバイス用正極の断面の前記集電体と前記導電層との境界に沿って2μm間隔で離れた10箇所の位置で測定される前記導電層の厚みの平均値が0.5~3.0μmである、請求項1~15のいずれか1項に記載の蓄電デバイス用正極。
- 前記10箇所の位置で測定される前記導電層の厚みの最小値は、0.1μm以上である、請求項16に記載の蓄電デバイス用正極。
- 電解質層と、
前記電解質層の第一主面に接触して配置された負極と、
前記電解質層の第二主面に接触して配置された、請求項1~17のいずれか1項に記載の蓄電デバイス用正極と、を備えた、
蓄電デバイス。
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