WO2018030280A1 - Condensateur à ions de métal alcalin non aqueux - Google Patents

Condensateur à ions de métal alcalin non aqueux Download PDF

Info

Publication number
WO2018030280A1
WO2018030280A1 PCT/JP2017/028303 JP2017028303W WO2018030280A1 WO 2018030280 A1 WO2018030280 A1 WO 2018030280A1 JP 2017028303 W JP2017028303 W JP 2017028303W WO 2018030280 A1 WO2018030280 A1 WO 2018030280A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkali metal
positive electrode
metal ion
ion capacitor
less
Prior art date
Application number
PCT/JP2017/028303
Other languages
English (en)
Japanese (ja)
Inventor
和照 梅津
宣宏 岡田
Original Assignee
旭化成株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭化成株式会社 filed Critical 旭化成株式会社
Priority to JP2018532990A priority Critical patent/JP6705899B2/ja
Publication of WO2018030280A1 publication Critical patent/WO2018030280A1/fr

Links

Classifications

    • 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
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • 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
    • H01G11/66—Current collectors
    • H01G11/70—Current collectors characterised by their structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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 a non-aqueous alkali metal ion capacitor and the like.
  • a high-efficiency engine and a power storage system for example, a hybrid electric vehicle
  • a fuel cell and a power storage system for example, a fuel cell electric vehicle
  • high output discharge characteristics in the power storage system are required during acceleration. Yes.
  • electric double layer capacitors, nickel metal hydride batteries, and the like have been developed as high power storage elements.
  • electric double layer capacitors those using activated carbon as electrodes have output characteristics of about 0.5 kW / L to about 1 kW / L.
  • This electric double layer capacitor has high durability (cycle characteristics and high temperature storage characteristics), and has been considered as an optimum device in the field where the high output is required.
  • its energy density is only about 1 Wh / L to about 5 Wh / L. Therefore, further improvement in energy density is necessary.
  • the nickel metal hydride battery currently employed in hybrid electric vehicles has a high output equivalent to that of an electric double layer capacitor and an energy density of about 160 Wh / L.
  • research for increasing the energy density and output and further improving durability (particularly stability at high temperatures) has been energetically advanced.
  • research for higher output is also being conducted in lithium ion batteries.
  • a lithium ion battery has been developed that can obtain a high output exceeding 3 kW / L at a depth of discharge (a value indicating what percentage of the discharge capacity of the storage element is discharged) 50%.
  • the energy density is 100 Wh / L or less, and the high energy density, which is the greatest feature of the lithium ion battery, is intentionally suppressed.
  • the electric double layer capacitor is characterized in that the positive and negative electrodes use activated carbon (energy density 1 time), and the positive and negative electrodes are charged and discharged by a non-Faraday reaction, resulting in high output and high durability.
  • the depth of discharge must be limited, and a lithium ion secondary battery can use only 10 to 50% of its energy.
  • a lithium ion capacitor uses activated carbon (energy density 1 time) for the positive electrode and a carbon material (10 times energy density) for the negative electrode, and is charged and discharged by a non-Faraday reaction at the positive electrode and a Faraday reaction at the negative electrode. It is a novel asymmetric capacitor that combines the features of a multilayer capacitor and a lithium ion secondary battery.
  • the essential lithium has a problem that the concentration in the crust is only about 20 ppm on average, and the production areas are unevenly distributed. In the future, it will be necessary to replace lithium with a more universally existing element, and research into using an alkali metal such as sodium or potassium for an electricity storage element is being actively pursued.
  • Non-Patent Documents 1 to 3 analysis of mesopores or micropores is described in Non-Patent Documents 1 to 3 for electrode active materials used for power storage elements or their raw materials.
  • the present invention has been made in view of the above situation. Therefore, the problem to be solved by the present invention is to provide a high-capacity and high-power non-aqueous alkali metal ion capacitor that suppresses gas generation due to electrolyte decomposition and alkali metal compound decomposition on the positive electrode. And it is suppressing the capacity
  • a non-aqueous alkali metal ion capacitor comprising a positive electrode containing activated carbon, a negative electrode, a separator, and a non-aqueous electrolyte containing two or more cations, wherein at least one of the two or more cations is
  • the negative electrode can occlude / release alkali metal ions, and the compound contained in the positive electrode is a compound of two or more alkali metals selected from the group consisting of Li, Na, K, Rb, and Cs.
  • the positive electrode includes a positive electrode current collector, the negative electrode includes a negative electrode current collector, and the positive electrode current collector and the negative electrode current collector are metal foils having no through holes. ]
  • the non-aqueous alkali metal ion capacitor according to any one of [1] to [3], wherein the alkali metal compound is at least one selected from the group consisting of carbonates, hydroxides, and oxides. .
  • the positive electrode has the positive electrode current collector, and a positive electrode active material layer including a positive electrode active material provided on one or both surfaces of the positive electrode current collector, and the positive electrode active material layer has the following formula (1) to (3): ⁇ In Formula (1), R 1 is an alkylene group having 1 to 4 carbon atoms or a halogenated alkylene group having 1 to 4 carbon atoms, and X 1 and X 2 are each independently — (COO) n (Where n is 0 or 1), and M 1 and M 2 are each independently an alkali metal selected from the group consisting of Li, Na, K, Rb, and Cs.
  • R 1 is an alkylene group having 1 to 4 carbon atoms or a halogenated alkylene group having 1 to 4 carbon atoms
  • R 2 is hydrogen, an alkyl group having 1 to 10 carbon atoms, carbon A group consisting of a mono- or polyhydroxyalkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a mono- or polyhydroxyalkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group X 1 and X 2 are each independently — (COO) n (where n is 0 or 1), and M 1 is Li, Na, K , Rb, and Cs.
  • R 1 is an alkylene group having 1 to 4 carbon atoms or a halogenated alkylene group having 1 to 4 carbon atoms
  • R 2 and R 3 are each independently hydrogen, 1 carbon atom
  • X 1 and X 2 are each independently — (COO) n (where n is 0 or 1).
  • the positive electrode active material layer has the following formulas (4) and (5): ⁇ In Formula (4), M 1 and M 2 are each independently an alkali metal selected from the group consisting of Li, Na, K, Rb, and Cs.
  • R 1 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or a mono- or polyhydroxyalkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 to 10 carbon atoms.
  • the non-aqueous electrolyte contains 2 or more and 4 or less alkali metal ions, and the mass ratio of the first alkali metal ions in the non-aqueous electrolyte is 1% or more and 99% or less, Any one of [1] to [6], wherein the substance amount ratio of the alkali metal ions is 1% or more and 99% or less, and the substance amount ratio of the third and fourth alkali metal ions is 0% or more and 98% or less.
  • the non-aqueous alkali metal ion capacitor according to one item.
  • the amount of mesopores V 1 (cc / g) derived from pores having a diameter of 20 to 500 mm calculated by the BJH method in the positive electrode active material contained in the positive electrode active material layer is 0.8 ⁇ V 1 ⁇ 2. 5 and the micropore amount V 2 (cc / g) derived from pores having a diameter of less than 20 mm calculated by the MP method satisfies 0.8 ⁇ V 2 ⁇ 3.0 and is measured by the BET method.
  • the negative electrode includes a negative electrode active material, and a lithium ion doping amount of the negative electrode active material is 50 mAh / g or more and 700 mAh / g or less per unit mass, according to any one of [1] to [16].
  • the internal resistance at the cell voltage of 4 V is Rb ( ⁇ )
  • the internal resistance before storage is Ra ( ⁇ )
  • the capacitance before storage is Fa (F)
  • the following requirements (a) and (b): (A) Rb / Ra is 3.0 or less, and (b) A value B obtained by normalizing the amount of gas generated when stored at a cell voltage of 4 V and an environmental temperature of 60 ° C. for 2 months with a capacitance Fa is 30.
  • a positive electrode precursor comprising activated carbon and an alkali metal compound having two or more alkali metal ions selected from the group consisting of Li, Na, K, Rb, and Cs as a cation, the first alkali metal compound
  • the substance amount ratio is 2% or more and 98% or less
  • the substance amount ratio of the second alkali metal compound is 2% or more and 98% or less
  • the substance amount ratio of the third and fourth alkali metal ions is 0%.
  • the positive electrode precursor which is 96% or less.
  • the positive electrode precursor according to [24] wherein the alkali metal compound is a carbonate, a hydroxide, or an oxide.
  • [26] [1] to [23] A power storage module using the nonaqueous alkali metal ion capacitor according to any one of [1] to [23].
  • [27] [1] A power regeneration system using the non-aqueous alkali metal ion capacitor according to any one of [23].
  • [28] [1] A power load leveling system using the non-aqueous alkali metal ion capacitor according to any one of [1] to [23].
  • [30] [1] A non-contact power feeding system using the non-aqueous alkali metal ion capacitor according to any one of [1] to [23].
  • [31] [1] An energy harvesting system using the non-aqueous alkali metal ion capacitor according to any one of [23]. [32] A power storage system using the non-aqueous alkali metal ion capacitor according to any one of [1] to [23].
  • the present invention has a high capacity and high output, suppresses gas generation due to electrolyte decomposition on the positive electrode and gas generation due to decomposition of the alkali metal compound, and suppresses capacity decrease in a high load charge / discharge cycle.
  • a water-based alkali metal ion capacitor is provided.
  • a non-aqueous alkali metal ion capacitor mainly includes a positive electrode, a negative electrode, a separator, an electrolytic solution, and an outer package.
  • an organic solvent in which an alkali metal salt is dissolved hereinafter referred to as a non-aqueous electrolytic solution.
  • the non-aqueous electrolyte includes two or more cations, at least one of the two or more cations is an alkali metal ion, and 2 A compound containing an element of the same kind as the cation of at least species is contained in the positive electrode in an amount of 1.0% by mass or more and 25.0% by mass or less.
  • the non-aqueous electrolyte includes one or more alkali metal ions and one or more alkaline earth metal ions, and the alkali having the alkali metal ions as cations.
  • the alkaline earth metal compound having a metal compound and / or alkaline earth metal ion as a cation is contained in the positive electrode active material layer of the positive electrode in an amount of 1.0% by mass or more and 20.0% by mass or less, and a nonaqueous electrolytic solution X / (X + Y) is 0.07 or more and 0.92 or less when the molar concentration of alkali metal ions in the solution is X (mol / L) and the molar concentration of alkaline earth metal ions is Y (mol / L). It is.
  • the positive electrode has a positive electrode current collector and a positive electrode active material layer present on one side or both sides thereof. Moreover, it is preferable that a positive electrode contains an alkali metal compound and / or an alkaline-earth metal compound as a positive electrode precursor before an electrical storage element assembly. As described later, in the present embodiment, it is preferable to pre-dope the negative electrode with alkali metal ions and / or alkaline earth metal ions in the storage element assembling step.
  • the positive electrode state before the alkali metal doping step is defined as the positive electrode precursor
  • the positive electrode state after the alkali metal doping step is defined as the positive electrode.
  • the positive electrode active material layer preferably contains a positive electrode active material containing a carbon material.
  • the positive electrode active material layer may contain optional components such as a conductive filler, a binder, and a dispersion stabilizer as necessary. Good.
  • the positive electrode active material layer of the positive electrode precursor preferably contains an alkali metal compound and / or an alkaline earth metal compound.
  • the alkali metal compound and the alkaline earth metal compound refer to an alkali metal compound other than the alkali metal-containing compound deposited in the positive electrode active material layer using a decomposition reaction of the active material and the precursor described later.
  • the positive electrode active material preferably contains a carbon material.
  • a carbon material it is more preferable to use a carbon nanotube, a conductive polymer, or a porous carbon material, and more preferably activated carbon.
  • One or more kinds of materials may be mixed and used for the positive electrode active material, and a material other than the carbon material (for example, a composite oxide of an alkali metal and a transition metal) may be included.
  • the content of the carbon material with respect to the total amount of the positive electrode active material is 50% by mass or more, and more preferably 70% by mass or more.
  • the content rate of the carbon material can be 100% by mass, it is preferably 90% by mass or less, for example, 80% by mass or less from the viewpoint of obtaining the effect of the combined use of other materials. Also good.
  • activated carbon as a positive electrode active material
  • the amount of mesopores derived from pores having a diameter of 20 to 500 mm calculated by the BJH method is V 1 (cc / g), and the amount of micropores derived from pores having a diameter of less than 20 mm calculated by the MP method.
  • Is V 2 (cc / g) (1) For high input / output characteristics, 0.3 ⁇ V 1 ⁇ 0.8 and 0.5 ⁇ V 2 ⁇ 1.0 are satisfied, and the specific surface area measured by the BET method is 1, Activated carbon (hereinafter also referred to as activated carbon 1) having a mass of 500 m 2 / g to 3,000 m 2 / g is preferred. (2) In order to obtain a high energy density, 0.8 ⁇ V 1 ⁇ 2.5 and 0.8 ⁇ V 2 ⁇ 3.0 are satisfied, and the specific surface area measured by the BET method is 2, Activated carbon (hereinafter also referred to as activated carbon 2) of 300 m 2 / g to 4,000 m 2 / g is preferable.
  • activated carbon 2 Activated carbon
  • the mesopore amount V 1 of the activated carbon 1 is preferably a value larger than 0.3 cc / g from the viewpoint of increasing the input / output characteristics when the positive electrode material is incorporated in the storage element. On the other hand, it is preferably 0.8 cc / g or less from the viewpoint of suppressing a decrease in the bulk density of the positive electrode. V 1 is more preferably 0.35 cc / g or more and 0.7 cc / g or less, and further preferably 0.4 cc / g or more and 0.6 cc / g or less.
  • the micropore amount V 2 of the activated carbon 1 is preferably 0.5 cc / g or more in order to increase the specific surface area of the activated carbon and increase the capacity. On the other hand, it is preferably 1.0 cc / g or less from the viewpoint of suppressing the bulk of the activated carbon, increasing the density as an electrode, and increasing the capacity per unit volume. V 2 is more preferably 0.6 cc / g or more and 1.0 cc / g or less, and further preferably 0.8 cc / g or more and 1.0 cc / g or less.
  • the ratio of meso Anaryou V 1 relative to the micropore volume V 2 (V 1 / V 2 ) is preferably in the range of 0.3 ⁇ V 1 / V 2 ⁇ 0.9. That is, V 1 / V 2 is 0.3 or more from the viewpoint of increasing the ratio of the mesopore amount to the micropore amount to such an extent that the decrease in output characteristics can be suppressed while maintaining a high capacity. preferable. On the other hand, V 1 / V 2 is 0.9 or less from the viewpoint of increasing the ratio of the micropore amount to the mesopore amount to such an extent that the decrease in capacity can be suppressed while maintaining high output characteristics.
  • the range of V 1 / V 2 is 0.4 ⁇ V 1 / V 2 ⁇ 0.7, and the more preferable range of V 1 / V 2 is 0.55 ⁇ V 1 / V 2 ⁇ 0.7. It is.
  • the upper limit value and lower limit value of V 1 and the upper limit value and lower limit value of V 2 can be arbitrarily combined. In the present specification, the same applies to the combination of the upper limit value and the lower limit value of other constituent elements.
  • the average pore diameter of the activated carbon 1 is preferably 17 mm or more, more preferably 18 mm or more, and most preferably 20 mm or more from the viewpoint of maximizing the output of the obtained electricity storage device. Moreover, from the point of maximizing the capacity, the average pore diameter of the activated carbon 1 is preferably 25 mm or less.
  • the carbon source used as a raw material for the activated carbon 1 is not particularly limited.
  • plant materials such as wood, wood flour, coconut husk, pulp by-products, bagasse, and molasses; peat, lignite, lignite, bituminous coal, anthracite, petroleum distillation residue components, petroleum pitch, coke, coal tar, etc.
  • Fossil-based raw materials various synthetic resins such as phenol resin, vinyl chloride resin, vinyl acetate resin, melamine resin, urea resin, resorcinol resin, celluloid, epoxy resin, polyurethane resin, polyester resin, polyamide resin; polybutylene, polybutadiene, polychloroprene, etc.
  • Synthetic rubber, other synthetic wood, synthetic pulp and the like, and carbides thereof are synththetic rubber, other synthetic wood, synthetic pulp and the like, and carbides thereof.
  • plant raw materials such as coconut shells and wood flour, and their carbides are preferable, and coconut shell carbides are particularly preferable.
  • a method of carbonization and activation for using these raw materials as the activated carbon known methods such as a fixed bed method, a moving bed method, a fluidized bed method, a slurry method, and a rotary kiln method can be employed.
  • a carbonization method of these raw materials nitrogen, carbon dioxide, helium, argon, xenon, neon, carbon monoxide, an exhaust gas such as combustion exhaust gas, or other gases mainly composed of these inert gases.
  • the method include baking using a mixed gas at about 400 to 700 ° C. (preferably 450 to 600 ° C.) for about 30 minutes to 10 hours.
  • a gas activation method in which firing is performed using an activation gas such as water vapor, carbon dioxide, or oxygen is used. Among these, a method using water vapor or carbon dioxide as the activation gas is preferable.
  • the carbide is supplied for 3 to 12 hours (preferably 5 to 11) while supplying an activation gas at a rate of 0.5 to 3.0 kg / h (preferably 0.7 to 2.0 kg / h). It is preferable to activate by heating up to 800 to 1,000 ° C. over a period of time, more preferably 6 to 10 hours.
  • the carbide may be activated in advance.
  • a method of gas activation by firing a carbon material at a temperature of less than 900 ° C. using an activation gas such as water vapor, carbon dioxide, oxygen or the like can be preferably employed.
  • an activation gas such as water vapor, carbon dioxide, oxygen or the like.
  • the average particle size When the average particle size is 2 ⁇ m or more, the capacity per electrode volume tends to be high because the density of the active material layer is high.
  • the average particle size if the average particle size is small, there may be a drawback that the durability is low. However, if the average particle size is 2 ⁇ m or more, such a defect hardly occurs.
  • the average particle size when the average particle size is 20 ⁇ m or less, it tends to be easily adapted to high-speed charge / discharge.
  • the average particle diameter is more preferably 2 to 15 ⁇ m, still more preferably 3 to 10 ⁇ m.
  • the mesopore amount V 1 of the activated carbon 2 is preferably a value larger than 0.8 cc / g from the viewpoint of increasing the output characteristics when the positive electrode material is incorporated in the electric storage element.
  • the mesopore amount V 1 is preferably 2.5 cc / g or less from the viewpoint of suppressing a decrease in the capacity of the power storage element.
  • V 1 is more preferably 1.00 cc / g or more and 2.0 cc / g or less, and further preferably 1.2 cc / g or more and 1.8 cc / g or less.
  • the micropore volume V 2 of the activated carbon 2 is preferably larger than 0.8 cc / g in order to increase the specific surface area of the activated carbon and increase the capacity.
  • the micropore amount V 2 is preferably 3.0 cc / g or less from the viewpoint of increasing the density of the activated carbon as an electrode and increasing the capacity per unit volume.
  • V 2 is more preferably greater than 1.0 cc / g and not greater than 2.5 cc / g, and still more preferably not less than 1.5 cc / g and not greater than 2.5 cc / g.
  • the carbonaceous material used as a raw material for the activated carbon 2 is not particularly limited as long as it is a carbon source that is usually used as a raw material for activated carbon.
  • Examples include fossil raw materials such as coke; various synthetic resins such as phenol resin, furan resin, vinyl chloride resin, vinyl acetate resin, melamine resin, urea resin, and resorcinol resin.
  • a phenol resin and a furan resin are particularly preferable because they are suitable for producing activated carbon having a high specific surface area.
  • Examples of the method for carbonizing these raw materials or the heating method during the activation treatment include known methods such as a fixed bed method, a moving bed method, a fluidized bed method, a slurry method, and a rotary kiln method.
  • the atmosphere at the time of heating is an inert gas such as nitrogen, carbon dioxide, helium, or argon, or a gas mixed with other gases containing these inert gases as a main component.
  • the carbonization temperature is about 400 to 700 ° C.
  • the firing is performed for about 0.5 to 10 hours.
  • Examples of the activation method of the carbide include a gas activation method in which firing is performed using an activation gas such as water vapor, carbon dioxide, and oxygen, and an alkali metal activation method in which heat treatment is performed after mixing with an alkali metal compound.
  • An alkali metal activation method is preferable for producing activated carbon.
  • mixing was performed so that the mass ratio of the carbide to the alkali metal compound such as KOH or NaOH was 1: 1 or more (the amount of the alkali metal compound was the same as or greater than the amount of the carbide). Thereafter, heating is performed in the range of 600 to 900 ° C.
  • a larger amount of carbides may be mixed with KOH when activated.
  • a larger amount of KOH may be used.
  • the average particle diameter of the activated carbon 2 is preferably 2 ⁇ m or more and 20 ⁇ m or less, more preferably 3 ⁇ m or more and 10 ⁇ m or less.
  • Each of the activated carbons 1 and 2 may be one type of activated carbon, or a mixture of two or more types of activated carbon, and each characteristic value described above may be shown as the entire mixture.
  • the activated carbons 1 and 2 may be used by selecting any one of them, or may be used by mixing both.
  • the positive electrode active material is a material other than activated carbon 1 and 2 (for example, activated carbon not having the specific V 1 and / or V 2 , or a material other than activated carbon (for example, a composite oxide of an alkali metal and a transition metal) )).
  • the content of the activated carbon 1, or the content of the activated carbon 2, or the total content of the activated carbons 1 and 2 is preferably more than 50% by mass of the total positive electrode active material, and 70% by mass or more. More preferably, it is more preferably 90% by mass or more, and most preferably 100% by mass.
  • the content ratio of the positive electrode active material in the positive electrode active material layer is preferably 35% by mass or more and 95% by mass or less based on the total mass of the positive electrode active material layer in the positive electrode precursor.
  • As an upper limit of the content rate of a positive electrode active material it is more preferable that it is 45 mass% or more, and it is further more preferable that it is 55 mass% or more.
  • As a minimum of the content rate of a positive electrode active material it is more preferable that it is 90 mass% or less, and it is still more preferable that it is 85 mass% or less.
  • the compound containing 2 or more types of elements of the same kind as 2 or more types of cations contained in electrolyte solution is contained in a positive electrode.
  • At least one of the two or more types of cations is an alkali metal ion.
  • the remaining cation is not particularly limited as long as it is involved in charging / discharging of the non-aqueous capacitor.
  • the compound may be, for example, an alkali metal compound, an alkaline earth metal compound, a transition metal compound, an aluminum compound, an ammonium salt, a pyridinium salt, an imidazolium salt, a phosphonium salt, or the like.
  • the capacity and output of the non-aqueous alkali metal ion capacitor are improved, gas generation due to electrolyte decomposition on the positive electrode and gas generation due to decomposition of the alkali metal compound are suppressed, and a high-load charge / discharge cycle From the viewpoint of suppressing the capacity decrease in the above, it is preferable that the compound contained in the positive electrode contains an alkali metal compound and an alkaline earth metal compound.
  • alkali metal compounds, alkaline earth metal compounds The alkali metal compound or an alkaline earth metal compound, in formula, the M A Li, Na, K, Rb, and one or more selected from the group consisting of Cs, Be the M B, Mg, Ca, Sr, And at least one selected from Ba, carbonates such as M A 2 CO 3 and M B CO 3 , oxides such as M A 2 O and M B O, M A OH and M B (OH) 2 Hydroxides, M A F, M A Cl, M A Br, M A I, M B F 2 , M B Cl 2 , M B Br 2 , M B I 2 and other halides, M A 2 (CO 2 ) 2, M B (CO 2 ) 2 and the like oxalates, RCOOM a, (RCOO) in 2 M B (wherein, 1 R is selected from H, alkyl group, or an aryl group) carboxylic acid salts such as More than species are preferably used.
  • carbonates, oxides, and hydroxides are more preferable, carbonates are more preferably used from the viewpoint that they can be handled in the air and have low basicity.
  • carbonates Li 2 CO 3 , Na 2 CO 3 , and K 2 CO 3 are used as alkaline metal carbonates from the viewpoint that the acid reduction potential of the cation forming the compound is low.
  • CaCO 3 is particularly preferably used as the metal carbonate.
  • a pulverizer such as a ball mill, a bead mill, a ring mill, a jet mill, or a rod mill can be used.
  • the amount of the alkali metal compound and / or alkaline earth metal compound contained in the positive electrode is preferably 1.0% by mass or more and 25.0% by mass or less, and more preferably 1.5% by mass or more and 20.0% by mass. It is below mass%. If the amount of the alkali metal compound and / or alkaline earth metal compound is 1.0% by mass or more, there is a sufficient amount of carbonate to adsorb the fluorine ions generated in the high load charge / discharge cycle, so that high load charge is possible. Discharge cycle characteristics are improved. When the amount of the alkali metal compound and / or the alkaline earth metal compound is 25.0% by mass or less, the energy density of the non-aqueous alkali metal ion capacitor can be increased.
  • an alkali having an alkali metal ion as a cation from the viewpoint of achieving high capacity and high output of the storage element and suppressing gas generation during charging and discharging.
  • the alkaline earth metal compound having a metal compound and / or alkaline earth metal ion as a cation is preferably contained in an amount of 1.0% by mass or more and 20.0% by mass or less based on the mass of the positive electrode active material layer. More preferably, the content is 2.0% by mass or more and 19.0% by mass or less.
  • the content ratio of the alkali metal compound and / or alkaline earth metal compound in the positive electrode precursor is preferably 10% by mass or more and 60% by mass or less based on the total mass of the positive electrode active material layer in the positive electrode precursor. More preferably, the content is from 50% by weight to 50% by weight.
  • a compound composed of a plurality of alkali metals and / or alkaline earth metal compounds by containing a compound composed of a plurality of alkali metals and / or alkaline earth metal compounds, a plurality of alkali metal ions and / or alkaline earth metal ions are present in the electrolyte during the alkali metal doping described later. This is preferable.
  • the positive electrode active material layer according to the present invention contains at least one compound selected from the following formulas (1) to (3) from 1.60 ⁇ 10 ⁇ 4 mol / g to 300 per unit mass of the positive electrode material. It is preferable to contain ⁇ 10 ⁇ 4 mol / g.
  • R 1 is an alkylene group having 1 to 4 carbon atoms or a halogenated alkylene group having 1 to 4 carbon atoms
  • X 1 and X 2 are each independently — (COO) n (Where n is 0 or 1)
  • M 1 and M 2 are each independently an alkali metal selected from the group consisting of Li, Na, K, Rb, and Cs.
  • R 1 is an alkylene group having 1 to 4 carbon atoms or a halogenated alkylene group having 1 to 4 carbon atoms
  • R 2 is hydrogen, an alkyl group having 1 to 10 carbon atoms, carbon A group consisting of a mono- or polyhydroxyalkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a mono- or polyhydroxyalkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group X 1 and X 2 are each independently — (COO) n (where n is 0 or 1), and M 1 is Li, Na, K , Rb, and Cs.
  • R 1 is an alkylene group having 1 to 4 carbon atoms or a halogenated alkylene group having 1 to 4 carbon atoms
  • R 2 and R 3 are each independently hydrogen, 1 carbon atom
  • X 1 and X 2 are each independently — (COO) n (where n is 0 or 1).
  • R 1 is an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms
  • X 1 and X 2 are each independently — (COO) n (Where n is 0 or 1).
  • Preferred compounds represented by formula (1) include MOC 2 H 4 OM, MOC 3 H 6 OM, MOC 2 H 4 OCOOM, MOCOOC 3 H 6 OM, MOCOOC 2 H 4 OCOOM and MOCOOC 3 H 6 OCOOM (wherein , M are each independently an alkali metal selected from the group consisting of Li, Na, K, Rb, and Cs.).
  • R 1 is an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms
  • R 2 is hydrogen, an alkyl group having 1 to 10 carbon atoms, 1 to 10 mono- or polyhydroxyalkyl group or lithium alkoxide thereof, alkenyl group having 2 to 10 carbon atoms, mono- or polyhydroxyalkenyl group having 2 to 10 carbon atoms, cycloalkyl group having 3 to 6 carbon atoms, and aryl group
  • X 1 and X 2 are each independently — (COO) n (where n is 0 or 1).
  • Preferred compounds represented by the formula (2) are MOC 2 H 4 OH, MOC 3 H 6 OH, MOC 2 H 4 OCOOH, MOC 3 H 6 OCOOH, MOCOOC 2 H 4 OCOOH, MOCOOC 3 H 6 OCOOH, MOC 2 H 4 OCH 3 , MOC 3 H 6 OCH 3 , MOC 2 H 4 OCOOCH 3 , MOC 3 H 6 OCOOCH 3 , MOCOOC 2 H 4 OCOOCH 3 , MOCOOC 3 H 6 OCOOCH 3 , MOC 2 H 4 OC 2 H 5 3 H 6 OC 2 H 5 , MOC 2 H 4 OCOOC 2 H 5 , MOC 3 H 6 OCOOC 2 H 5 , MOCOOC 2 H 4 OCOOC 2 H 5 , or MOCOOC 3 H 6 OCOOC 2 H 5 (where M is Each independently composed of Li, Na, K, Rb, and Cs From an alkali metal selected.) Is a compound represented by the.
  • R 1 is an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms
  • R 2 and R 3 are each independently hydrogen, 10 alkyl groups, mono- or polyhydroxyalkyl groups having 1 to 10 carbon atoms or lithium alkoxides thereof, alkenyl groups having 2 to 10 carbon atoms, mono- or polyhydroxyalkenyl groups having 2 to 10 carbon atoms, 3 to 6 carbon atoms
  • Preferred compounds represented by formula (3) are HOC 2 H 4 OH, HOC 3 H 6 OH, HOC 2 H 4 OCOOH, HOC 3 H 6 OCOOH, HOCOOC 2 H 4 OCOOH, HOCOOC 3 H 6 OCOOH, HOC 2 H 4 OCH 3, HOC 3 H 6 OCH 3, HOC 2 H 4 OCOOCH 3, HOC 3 H 6 OCOOCH 3, HOCOOC 2 H 4 OCOOCH 3, HOCOOC 3 H 6 OCOOCH 3, HOC 2 H 4 OC 2 H 5, HOC 3 H 6 OC 2 H 5 , HOC 2 H 4 OCOOC 2 H 5 , HOC 3 H 6 OCOOC 2 H 5 , HOCOOC 2 H 4 OCOOC 2 H 5 , HOCOOC 3 H 6 OCOOC 2 H 5 , CH 3 OC 2 H 4 OCH 3 , CH 3 OC 3 H 6 OCH 3 , CH 3 OC 2 H 4 OCOOCH 3 , CH 3 OC 3 H 6 OCOOCH 3 ,
  • a compound represented by the following formula (4) or formula (5) is converted from 2.70 ⁇ 10 ⁇ 4 mol / g to 150 ⁇ 10 ⁇ 4 mol per unit mass of the positive electrode active material layer.
  • / G is preferable, and more preferably 2.70 ⁇ 10 ⁇ 4 mol / g to 130 ⁇ 10 ⁇ 4 mol / g.
  • M 1 and M 2 are each independently an alkali metal selected from the group consisting of Li, Na, K, Rb, and Cs.
  • a method for containing the above-mentioned compound in the present invention in the positive electrode active material layer for example, A method of mixing the compound in the positive electrode active material layer; A method of adsorbing the compound on the positive electrode active material layer; Examples thereof include a method of electrochemically depositing the compound on the positive electrode active material layer.
  • a non-aqueous electrolyte solution contains a precursor that can be decomposed to produce the compound, and a positive electrode active material layer is obtained by utilizing a decomposition reaction of the precursor in a step of manufacturing an electricity storage device. A method of depositing the compound therein is preferred.
  • the precursor for forming the compound it is preferable to use at least one organic solvent selected from ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate and fluoroethylene carbonate, and ethylene carbonate and propylene carbonate are used. More preferably.
  • the total amount of the compound is preferably 1.60 ⁇ 10 ⁇ 4 mol / g or more, and more preferably 5.0 ⁇ 10 ⁇ 4 mol / g or more per unit mass of the positive electrode active material. Most preferred.
  • the total amount of the compound is 300 ⁇ 10 ⁇ 4 mol / g or less, preferably 150 ⁇ 10 ⁇ 4 mol / g or less, and 100 ⁇ 10 ⁇ 4 mol / unit, per unit mass of the positive electrode active material. / G or less is more preferable.
  • the total amount of the compound is 300 ⁇ 10 ⁇ 4 mol / g or less per unit mass of the positive electrode active material, high input / output characteristics can be exhibited without inhibiting the diffusion of alkali metal ions.
  • a film made of a fluorine-containing compound on the surface of the alkali metal compound and / or alkaline earth metal compound to suppress the reaction of the alkali metal compound and / or alkaline earth metal compound.
  • the upper limit value and lower limit value of the above compounds can be arbitrarily combined.
  • the method for forming the coating film of the fluorine-containing compound is not particularly limited, but a fluorine-containing compound that decomposes at a high potential is contained in the electrolytic solution, and a high voltage that is higher than the decomposition potential of the fluorine-containing compound is applied to the non-aqueous alkali metal ion capacitor. And a method of applying a temperature higher than the decomposition temperature.
  • the element mapping obtained by SEM-EDX on the positive electrode surface is obtained by calculating the area overlapping rate of fluorine mapping for the oxygen mapping binarized based on the average value of luminance values. It is done.
  • the measurement conditions for elemental mapping of SEM-EDX are not particularly limited, but the number of pixels is preferably in the range of 128 ⁇ 128 pixels to 512 ⁇ 512 pixels, and there is no pixel that reaches the maximum luminance value in the mapping image, and the luminance value It is preferable to adjust the luminance and contrast so that the average value falls within the range of 40% to 60% of the maximum luminance value.
  • the average value fluorine mapping area overlap ratio A 2 of for binarization oxygen mapped on the basis of the luminance values is 60% or less than 10%. If A 2 is 10% or more, it is possible to suppress the decomposition of the alkali metal compound. If A 2 is 60% or less, the alkali metal compound is not fluorinated up to the inside, so the vicinity of the positive electrode can be kept basic and excellent in high duty cycle characteristics.
  • the mixing amount of the conductive filler in the positive electrode active material layer is preferably 0 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • the conductive filler is preferably mixed from the viewpoint of high input. However, when the mixing amount is more than 20 parts by mass, the content ratio of the positive electrode active material in the positive electrode active material layer is decreased, so that the energy density per volume of the positive electrode active material layer is lowered, which is not preferable.
  • the binder is not particularly limited.
  • PVdF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • polyimide latex
  • styrene-butadiene copolymer fluororubber
  • acrylic copolymer etc.
  • the amount of the binder used is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 27 parts by mass or less, and further preferably 5 parts by mass or more with respect to 100 parts by mass of the positive electrode active material. 25 parts by mass or less.
  • the amount of the binder is 1% by mass or more, sufficient electrode strength is exhibited.
  • the amount of the binder when the amount of the binder is 30 parts by mass or less, high input / output characteristics are exhibited without hindering the entry / exit and diffusion of ions to / from the positive electrode active material.
  • a dispersion stabilizer For example, PVP (polyvinyl pyrrolidone), PVA (polyvinyl alcohol), a cellulose derivative etc. can be used.
  • the amount of the dispersion stabilizer used is preferably 0 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material. When the amount of the dispersion stabilizer is 10 parts by mass or less, high input / output characteristics are exhibited without hindering the entry / exit and diffusion of ions to / from the positive electrode active material.
  • the material constituting the positive electrode current collector in the present invention is not particularly limited as long as it is a material that has high electron conductivity and does not deteriorate due to elution into an electrolytic solution and reaction with an electrolyte or ions. Is preferred.
  • an aluminum foil is particularly preferable as the positive electrode current collector in the non-aqueous alkali metal ion capacitors of the first, second and third embodiments.
  • the metal foil may be a normal metal foil having no irregularities or through holes, or a metal foil having irregularities subjected to embossing, chemical etching, electrolytic deposition, blasting, etc., expanded metal, punching metal Alternatively, a metal foil having a through hole such as an etching foil may be used.
  • the thickness of the positive electrode current collector is not particularly limited as long as the shape and strength of the positive electrode can be sufficiently maintained, but for example, 1 to 100 ⁇ m is preferable.
  • the positive electrode precursor serving as the positive electrode of the non-aqueous alkali metal ion capacitor can be manufactured by an electrode manufacturing technique in a known lithium ion battery, electric double layer capacitor, or the like.
  • a positive electrode active material, an alkali metal compound, and other optional components used as necessary are dispersed or dissolved in water or an organic solvent to prepare a slurry-like coating liquid, and this coating liquid is used as the positive electrode
  • a positive electrode precursor can be obtained by coating on one or both sides of the current collector to form a coating film and drying it. Furthermore, you may press the obtained positive electrode precursor, and may adjust the film thickness and bulk density of a positive electrode active material layer.
  • the positive electrode active material and the alkali metal compound, and other optional components used as needed are mixed in a dry process, and the resulting mixture is press-molded, and then the conductive adhesive is added.
  • a method of using and sticking to the positive electrode current collector is also possible.
  • the positive electrode precursor coating solution is prepared by dry blending part or all of various material powders including the positive electrode active material, and then water or an organic solvent, and / or a binder or a dispersion stabilizer are dissolved therein. Alternatively, it may be prepared by adding a dispersed liquid or slurry substance.
  • various material powders containing a positive electrode active material may be added to a liquid or slurry substance in which a binder or dispersion stabilizer is dissolved or dispersed in water or an organic solvent.
  • a positive electrode active material and an alkali metal compound, and a conductive filler as necessary are premixed using a ball mill or the like, and a conductive material is coated on a low conductivity alkali metal compound. You may mix. Thereby, an alkali metal compound becomes easy to decompose
  • water is used as the solvent of the coating solution, the addition of an alkali metal compound may make the coating solution alkaline, so a pH adjuster may be added as necessary.
  • the preparation of the positive electrode precursor coating solution is not particularly limited, but preferably a disperser such as a homodisper, a multiaxial disperser, a planetary mixer, a thin film swirl type high speed mixer, or the like can be used. .
  • a disperser such as a homodisper, a multiaxial disperser, a planetary mixer, a thin film swirl type high speed mixer, or the like can be used.
  • a peripheral speed of 1 m / s or more is preferable because various materials can be dissolved or dispersed well.
  • the particle size measured with a particle gauge is preferably 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the particle size is more preferably 80 ⁇ m or less, and further preferably the particle size is 50 ⁇ m or less.
  • the particle size is not more than the particle size of various material powders including the positive electrode active material, which is not preferable because the material is crushed during preparation of the coating liquid.
  • the particle size is 100 ⁇ m or less, coating can be stably performed without clogging during coating liquid discharge or generation of streaks in the coating film.
  • the viscosity ( ⁇ b) of the coating solution for the positive electrode precursor is preferably 1,000 mPa ⁇ s to 20,000 mPa ⁇ s, more preferably 1,500 mPa ⁇ s to 10,000 mPa ⁇ s, and still more preferably 1 700 mPa ⁇ s to 5,000 mPa ⁇ s.
  • the viscosity ( ⁇ b) is 1,000 mPa ⁇ s or more, dripping at the time of coating film formation is suppressed, and the coating film width and thickness can be controlled well.
  • the TI value (thixotropic index value) of the coating solution is preferably 1.1 or more, more preferably 1.2 or more, and further preferably 1.5 or more.
  • the coating film width and thickness can be favorably controlled.
  • the formation of the coating film of the positive electrode precursor is not particularly limited, but preferably a coating machine such as a die coater, a comma coater, a knife coater, or a gravure coating machine can be used.
  • the coating film may be formed by single layer coating or may be formed by multilayer coating.
  • the coating solution composition may be adjusted so that the content of the alkali metal compound in each layer of the coating film is different.
  • the coating speed is preferably from 0.1 m / min to 100 m / min, more preferably from 0.5 m / min to 70 m / min, still more preferably from 1 m / min to 50 m / min.
  • the drying of the coating film of the positive electrode precursor is not particularly limited, but preferably a drying method such as hot air drying or infrared (IR) drying can be used.
  • the coating film may be dried at a single temperature or may be dried by changing the temperature in multiple stages. Moreover, you may dry combining several drying methods.
  • the drying temperature is preferably 25 ° C. or higher and 200 ° C. or lower, more preferably 40 ° C. or higher and 180 ° C. or lower, and further preferably 50 ° C. or higher and 160 ° C. or lower.
  • the drying temperature is 25 ° C. or higher, the solvent in the coating film can be sufficiently volatilized.
  • it is 200 degrees C or less, the crack of the coating film by rapid volatilization of a solvent, the uneven distribution of the binder by migration, and the oxidation of a positive electrode collector or a positive electrode active material layer can be suppressed.
  • the press of the positive electrode precursor is not particularly limited, but preferably a press such as a hydraulic press or a vacuum press can be used.
  • the film thickness, bulk density, and electrode strength of the positive electrode active material layer can be adjusted by the press pressure, gap, and surface temperature of the press part described later.
  • the pressing pressure is preferably 0.5 kN / cm or more and 20 kN / cm or less, more preferably 1 kN / cm or more and 10 kN / cm or less, and further preferably 2 kN / cm or more and 7 kN / cm or less. If the pressing pressure is 0.5 kN / cm or more, the electrode strength can be sufficiently increased.
  • the positive electrode precursor can be adjusted to a desired positive electrode active material layer thickness and bulk density without causing bending or wrinkles.
  • the gap between the press rolls can be set to an arbitrary value according to the thickness of the positive electrode precursor after drying so as to have a desired film thickness or bulk density of the positive electrode active material layer.
  • the press speed can be set to an arbitrary speed at which the positive electrode precursor does not bend or wrinkle.
  • the surface temperature of a press part may be room temperature, and may be heated if necessary. The lower limit of the surface temperature of the press part in the case of heating is preferably the melting point minus 60 ° C. or more of the binder used, more preferably 45 ° C.
  • the upper limit of the surface temperature of the press part in the case of heating is preferably the melting point of the binder used plus 50 ° C. or less, more preferably 30 ° C. or less, and further preferably 20 ° C. or less.
  • PVdF polyvinylidene fluoride: melting point 150 ° C.
  • it is preferably heated to 90 ° C. or higher and 200 ° C. or lower, more preferably 105 ° C. or higher and 180 ° C. or lower, and even more preferably 120 ° C. or higher. Heating to 170 ° C. or lower.
  • a styrene-butadiene copolymer (melting point 100 ° C.) is used as the binder, it is preferably heated to 40 ° C. or higher and 150 ° C. or lower, more preferably 55 ° C. or higher and 130 ° C. or lower, and still more preferably 70 ° C. It is heating up to 120 ° C. or higher.
  • the melting point of the binder can be determined at the endothermic peak position of DSC (Differential Scanning Calorimetry). For example, using a differential scanning calorimeter “DSC7” manufactured by PerkinElmer Co., Ltd., 10 mg of sample resin is set in a measurement cell, and the temperature is increased from 30 ° C. to 250 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen gas atmosphere. The temperature is raised, and the endothermic peak temperature in the temperature raising process becomes the melting point. Moreover, you may press several times, changing the conditions of press pressure, a clearance gap, speed
  • DSC7 Different Scanning Calorimetry
  • the thickness of the positive electrode active material layer is preferably 20 ⁇ m or more and 200 ⁇ m or less per side of the positive electrode current collector, more preferably 25 ⁇ m or more and 100 ⁇ m or less, more preferably 30 ⁇ m or more and 80 ⁇ m or less. If this thickness is 20 ⁇ m or more, sufficient charge / discharge capacity can be exhibited. On the other hand, if this thickness is 200 ⁇ m or less, the ion diffusion resistance in the electrode can be kept low. As a result, sufficient output characteristics can be obtained, the cell volume can be reduced, and therefore the energy density can be increased.
  • the negative electrode of the present invention has a negative electrode current collector and a negative electrode active material layer present on one side or both sides thereof.
  • the negative electrode active material layer includes a negative electrode active material that can occlude / release alkali metal ions and / or alkaline earth metal ions.
  • optional components such as a conductive filler, a binder, and a dispersion stabilizer may be included as necessary.
  • the negative electrode active material a material capable of occluding and releasing alkali metal ions and / or alkaline earth metal ions can be used. Specific examples include carbon materials, titanium oxide, silicon, silicon oxide, silicon alloys, silicon compounds, tin and tin compounds.
  • the content of the carbon material with respect to the total amount of the negative electrode active material is 50% by mass or more, and more preferably 70% by mass or more.
  • the content rate of the carbon material can be 100% by mass, it is preferably 90% by mass or less, for example, 80% by mass or less from the viewpoint of obtaining the effect of the combined use of other materials. Also good.
  • the negative electrode active material is preferably doped with two or more kinds of alkali metal ions and / or alkaline earth metal ions.
  • the two or more types of alkali metal ions and / or alkaline earth metal ions doped in the negative electrode active material mainly include three forms.
  • the first form is two or more types of alkali metal ions and / or alkaline earth metal ions that are stored in the negative electrode active material in advance as a design value before producing a non-aqueous alkali metal ion capacitor.
  • the second form is two or more types of alkali metal ions and / or alkaline earth metal ions occluded in the negative electrode active material when a non-aqueous alkali metal ion capacitor is manufactured and shipped.
  • As 3rd form it is 2 or more types of alkali metal ions and / or alkaline-earth metal ions occluded by the negative electrode active material after using a non-aqueous alkali metal ion capacitor as a device.
  • Examples of the carbon material include non-graphitizable carbon materials; graphitizable carbon materials; carbon black; carbon nanoparticles; activated carbon; artificial graphite; natural graphite; graphitized mesophase carbon spherules; Amorphous carbonaceous materials such as petroleum-based pitch, coal-based pitch, mesocarbon microbeads, coke, carbonaceous materials obtained by heat treatment of carbon precursors such as synthetic resins (for example, phenol resins); furfuryl alcohol Examples include thermal decomposition products of resins or novolac resins; fullerenes; carbon nanophones; and composite carbon materials thereof.
  • the pitch composite carbon material are pitch composite carbon materials 1a and 2a described later. Either of these may be selected and used, or both of them may be used in combination.
  • the pitch composite carbon material 1a is obtained by heat treatment in a state where at least one carbon material having a BET specific surface area of 100 m 2 / g or more and 3000 m 2 / g or less and petroleum-based pitch or coal-based pitch coexist. Can do.
  • the carbon material is not particularly limited, and activated carbon, carbon black, template porous carbon, high specific surface area graphite, carbon nanoparticles, and the like can be suitably used.
  • the mass ratio of the carbonaceous material to the base material in the composite carbon material 1a is preferably 10% or more and 200% or less. This mass ratio is preferably 12% to 180%, more preferably 15% to 160%, and particularly preferably 18% to 150%. If the mass ratio of the carbonaceous material is 10% or more, the micropores of the base material can be appropriately filled with the carbonaceous material, and two or more kinds of alkali metal ions and / or alkaline earths can be filled. Since the charge / discharge efficiency of metal ions is improved, good cycle durability can be exhibited.
  • the mass ratio of the carbonaceous material is 200% or less, the pores can be appropriately maintained, and the diffusion of two or more kinds of alkali metal ions and / or alkaline earth metal ions becomes good. Input / output characteristics can be shown.
  • lithium ions having the smallest ionic radius indicate the largest doping amount. Therefore, it is preferable to adjust the doping amount of alkali metal ions based on the doping amount of lithium ions.
  • the negative electrode containing the composite carbon material 1a doped with the ions when the negative electrode containing the composite carbon material 1a doped with the ions is combined with the positive electrode, the voltage of the non-aqueous alkali metal ion capacitor is increased and the utilization capacity of the positive electrode is increased. Therefore, the capacity and energy density of the obtained non-aqueous alkali metal ion capacitor are increased. If the doping amount of the lithium ions is 530 mAh / g or more, the ions are also present on irreversible sites that cannot be desorbed once the two or more kinds of alkali metal ions and / or alkaline earth metal ions in the composite carbon material 1a are inserted.
  • the composite carbon material 1a using activated carbon as the base material will be described.
  • the amount of mesopores derived from pores having a diameter of 20 to 500 mm calculated by the BJH method is Vm1 (cc / g) and the amount of micropores derived from pores having a diameter of less than 20 mm calculated by the MP method Is Vm2 (cc / g), it is preferable that 0.010 ⁇ Vm1 ⁇ 0.300 and 0.001 ⁇ Vm2 ⁇ 0.650.
  • the mesopore amount Vm1 is more preferably 0.010 ⁇ Vm1 ⁇ 0.225, and further preferably 0.010 ⁇ Vm1 ⁇ 0.200.
  • the micropore amount Vm2 is more preferably 0.001 ⁇ Vm2 ⁇ 0.200, further preferably 0.001 ⁇ Vm2 ⁇ 0.150, and particularly preferably 0.001 ⁇ Vm2 ⁇ 0.100.
  • the mesopore amount Vm1 is 0.300 cc / g or less, the BET specific surface area can be increased, and the doping amount of two or more kinds of alkali metal ions and / or alkaline earth metal ions can be increased.
  • the bulk density of the negative electrode can be increased.
  • the micropore amount Vm2 is 0.650 cc / g or less, high charge / discharge efficiency for the ions can be maintained.
  • the mesopore volume Vm1 and the micropore volume Vm2 are equal to or higher than the lower limit (0.010 ⁇ Vm1, 0.001 ⁇ Vm2), high input / output characteristics can be obtained.
  • the BET specific surface area of the composite carbon material 1a is preferably from 100 m 2 / g to 1,500 m 2 / g, more preferably from 150 m 2 / g to 1,100 m 2 / g, and even more preferably from 180 m 2 / g to 550 m. 2 / g or less. If this BET specific surface area is 100 m 2 / g or more, the pores can be appropriately maintained, and therefore, the diffusion of two or more kinds of alkali metal ions and / or alkaline earth metal ions becomes good. Input / output characteristics can be shown. Moreover, since the dope amount of the ions can be increased, the negative electrode can be thinned. On the other hand, since it is 1,500 m 2 / g or less, the charge / discharge efficiency of the ions is improved, so that the cycle durability is not impaired.
  • the average pore diameter of the composite carbon material 1a is preferably 20 mm or more, more preferably 25 mm or more, and further preferably 30 mm or more from the viewpoint of high input / output characteristics. On the other hand, from the viewpoint of high energy density, the average pore diameter is preferably 65 mm or less, more preferably 60 mm or less.
  • the average particle size of the composite carbon material 1a is preferably 1 ⁇ m or more and 10 ⁇ m or less. About a lower limit, More preferably, it is 2 micrometers or more, More preferably, it is 2.5 micrometers or more. About an upper limit, More preferably, it is 6 micrometers or less, More preferably, it is 4 micrometers or less. If the average particle diameter is 1 ⁇ m or more and 10 ⁇ m or less, good durability is maintained.
  • the hydrogen atom / carbon atom number ratio (H / C) of the composite carbon material 1a is preferably 0.05 or more and 0.35 or less, and more preferably 0.05 or more and 0.15 or less. .
  • H / C is 0.35 or less, the structure (typically polycyclic aromatic conjugated structure) of the carbonaceous material deposited on the activated carbon surface is well developed and the capacity (energy Density) and charge / discharge efficiency are increased.
  • H / C is 0.05 or more, since carbonization does not proceed excessively, a good energy density can be obtained.
  • H / C is measured by an elemental analyzer.
  • the composite carbon material 1a has an amorphous structure derived from the activated carbon of the base material, but at the same time has a crystal structure mainly derived from the deposited carbonaceous material.
  • the composite carbon material A has a (002) plane spacing d002 of 3.60 mm to 4.00 mm, and a c-axis direction crystallite obtained from the half width of this peak.
  • the size Lc is preferably 8.0 to 20.0 and d002 is 3.60 to 3.75 and the crystallite size Lc in the c-axis direction obtained from the half width of this peak is 11.
  • the range of 0 to 16.0 is more preferable.
  • the activated carbon used as the base material of the composite carbon material 1a is not particularly limited as long as the obtained composite carbon material 1a exhibits desired characteristics.
  • commercially available products obtained from various raw materials such as petroleum-based, coal-based, plant-based, and polymer-based materials can be used.
  • the average particle diameter is more preferably 2 ⁇ m or more and 10 ⁇ m or less.
  • the pore distribution of the activated carbon used for the substrate is important.
  • the amount of mesopores derived from pores having a diameter of 20 to 500 mm calculated by the BJH method is V1 (cc / g)
  • the amount of micropores derived from pores having a diameter of less than 20 mm calculated by the MP method is used.
  • V2 (cc / g) 0.050 ⁇ V1 ⁇ 0.500, 0.005 ⁇ V2 ⁇ 1.000, and 0.2 ⁇ V1 / V2 ⁇ 20.0 are preferable.
  • the mesopore amount V1 is more preferably 0.050 ⁇ V1 ⁇ 0.350, and further preferably 0.100 ⁇ V1 ⁇ 0.300.
  • the micropore amount V2 is more preferably 0.005 ⁇ V2 ⁇ 0.850, and further preferably 0.100 ⁇ V2 ⁇ 0.800.
  • the ratio of mesopore amount / micropore amount is more preferably 0.22 ⁇ V1 / V2 ⁇ 15.0, and further preferably 0.25 ⁇ V1 / V2 ⁇ 10.0.
  • the pore structure can be easily controlled.
  • the mesopore amount V1 of the activated carbon is 0.050 or more
  • the micropore amount V2 is 0.005 or more
  • V1 / V2 is 0.2 or more
  • V1 / V2 is 20.0.
  • the structure can be easily obtained even in the following cases.
  • the carbonaceous material precursor used as a raw material of the composite carbon material 1a is an organic material that can be dissolved in a solid, liquid, or solvent, which can deposit the carbonaceous material on activated carbon by heat treatment.
  • the carbonaceous material precursor include pitch, mesocarbon microbeads, coke, and synthetic resin (for example, phenol resin).
  • Pitch is roughly divided into petroleum pitch and coal pitch.
  • petroleum pitches include crude oil distillation residue, fluid catalytic cracking residue (decant oil, etc.), bottom oil derived from thermal crackers, ethylene tar obtained during naphtha cracking, and the like.
  • the pitch When the pitch is used, the pitch is heat-treated in the presence of activated carbon, and a carbonaceous material is deposited on the activated carbon by thermally reacting the volatile component or pyrolysis component of the pitch on the surface of the activated carbon. Material 1a is obtained.
  • the deposition of pitch volatile components or pyrolysis components into the activated carbon pores proceeds at a temperature of about 200 to 500 ° C., and the reaction that the deposited components become carbonaceous materials proceeds at 400 ° C. or higher.
  • the peak temperature (maximum temperature reached) during the heat treatment is appropriately determined depending on the characteristics of the composite carbon material 1a to be obtained, the thermal reaction pattern, the thermal reaction atmosphere, etc., but is preferably 400 ° C. or higher.
  • the softening point of the pitch used is preferably 30 ° C. or higher and 250 ° C. or lower, and more preferably 60 ° C. or higher and 130 ° C. or lower.
  • a pitch having a softening point of 30 ° C. or higher can be handled with high accuracy without any problem in handling properties.
  • the pitch having a softening point of 250 ° C. or less contains a large amount of relatively low molecular weight compounds. Therefore, when the pitch is used, fine pores in the activated carbon can be deposited.
  • activated carbon is heat-treated in an inert atmosphere containing hydrocarbon gas volatilized from a carbonaceous material precursor, and the carbonaceous material is coated in a gas phase.
  • the method of making it wear is mentioned.
  • a method in which activated carbon and a carbonaceous material precursor are mixed in advance and heat-treated, or a method in which a carbonaceous material precursor dissolved in a solvent is applied to activated carbon and dried is then heat-treated.
  • the mass ratio of the carbonaceous material to the activated carbon in the composite carbon material 1a is 10% or more and 100% or less. This mass ratio is preferably 15% or more and 80% or less. If the mass ratio of the carbonaceous material is 10% or more, the micropores possessed by the activated carbon can be appropriately filled with the carbonaceous material, and two or more kinds of alkali metal ions and / or alkaline earth metals can be filled. Since the charge / discharge efficiency of ions is improved, cycle durability is not impaired. Further, if the mass ratio of the carbonaceous material is 100% or less, the pores of the composite carbon material 1a are appropriately maintained and the specific surface area is maintained large. Therefore, from the result that the doping amount of two or more kinds of alkali metal ions and / or alkaline earth metal ions can be increased, high output density and high durability can be maintained even if the negative electrode is thinned.
  • the composite carbon material 1b is the composite carbon material using one or more carbon materials having a BET specific surface area of 0.5 m 2 / g or more and 80 m 2 / g or less as the base material.
  • the base material is not particularly limited, and natural graphite, artificial graphite, low crystal graphite, hard carbon, soft carbon, carbon black and the like can be suitably used.
  • BET specific surface area of the composite carbon material 1b, 1 m 2 / g or more 50 m 2 / g or less, more preferably 1.5 m 2 / g or more 40 m 2 / g or less, more preferably 2m 2 / g or more 25 m 2 / g or less. If the BET specific surface area is 1 m 2 / g or more, a sufficient reaction field with two or more kinds of alkali metal ions and / or alkaline earth metal ions can be secured, and thus high input / output characteristics can be exhibited.
  • the average particle size of the composite carbon material 1b is preferably 1 ⁇ m or more and 10 ⁇ m or less.
  • the average particle diameter is more preferably 2 ⁇ m or more and 8 ⁇ m or less, and further preferably 3 ⁇ m or more and 6 ⁇ m or less. If the average particle diameter is 1 ⁇ m or more, the charge / discharge efficiency of two or more kinds of alkali metal ions and / or alkaline earth metal ions can be improved, and thus high cycle durability can be exhibited. On the other hand, if it is 10 ⁇ m or less, the reaction area between the composite carbon material 1b and the non-aqueous electrolyte increases, so that high input / output characteristics can be exhibited.
  • the mass ratio of the carbonaceous material is 20% or less, two or more kinds of alkali metal ions and / or alkaline earth metal ions between the carbonaceous material and the base material are favorably diffused in the solid. Since it can be held, high input / output characteristics can be exhibited. Moreover, since the charge / discharge efficiency of the ions can be improved, high cycle durability can be exhibited.
  • the doping amount of lithium ions per unit mass of the composite carbon material 1b is preferably 50 mAh / g or more and 700 mAh / g or less, more preferably 70 mAh / g or more and 650 mAh / g or less, and further preferably 90 mAh / g or more and 600 mAh. / G or less, particularly preferably 100 mAh / g or more and 550 mAh / g or less.
  • the negative electrode potential is lowered.
  • the negative electrode containing the composite carbon material 1b doped with the ions when the negative electrode containing the composite carbon material 1b doped with the ions is combined with the positive electrode, the voltage of the non-aqueous alkali metal ion capacitor is increased and the utilization capacity of the positive electrode is increased. Therefore, the capacity and energy density of the obtained non-aqueous alkali metal ion capacitor are increased.
  • the doping amount is 50 mAh / g or more, the ions are good even at irreversible sites that cannot be desorbed once the alkali metal ions and / or alkaline earth metal ions in the composite carbon material 1b are once inserted. Since it is doped, a high energy density is obtained. The larger the doping amount, the lower the negative electrode potential, and the input / output characteristics, energy density, and durability are improved.
  • the doping amount of lithium ions is 700 mAh / g or less, there is no possibility that side effects such as precipitation of alkali metal occur.
  • the composite carbon material 1b using a graphite material as the base material will be described.
  • the average particle size of the composite carbon material 1b is preferably 1 ⁇ m or more and 10 ⁇ m or less.
  • the average particle diameter is more preferably 2 ⁇ m or more and 8 ⁇ m or less, and further preferably 3 ⁇ m or more and 6 ⁇ m or less. If the average particle diameter is 1 ⁇ m or more, the charge / discharge efficiency of two or more kinds of alkali metal ions and / or alkaline earth metal ions can be improved, and thus high cycle durability can be exhibited. On the other hand, if it is 10 ⁇ m or less, the reaction area between the composite carbon material 1b and the non-aqueous electrolyte increases, so that high input / output characteristics can be exhibited.
  • the BET specific surface area of the composite carbon material 1b is preferably 1 m 2 / g or more and 20 m 2 / g or less, more preferably 1 m 2 / g or more and 15 m 2 / g or less. If the BET specific surface area is 1 m 2 / g or more, a sufficient reaction field with two or more kinds of alkali metal ions and / or alkaline earth metal ions can be secured, and thus high input / output characteristics can be exhibited.
  • the graphite material used as the substrate is not particularly limited as long as the obtained composite carbon material 1b exhibits desired characteristics.
  • artificial graphite, natural graphite, graphitized mesophase carbon spherules, graphite whiskers and the like can be used.
  • the average particle diameter of the graphite material is preferably 1 ⁇ m or more and 10 ⁇ m or less, more preferably 2 ⁇ m or more and 8 ⁇ m or less.
  • the carbonaceous material precursor used as a raw material of the composite carbon material 1b is an organic material that can be dissolved in a solid, liquid, or solvent that can be composited with a graphite material by heat treatment.
  • the carbonaceous material precursor include pitch, mesocarbon microbeads, coke, and synthetic resin (for example, phenol resin).
  • Pitch is roughly divided into petroleum pitch and coal pitch.
  • petroleum pitches include crude oil distillation residue, fluid catalytic cracking residue (decant oil, etc.), bottom oil derived from thermal crackers, ethylene tar obtained during naphtha cracking, and the like.
  • the mass ratio of the carbonaceous material to the graphite material in the composite carbon material 1b is preferably 1% or more and 10% or less. This mass ratio is more preferably 1.2% or more and 8% or less, further preferably 1.5% or more and 6% or less, and particularly preferably 2% or more and 5% or less. If the mass ratio of the carbonaceous material is 1% or more, the carbonaceous material can sufficiently increase the reaction sites with two or more kinds of alkali metal ions and / or alkaline earth metal ions, and removes the ions. Since the sum is easy, high input / output characteristics can be exhibited.
  • the mass ratio of the carbonaceous material is 20% or less, the diffusion of the ions in the solid between the carbonaceous material and the graphite material can be favorably maintained, so that high input / output characteristics can be exhibited. Moreover, since the charge / discharge efficiency of the ions can be improved, high cycle durability can be exhibited.
  • the negative electrode active material layer in the present invention may contain optional components such as a conductive filler, a binder, and a dispersion stabilizer in addition to the negative electrode active material as necessary.
  • the type of the conductive filler is not particularly limited, and examples thereof include acetylene black, ketjen black, and vapor grown carbon fiber.
  • the amount of the conductive filler used is preferably 0 parts by mass or more and 30 parts by mass or less, more preferably 0 parts by mass or more and 20 parts by mass or less, further preferably more than 0 parts by mass with respect to 100 parts by mass of the negative electrode active material. 15 parts by mass or less.
  • the binder is not particularly limited. For example, PVdF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), polyimide, latex, styrene-butadiene copolymer, fluororubber, acrylic copolymer, etc.
  • the amount of the binder used is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 27 parts by mass or less, and further preferably 3 parts by mass or more with respect to 100 parts by mass of the negative electrode active material. 25 parts by mass or less.
  • the amount of the binder is 1% by mass or more, sufficient electrode strength is exhibited.
  • the amount of the binder is 30 parts by mass or less, high input / output characteristics are exhibited without inhibiting the entry and exit of alkali metal ions and / or alkaline earth metal ions into the negative electrode active material.
  • a dispersion stabilizer for example, PVP (polyvinyl pyrrolidone), PVA (polyvinyl alcohol), a cellulose derivative etc. can be used.
  • the amount of the dispersion stabilizer used is preferably 0 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material. When the amount of the dispersion stabilizer is 10 parts by mass or less, high input / output characteristics are exhibited without inhibiting the entry and exit of alkali metal ions and / or alkaline earth metal ions into the negative electrode active material.
  • the material constituting the negative electrode current collector in the present invention is preferably a metal foil that has high electron conductivity and does not deteriorate due to elution into the electrolytic solution and reaction with the electrolyte or ions.
  • a metal foil that has high electron conductivity and does not deteriorate due to elution into the electrolytic solution and reaction with the electrolyte or ions.
  • metal foil For example, aluminum foil, copper foil, nickel foil, stainless steel foil, etc. are mentioned.
  • the negative electrode current collector in the non-aqueous alkali metal ion capacitor of the first and second embodiments is preferably a copper foil.
  • the metal foil may be a normal metal foil having no irregularities or through holes, or a metal foil having irregularities subjected to embossing, chemical etching, electrolytic deposition, blasting, etc., expanded metal, punching metal Alternatively, a metal foil having a through hole such as an etching foil may be used.
  • the thickness of the negative electrode current collector is not particularly limited as long as the shape and strength of the negative electrode can be sufficiently maintained, but for example, 1 to 100 ⁇ m is preferable.
  • the negative electrode has a negative electrode active material layer on one side or both sides of a negative electrode current collector.
  • the negative electrode active material layer is fixed to the negative electrode current collector.
  • the negative electrode can be manufactured by an electrode manufacturing technique in a known lithium ion battery, electric double layer capacitor or the like. For example, various materials including a negative electrode active material are dispersed or dissolved in water or an organic solvent to prepare a slurry-like coating liquid, and this coating liquid is applied to one or both surfaces on a negative electrode current collector.
  • a negative electrode can be obtained by forming a coating film and drying it. Further, the obtained negative electrode may be pressed to adjust the film thickness and bulk density of the negative electrode active material layer.
  • the viscosity ( ⁇ b) of the coating solution is preferably 1,000 mPa ⁇ s to 20,000 mPa ⁇ s, more preferably 1,500 mPa ⁇ s to 10,000 mPa ⁇ s, and still more preferably 1,700 mPa ⁇ s. It is 5,000 mPa ⁇ s or less.
  • the viscosity ( ⁇ b) is 1,000 mPa ⁇ s or more, dripping at the time of coating film formation is suppressed, and the coating film width and thickness can be controlled well.
  • the coating film may be formed by single layer coating or may be formed by multilayer coating.
  • the coating speed is preferably from 0.1 m / min to 100 m / min, more preferably from 0.5 m / min to 70 m / min, still more preferably from 1 m / min to 50 m / min. If the coating speed is 0.1 m / min or more, stable coating can be achieved. On the other hand, if it is 100 m / min or less, sufficient coating accuracy can be secured.
  • the drying of the coating film is not particularly limited, a drying method such as hot air drying or infrared (IR) drying can be preferably used.
  • the coating film may be dried at a single temperature or may be dried by changing the temperature in multiple stages. Moreover, you may dry combining several drying methods.
  • the drying temperature is preferably 25 ° C. or higher and 200 ° C. or lower, more preferably 40 ° C. or higher and 180 ° C. or lower, and further preferably 50 ° C. or higher and 160 ° C. or lower. When the drying temperature is 25 ° C. or higher, the solvent in the coating film can be sufficiently volatilized.
  • the press of the negative electrode is not particularly limited, a press such as a hydraulic press or a vacuum press can be preferably used.
  • the film thickness, bulk density, and electrode strength of the negative electrode active material layer can be adjusted by the press pressure, gap, and surface temperature of the press part described later.
  • the pressing pressure is preferably 0.5 kN / cm or more and 20 kN / cm or less, more preferably 1 kN / cm or more and 10 kN / cm or less, and further preferably 2 kN / cm or more and 7 kN / cm or less. If the pressing pressure is 0.5 kN / cm or more, the electrode strength can be sufficiently increased. On the other hand, if it is 20 kN / cm or less, the negative electrode is not bent or wrinkled, and can be adjusted to the desired negative electrode active material layer thickness and bulk density. In addition, the gap between the press rolls can be set to an arbitrary value according to the negative electrode film thickness after drying so as to be a desired film thickness or bulk density of the negative electrode active material layer.
  • PVdF polyvinylidene fluoride: melting point 150 ° C.
  • it is preferably heated to 90 ° C. or higher and 200 ° C. or lower, more preferably 105 ° C. or higher and 180 ° C. or lower, and still more preferably 120 ° C. or higher. Heating to 170 ° C. or lower.
  • a styrene-butadiene copolymer melting point 100 ° C.
  • it is preferably heated to 40 ° C. or higher and 150 ° C. or lower, more preferably 55 ° C. or higher and 130 ° C. or lower, and still more preferably 70 ° C. It is heating up to 120 ° C. or higher.
  • the thickness of the negative electrode active material layer in the case where the current collector has through-holes or irregularities refers to the average value of the thickness of one side of the current collector that does not have through-holes or irregularities.
  • the bulk density of the negative electrode active material layer is preferably 0.30 g / cm 3 or more and 1.8 g / cm 3 or less, more preferably 0.40 g / cm 3 or more and 1.5 g / cm 3 or less, and still more preferably 0. .45g / cm 3 or more 1.3g / cm 3 or less.
  • the bulk density is 0.30 g / cm 3 or more, sufficient strength can be maintained and sufficient conductivity between the negative electrode active materials can be exhibited.
  • the BET specific surface area, mesopore volume, and micropore volume in the present invention are values determined by the following methods, respectively.
  • the sample is vacuum-dried at 200 ° C. all day and night, and adsorption and desorption isotherms are measured using nitrogen as an adsorbate.
  • the BET specific surface area is calculated by the BET multipoint method or the BET single point method
  • the mesopore amount is calculated by the BJH method
  • the micropore amount is calculated by the MP method.
  • the BJH method is a calculation method generally used for analysis of mesopores, and was proposed by Barrett, Joyner, Halenda et al. (Non-patent Document 1).
  • the MP method means a method for obtaining the micropore volume, the micropore area, and the micropore distribution using the “t-plot method” (Non-Patent Document 2). This is a method devised by Mikhal, Brunauer, and Bodor (Non-patent Document 3).
  • the positive electrode precursor and the negative electrode are laminated or wound via a separator to form an electrode laminate having the positive electrode precursor, the negative electrode, and the separator.
  • a separator a polyethylene microporous film or a polypropylene microporous film used in a lithium ion secondary battery, a cellulose nonwoven paper used in an electric double layer capacitor, or the like can be used.
  • a film made of organic or inorganic fine particles may be laminated on one side or both sides of these separators. Further, organic or inorganic fine particles may be contained inside the separator.
  • the thickness of the separator is preferably 5 ⁇ m or more and 35 ⁇ m or less.
  • a thickness of 5 ⁇ m or more is preferable because self-discharge due to internal micro-shorts tends to be small. On the other hand, a thickness of 35 ⁇ m or less is preferable because the output characteristics of the electricity storage element tend to be high.
  • the film made of organic or inorganic fine particles is preferably 1 ⁇ m to 10 ⁇ m. A thickness of 1 ⁇ m or more is preferable because self-discharge due to internal micro-shorts tends to be small. On the other hand, the thickness of 10 ⁇ m or less is preferable because the output characteristics of the electricity storage element tend to be high.
  • a metal can, a laminate film, or the like can be used as the exterior body.
  • the metal can is preferably made of aluminum.
  • As the laminate film a film in which a metal foil and a resin film are laminated is preferable, and an example of a three-layer structure composed of an outer layer resin film / metal foil / interior resin film is exemplified.
  • the outer layer resin film is for preventing the metal foil from being damaged by contact or the like, and a resin such as nylon or polyester can be suitably used.
  • the metal foil is for preventing the permeation of moisture and gas, and foils of copper, aluminum, stainless steel and the like can be suitably used.
  • the interior resin film protects the metal foil from the electrolyte contained in the interior, and melts and seals the exterior body during heat sealing. Polyolefin, acid-modified polyolefin, and the like can be suitably used.
  • alkali metal ion ions are contained in the electrolyte solution of a non-aqueous alkali metal ion capacitor, and 2 or more types and 4 or less types of alkali metal ions are contained. More preferably it is included.
  • an alkali metal ion insertion / desorption reaction proceeds on the surface of the positive electrode activated carbon.
  • the alkali metal ions having a large ionic radius expand the pores of the activated carbon, so that the alkali metal ions having a small ionic radius are more efficient.
  • the insertion / elimination reaction can be performed and the high output characteristics are improved.
  • the substance amount ratio of the first alkali metal ion in the non-aqueous electrolyte is 1% or more and 99% or less, and the substance amount ratio of the second alkali metal ion is 1% or more and 99% or less
  • the mass ratio of the third and fourth alkali metal ions is preferably 0% or more and 98% or less. More preferably, the substance amount ratio of the first alkali metal ions in the non-aqueous electrolyte is 3% or more and 97% or less, and the substance amount ratio of the second alkali metal ions is 3% or more and 97% or less,
  • the substance amount ratio of the third and fourth alkali metal ions is 0% or more and 94% or less.
  • the substance amount ratio of the first alkali metal ions in the non-aqueous electrolyte is 5% or more and 95% or less, and the substance amount ratio of the second alkali metal ions is 5% or more and 95% or less,
  • the substance amount ratio of the third and fourth alkali metal ions is 0% or more and 90% or less. More preferably, the substance amount ratio of the third and fourth alkali metal ions is 1% to 90%, or 5% to 90%.
  • Two or more alkali metal ions may be present in the electrolytic solution, and three or more alkali metal ions may be included. It is preferable that each alkali metal ion is contained in an amount of 1% or more because ions involved in expanding and charging / discharging the pores of the activated carbon can act.
  • the method for containing different alkali metal ions in the electrolytic solution is not particularly limited, and two or more kinds of alkali metal salts can be dissolved in the electrolytic solution, and two or more kinds of alkali metal compounds can be contained in the positive electrode or the negative electrode. It can be contained and redox-decomposed, or an alkali metal salt to be dissolved in the electrolytic solution and an alkali metal compound to be contained in the positive electrode or the negative electrode and redox-decomposed can be used.
  • the method of adding a plurality of alkali metal compounds (compounds 1 to 4) to the positive electrode precursor and performing oxidation-reduction decomposition is particularly preferable because a plurality of alkali metal ions can be contained in the electrolytic solution.
  • the non-aqueous electrolyte solution in the first and second embodiments is, for example, (MN (SO 2 F) 2 ), MN (SO 2 CF 3 ) 2 , MN (SO 2 C 2 F 5 ) as an alkali metal salt.
  • M is an alkali selected from Li, Na, K, Rb, Cs independently of each other
  • Metal may be used alone, or two or more may be used in combination. It is preferable to include MPF 6 and / or MN (SO 2 F) 2 because high conductivity can be expressed.
  • the positive electrode exhibits a capacity by the electric double layer formed at the interface of the positive electrode active material. For this reason, the capacity
  • the electrolytic solution in the second embodiment of the present invention is a non-aqueous electrolytic solution containing alkali metal ions and alkaline earth metal ions.
  • the non-aqueous electrolyte contains a non-aqueous solvent described later.
  • the non-aqueous electrolyte solution preferably contains 0.5 mol / L or more of an alkali metal salt and / or an alkaline earth metal salt based on the total volume of the non-aqueous electrolyte solution.
  • M is independently from Li, Na, K, Rb and Cs
  • An alkali metal selected from the group consisting of: a single group, or a mixture of two or more types.
  • the non-aqueous electrolyte preferably contains MPF 6 and / or MN (SO 2 F) 2 because high conductivity can be expressed.
  • the non-aqueous electrolyte solution in the second embodiment of the present invention is, for example, M [N (SO 2 F) 2 ] 2 , M [N (SO 2 CF 3 ) 2 ] 2 , M as an alkaline earth metal salt.
  • the nonaqueous electrolytic solution preferably contains M (PF 6 ) 2 and / or M [N (SO 2 F) 2 ] 2 .
  • an alkaline earth metal salt can be used alone when preparing the non-aqueous electrolyte, or when the alkaline earth metal compound is contained in the positive electrode precursor.
  • the alkali metal salt can be used alone when preparing the non-aqueous electrolyte.
  • 1 or more types of alkali metal ion and alkaline-earth metal ion can each exist in the non-aqueous electrolyte solution after a pre dope.
  • the non-aqueous electrolyte after pre-doping contains at least one selected from the group consisting of lithium ions, sodium ions and potassium ions as alkali metal ions, and / or as alkaline earth metal ions, Preferably, calcium ions are included.
  • X / (X + Y) is 0.07. It is preferable that it is 0.92 or less. If X / (X + Y) is 0.07 or more, a sufficient amount of alkali metal ions are present in the nonaqueous electrolytic solution, so that the resistance of the energy storage device can be reduced. When X / (X + Y) is 0.92 or less, a sufficient amount of alkaline earth metal ions are present in the nonaqueous electrolytic solution, so that the capacity of the energy storage device can be increased. X / (X + Y) is more preferably 0.09 or more and less than 0.93, and still more preferably 0.10 or more and 0.90 or less.
  • the concentration of the alkali metal salt and / or alkaline earth metal salt in the non-aqueous electrolyte is preferably 0.5 mol / L or more, more preferably in the range of 0.5 to 2.0 mol / L. preferable.
  • the total value is preferably in the range of 0.5 to 2.0 mol / L. If the concentration of the alkali metal salt and / or alkaline earth metal salt is 0.5 mol / L or more, since the anion is sufficiently present, the capacity of the energy storage device can be sufficiently increased.
  • the concentration of the alkali metal salt and / or alkaline earth metal salt is 2.0 mol / L or less, the undissolved alkali metal salt and / or alkaline earth metal salt is deposited in the non-aqueous electrolyte. And the viscosity of the electrolyte solution can be prevented from becoming too high, the conductivity is not lowered, and the output characteristics are not lowered.
  • the nonaqueous electrolytic solution preferably contains a cyclic carbonate and a chain carbonate as a nonaqueous solvent.
  • the nonaqueous electrolytic solution containing a cyclic carbonate and a chain carbonate is advantageous in that a desired concentration of an alkali metal salt is dissolved and a high alkali metal ion conductivity is exhibited.
  • the cyclic carbonate include alkylene carbonate compounds represented by ethylene carbonate, propylene carbonate, butylene carbonate, and the like. The alkylene carbonate compound is typically unsubstituted.
  • Examples of the chain carbonate include dialkyl carbonate compounds represented by dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, dibutyl carbonate and the like.
  • the dialkyl carbonate compound is typically unsubstituted.
  • the lower limit of the total content of the cyclic carbonate and the chain carbonate is preferably 50% by mass or more, more preferably 65% by mass or more, based on the total amount of the nonaqueous electrolytic solution.
  • the upper limit of the total content is preferably 95% by mass or less, more preferably 90% by mass or less, based on the total amount of the non-aqueous electrolyte solution.
  • electrolyte solution can further contain the additive mentioned later.
  • 1,4-butane sultone, 1,3-butane sultone or 2,4-pentane sultone is preferable.
  • unsaturated cyclic sultone compound 1,3-propene sultone or 1,4-butene sultone is preferable, and as other sultone compounds, Are methylene bis (benzenesulfonic acid), methylene bis (phenylmethanesulfonic acid), methylene bis (ethanesulfonic acid), methylene bis (2,4,6, trimethylbenzenesulfonic acid), and methylene bis (2-trifluoromethylbenzenesulfonic acid). Or you can mention It is preferable to select at least one selected.
  • the total content of sultone compounds in the non-aqueous electrolyte solution of the non-aqueous alkali metal ion capacitor is preferably 0.1% by mass to 15% by mass based on the total amount of the non-aqueous electrolyte solution. If the total content of sultone compounds in the non-aqueous electrolyte solution is 0.1% by mass or more, it is possible to suppress gas generation by suppressing decomposition of the electrolyte solution at a high temperature. On the other hand, if the total content is 15% by mass or less, a decrease in the ionic conductivity of the electrolytic solution can be suppressed, and high input / output characteristics can be maintained.
  • the content of the sultone compound present in the non-aqueous electrolyte of the non-aqueous alkali metal ion capacitor is preferably 0.5% by mass or more and 10% by mass or less from the viewpoint of achieving both high input / output characteristics and durability. More preferably, it is 1 mass% or more and 5 mass% or less.
  • the cyclic phosphazene include ethoxypentafluorocyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, and the like, and one or more selected from these are preferable.
  • the content of cyclic phosphazene in the non-aqueous electrolyte is preferably 0.5% by mass to 20% by mass based on the total amount of the non-aqueous electrolyte. If this value is 0.5% by mass or more, it is possible to suppress gas generation by suppressing decomposition of the electrolyte solution at high temperatures. On the other hand, if this value is 20% by mass or less, a decrease in the ionic conductivity of the electrolytic solution can be suppressed, and high input / output characteristics can be maintained.
  • the content of cyclic phosphazene is preferably 2% by mass or more and 15% by mass or less, and more preferably 4% by mass or more and 12% by mass or less.
  • cyclic phosphazenes may be used alone or in combination of two or more.
  • acyclic fluorine-containing ether examples include HCF 2 CF 2 OCH 2 CF 2 CF 2 H, CF 3 CFHCF 2 OCH 2 CF 2 CF 2 H, HCF 2 CF 2 CH 2 OCH 2 CF 2 CF 2 H, and CF 3 CFHCF.
  • 2 OCH 2 CF 2 CFHCF 3 and the like are mentioned, and among them, HCF 2 CF 2 OCH 2 CF 2 CF 2 H is preferable from the viewpoint of electrochemical stability.
  • the content of the non-cyclic fluorine-containing ether is preferably 0.5% by mass or more and 15% by mass or less, and more preferably 1% by mass or more and 10% by mass or less, based on the total amount of the non-aqueous electrolyte solution.
  • the content of the non-cyclic fluorine-containing ether is 0.5% by mass or more, the stability of the non-aqueous electrolyte solution against oxidative decomposition is improved, and an electricity storage device having high durability at high temperatures can be obtained.
  • the content of the non-cyclic fluorine-containing ether is 15% by mass or less, the solubility of the electrolyte salt can be kept good, and the ionic conductivity of the non-aqueous electrolyte can be kept high. It is possible to develop input / output characteristics.
  • the acyclic fluorine-containing ether may be used alone or in combination of two or more.
  • the fluorine-containing cyclic carbonate is preferably selected from fluoroethylene carbonate (FEC) and difluoroethylene carbonate (dFEC) from the viewpoint of compatibility with other nonaqueous solvents.
  • the content of the cyclic carbonate containing a fluorine atom is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 5% by mass or less, based on the total amount of the non-aqueous electrolyte solution. .
  • the content of the cyclic carbonate containing a fluorine atom is 0.5% by mass or more, a good-quality film can be formed on the negative electrode, and by suppressing the reductive decomposition of the electrolytic solution on the negative electrode, A highly durable power storage element can be obtained.
  • the content of the cyclic carbonate containing a fluorine atom is 10% by mass or less, the solubility of the electrolyte salt can be kept good, and the ionic conductivity of the non-aqueous electrolyte can be kept high. It is possible to develop advanced input / output characteristics.
  • the cyclic carbonate containing a fluorine atom may be used alone or in combination of two or more.
  • the content of the cyclic carbonate is preferably 0.5% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less, based on the total amount of the nonaqueous electrolytic solution. If the content of the cyclic carbonate is 0.5% by mass or more, a good-quality film on the negative electrode can be formed, and by suppressing the reductive decomposition of the electrolyte solution on the negative electrode, durability at high temperatures can be achieved. A high power storage element can be obtained.
  • the solubility of the electrolyte salt can be kept good, and the ionic conductivity of the non-aqueous electrolyte can be kept high, so that high input / output characteristics can be obtained.
  • the cyclic carboxylic acid ester include gamma butyrolactone, gamma valerolactone, gamma caprolactone, epsilon caprolactone, and the like, and it is preferable to use one or more selected from these.
  • gamma-butyrolactone is particularly preferable from the viewpoint of improving battery characteristics resulting from an improvement in the degree of dissociation of alkali metal ions.
  • the content of the cyclic carboxylic acid ester is preferably 0.5% by mass or more and 15% by mass or less, and more preferably 1% by mass or more and 5% by mass or less, based on the total amount of the nonaqueous electrolytic solution. If the content of the cyclic acid anhydride is 0.5% by mass or more, a high-quality film on the negative electrode can be formed, and by suppressing reductive decomposition of the electrolytic solution on the negative electrode, durability at high temperatures Can be obtained.
  • the content of the cyclic carboxylic acid ester is 5% by mass or less, the solubility of the electrolyte salt can be kept good, and the ionic conductivity of the non-aqueous electrolyte can be kept high, so that a high degree of input / output is possible. It becomes possible to express characteristics.
  • the said cyclic carboxylic acid ester may be used individually, or 2 or more types may be mixed and used for it.
  • the cyclic acid anhydride is preferably at least one selected from succinic anhydride, maleic anhydride, citraconic anhydride, and itaconic anhydride. Among them, it is preferable to select from succinic anhydride and maleic anhydride from the viewpoint that the production cost of the electrolytic solution can be suppressed due to industrial availability and that the electrolytic solution can be easily dissolved in the non-aqueous electrolytic solution.
  • the content of the cyclic acid anhydride is preferably 0.5% by mass or more and 15% by mass or less, and more preferably 1% by mass or more and 10% by mass or less, based on the total amount of the nonaqueous electrolytic solution.
  • the content of the cyclic acid anhydride is 0.5% by mass or more, a high-quality film can be formed on the negative electrode, and by suppressing the reductive decomposition of the electrolyte solution on the negative electrode, durability at high temperatures can be achieved. A high power storage element can be obtained.
  • the content of the cyclic acid anhydride is 10% by mass or less, the solubility of the electrolyte salt can be kept good, and the ionic conductivity of the non-aqueous electrolyte can be kept high, so that a high degree of input / output is possible. It becomes possible to express characteristics.
  • the said cyclic acid anhydride may be used individually, or 2 or more types may be mixed and used for it.
  • the electrode laminate obtained in the assembly process is obtained by connecting a positive electrode terminal and a negative electrode terminal to a laminate obtained by laminating a positive electrode precursor and a negative electrode cut into a sheet shape via a separator.
  • the electrode winding body is obtained by connecting a positive electrode terminal and a negative electrode terminal to a winding body obtained by winding a positive electrode precursor and a negative electrode through a separator.
  • the shape of the electrode winding body may be a cylindrical shape or a flat shape.
  • a method for connecting the positive electrode terminal and the negative electrode terminal is not particularly limited, but a method such as resistance welding or ultrasonic welding can be used. It is preferable to remove the residual solvent by drying the electrode laminate or the electrode winding body to which the terminals are connected.
  • the drying method it dries by vacuum drying etc.
  • the residual solvent is preferably 1.5% or less per weight of the positive electrode active material layer or the negative electrode active material layer. If the residual solvent is more than 1.5%, the solvent remains in the system and deteriorates the self-discharge characteristics, which is not preferable.
  • the dried electrode laminate or electrode wound body is preferably housed in an exterior body typified by a metal can or laminate film in a dry environment with a dew point of ⁇ 40 ° C. or less, leaving only one opening. It is preferable to seal in a closed state.
  • the sealing method of an exterior body is not specifically limited, Methods, such as heat sealing and impulse sealing, can be used.
  • the non-aqueous alkali metal ion capacitor after injection is placed in a decompression chamber with the exterior body opened, and the inside of the chamber is decompressed using a vacuum pump. And a method of returning to atmospheric pressure again can be used. After completion of the impregnation step, the nonaqueous alkali metal ion capacitor with the exterior body opened is sealed while being decompressed.
  • an alkali in the positive electrode precursor is decomposed by applying a voltage between the positive electrode precursor and the negative electrode to decompose the alkali metal compound and / or alkaline earth metal compound.
  • a negative electrode active material by decomposing a metal compound and / or alkaline earth metal compound to release alkali metal ions and / or alkaline earth metal ions and reducing the alkali metal ions and / or alkaline earth metal ions at the negative electrode
  • the layer is pre-doped with alkali metal ions and / or alkaline earth metal ions.
  • the non-aqueous alkali metal ion capacitor After completion of the alkali metal doping step.
  • the solvent in the electrolytic solution is decomposed at the positive electrode and the negative electrode, and an alkali metal ion and / or alkaline earth metal ion permeable solid polymer film is formed on the surfaces of the positive electrode and the negative electrode.
  • the aging method is not particularly limited, and for example, a method of reacting a solvent in an electrolytic solution under a high temperature environment can be used.
  • the degassing process After the aging step is completed, it is preferable to further degas to reliably remove the gas remaining in the electrolytic solution, the positive electrode, and the negative electrode. In the state where gas remains in at least a part of the electrolytic solution, the positive electrode, and the negative electrode, ion conduction is inhibited, and thus the resistance of the obtained nonaqueous alkali metal ion capacitor is increased.
  • the degassing method is not particularly limited. For example, a method in which a non-aqueous alkali metal ion capacitor is placed in a decompression chamber with the exterior body opened, and the inside of the chamber is decompressed using a vacuum pump, etc. Can be used.
  • the capacitance F (F) is a value obtained by the following method: First, constant-current charging is performed in a thermostatic chamber in which a cell corresponding to a non-aqueous alkali metal ion capacitor is set to 25 ° C. until reaching 3.8 V at a current value of 2 C, and then a constant voltage of 3.8 V is applied. The applied constant voltage charge is performed for a total of 30 minutes. Then, let Q (C) be the capacity when constant current discharge is performed at a current value of 2C up to 2.2V.
  • the C rate of current refers to a current value at which discharge is completed in one hour when constant current discharge is performed from the upper limit voltage to the lower limit voltage.
  • the current value at which discharge is completed in 1 hour is defined as 1C.
  • the internal resistance Ra ( ⁇ ) is a value obtained by the following method, respectively: First, constant-current charging in which a non-aqueous alkali metal ion capacitor is set in a thermostat set at 25 ° C. until reaching 3.8 V at a current value of 20 C, followed by constant-voltage charging in which a constant voltage of 3.8 V is applied. For a total of 30 minutes. Subsequently, the sampling interval is set to 0.1 second, and a constant current discharge is performed up to 2.2 V at a current value of 20 C to obtain a discharge curve (time-voltage).
  • the amount of gas generated during the high temperature storage test is measured by the following method: First, in a thermostatic chamber set at 25 ° C. with a cell corresponding to a non-aqueous alkali metal ion capacitor, constant current charging is performed until the voltage reaches 100 V at a current value of 100 C, and then a constant voltage of 4.0 V is applied. Perform constant voltage charging for 10 minutes. Thereafter, the cell is stored in a 60 ° C. environment, taken out from the 60 ° C. environment every two weeks, charged to a cell voltage of 4.0 V in the above charging step, and then stored again in the 60 ° C. environment. .
  • the resistance value obtained using the same measurement method as that for the room temperature internal resistance is defined as the internal resistance after the high-temperature storage test.
  • Rb / Ra is 3.0 or less from the viewpoint of developing sufficient charge capacity and discharge capacity for a large current when exposed to a high temperature environment for a long time. Preferably, it is 1.5 or less, more preferably 1.2 or less. If Rc / Ra is equal to or less than the above upper limit value, excellent output characteristics can be obtained stably for a long period of time, leading to a longer life of the device.
  • the value B obtained by normalizing the amount of gas generated when stored for 2 months at a cell voltage of 4.0 V and an environmental temperature of 60 ° C. by the capacitance Fa deteriorates the characteristics of the element due to the generated gas.
  • the value measured at 25 ° C. is preferably 30 ⁇ 10 ⁇ 3 cc / F or less, more preferably 15 ⁇ 10 ⁇ 3 cc / F or less, and further preferably 5 ⁇ 10 10. -3 cc / F or less. If the amount of gas generated under the above conditions is less than or equal to the above upper limit value, there is no possibility that the cell expands due to gas generation even when the device is exposed to a high temperature for a long time. Therefore, a power storage element having sufficient safety and durability can be obtained.
  • the capacity maintenance rate after the high load charge / discharge cycle test is measured by the following method: First, constant-current charging is performed until the temperature reaches 3.8 V at a current value of 200 C in a thermostatic chamber set to 25 ° C. with a cell corresponding to the non-aqueous alkali metal ion capacitor, and then 2.2 V at a current value of 200 C. The constant current discharge is performed until it reaches. The charging / discharging process is repeated 60000 times, and after reaching a voltage of 4.5 V at a current value of 20 C, charging is performed at a constant voltage for 1 hour.
  • Fb is obtained by measuring the capacitance by the above-mentioned method, and the capacity maintenance ratio after the high load charge / discharge cycle test with respect to before the test is obtained by comparing with Fc before the test is started. It is done. At this time, it is preferable that Fb / Fa is 1.01 or more because, for example, a sufficient amount of energy can be taken out even in a power storage element that has been charged and discharged for a long period of time, so that the replacement cycle of the power storage element can be extended. .
  • the identification method of the alkali metal compound contained in a positive electrode is not specifically limited, For example, it can identify by the following method. For identification of an alkali metal compound and / or an alkaline earth metal compound, it is preferable to identify by combining a plurality of analysis methods described below. When measuring the SEM-EDX, Raman, and XPS described below, the nonaqueous alkaline metal ion capacitor is disassembled in an argon box, the positive electrode is taken out, and the electrolyte attached to the positive electrode surface is washed before the measurement is performed. Is preferred.
  • the method for cleaning the positive electrode it is only necessary to wash away the electrolyte adhering to the surface of the positive electrode. Therefore, carbonate solvents such as dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate can be suitably used.
  • the positive electrode is immersed in a diethyl carbonate solvent 50 to 100 times the weight of the positive electrode for 10 minutes or more, and then the solvent is changed and the positive electrode is immersed again.
  • the positive electrode is taken out from diethyl carbonate and dried in a vacuum (temperature: 0 to 200 ° C., pressure: 0 to 20 kPa, time: 1 to 40 hours, so that the residual amount of diethyl carbonate in the positive electrode is 1% by mass or less.
  • the residual amount of diethyl carbonate can be determined based on a calibration curve prepared in advance by measuring the GC / MS of water after washing with distilled water and adjusting the liquid volume, which will be described later. -Perform EDX, Raman and XPS analysis.
  • anions can be identified by analyzing the water after washing the positive electrode with distilled water.
  • ICP emission spectroscopic analysis ICP-OES, ICP-MS, or the like, an alkali metal and / or alkaline earth metal element can be identified.
  • the alkali metal compound and / or alkaline earth metal compound containing oxygen and the positive electrode active material can be discriminated by oxygen mapping using a SEM-EDX image of the positive electrode surface measured at an observation magnification of 1000 to 4000 times.
  • the acceleration voltage is 10 kV
  • the emission current is 1 ⁇ A
  • the number of measurement pixels is 256 ⁇ 256 pixels
  • the number of integration can be measured 50 times.
  • gold, platinum, osmium, or the like can be surface-treated by a method such as vacuum deposition or sputtering.
  • the luminance and contrast are adjusted so that there is no pixel that reaches the maximum luminance value in the mapping image, and the average value of the luminance values falls within the range of the maximum luminance value of 40% to 60%. preferable.
  • particles containing 50% or more of bright areas binarized based on the average value of luminance values are defined as alkali metal compounds and / or alkaline earth metal compounds.
  • the bonding state of the alkali metal and / or alkaline earth metal can be determined.
  • the X-ray source is monochromatic AlK ⁇
  • the X-ray beam diameter is 100 ⁇ m ⁇ (25 W, 15 kV)
  • the path energy is narrow scan: 58.70 eV
  • there is charge neutralization and the number of sweeps is narrow scan: 10 times (Carbon, oxygen) 20 times (fluorine) 30 times (phosphorus) 40 times (alkali metal) 50 times (silicon)
  • the energy step can be measured under the conditions of narrow scan: 0.25 eV.
  • the peak of O1s binding energy of 527 to 530 eV is O 2 ⁇
  • the peak of 531 to 532 eV is CO, CO 3 , OH
  • SiO x (x is an integer of 1 to 4) ), C-O peak of 533 eV, SiO x (x is an integer of 1-4)
  • the peak of binding energy 685eV of F1s F - a peak of 687 eV C-F bond
  • M x PO y F z M is Li, Na, K, Rb, alkali metal selected from Cs, x, y, z is an integer of 1 ⁇ 6), PF 6 - , for the binding energy of the P2p, 133
  • the existing alkali metal compound and / or alkaline earth metal compound can be identified from the measurement result of the electronic state and the result of the existing element ratio obtained above.
  • measurement can be performed by combining a mass spectrometer or a charged particle device, it is possible to use an appropriate measurement based on the alkali metal compound and / or alkaline earth metal compound identified from the analysis results of SEM-EDX, Raman, and XPS. It is preferable to combine a column and a detector.
  • the sample retention time is constant for each ion species component if conditions such as the column to be used and the eluent are determined, and the magnitude of the peak response varies with each ion species but is proportional to the concentration. It is possible to qualitatively and quantitatively determine the ionic species component by measuring in advance a standard solution having a known concentration in which traceability is ensured.
  • each element can be quantified based on a calibration curve prepared in advance using a standard solution for chemical analysis.
  • X / (X + Y) can be calculated from the measurement results obtained, where X is the molar concentration of alkali metal ions and Y is the molar concentration of alkaline earth metal ions.
  • a method for quantifying the alkali metal compound and / or alkaline earth metal compound contained in the positive electrode is described below.
  • the positive electrode is washed with an organic solvent, then washed with distilled water, and the alkali metal compound and / or alkaline earth metal compound can be quantified from the change in the weight of the positive electrode before and after washing with distilled water.
  • Area of measurement for the positive electrode is not particularly limited but is preferably from the viewpoint of reducing the variation in measurement is 5 cm 2 or more 200 cm 2 or less, more preferably 25 cm 2 or more 150 cm 2 or less. If the area is 5 cm 2 or more, the reproducibility of the measurement is ensured.
  • the positive electrode is sufficiently immersed in an ethanol solution 50 to 100 times the weight of the positive electrode for 3 days or more. At this time, it is preferable to take measures such as covering the container so that ethanol does not volatilize. Thereafter, the positive electrode is taken out from the ethanol and dried in a vacuum (temperature: 100 to 200 ° C., pressure: 0 to 10 kPa, time: 5 to 20 hours under the condition that the remaining amount of ethanol in the positive electrode is 1% by mass or less. The residual amount of can be determined by measuring the GC / MS of water after washing with distilled water, which will be described later, and quantifying it based on a calibration curve prepared in advance.) The weight of the positive electrode at that time is M 0 (g).
  • the positive electrode is sufficiently immersed in distilled water 100 times the weight of the positive electrode (100 M 0 (g)) for 3 days or more. At this time, it is preferable to take measures such as covering the container so that distilled water does not volatilize. After soaking for 3 days or more, the positive electrode is taken out from distilled water (when measuring the ion chromatography, the amount of liquid is adjusted so that the amount of distilled water is 100 M 0 (g)), and the ethanol Vacuum dry as with washing.
  • the positive electrode active material layer on the current collector was measured using a spatula, brush, brush, etc.
  • Example 1 ⁇ Preparation of positive electrode active material>
  • the crushed coconut shell carbide was carbonized in a small carbonization furnace in nitrogen at 500 ° C. for 3 hours to obtain a carbide.
  • the obtained carbide was put into an activation furnace, 1 kg / h of steam was heated in the preheating furnace, introduced into the activation furnace, and heated to 900 ° C. over 8 hours for activation.
  • the activated carbide was taken out and cooled in a nitrogen atmosphere to obtain activated activated carbon.
  • the obtained activated carbon was washed with water for 12 hours and then drained.
  • the BET specific surface area was 2330 m 2 / g
  • the mesopore volume (V 1 ) was 0.52 cc / g
  • the micropore volume (V 2 ) was 0.88 cc / g
  • V 1 / V 2 0.59. there were.
  • a coating solution was obtained by dispersing under conditions.
  • the viscosity ( ⁇ b) and TI value of the obtained coating solution were measured using an E-type viscometer TVE-35H manufactured by Toki Sangyo Co., Ltd.
  • the viscosity ( ⁇ b) was 2,360 mPa ⁇ s
  • the TI value was 3.7.
  • the dispersion degree of the obtained coating liquid was measured using the grain gauge made from Yoshimitsu Seiki. As a result, the particle size was 31 ⁇ m.
  • the coating solution was applied to one or both sides of an aluminum foil having a thickness of 15 ⁇ m at a coating speed of 1 m / s, and dried at a drying temperature of 120 ° C.
  • a positive electrode precursor 1 (single side) and a positive electrode precursor 1 (both sides) were obtained.
  • the obtained positive electrode precursor 1 (one side) and positive electrode precursor 1 (both sides) were pressed using a roll press machine under conditions of a pressure of 6 kN / cm and a surface temperature of the pressed part of 25 ° C.
  • the thickness of the positive electrode precursor 1 (single side) and the positive electrode active material layer of the positive electrode precursor 1 (both sides) obtained above was measured using a thickness gauge Linear Gauge Sensor GS-551 manufactured by Ono Keiki Co., Ltd.
  • the thickness of the aluminum foil was subtracted from the average value of the thicknesses measured at any 10 points. As a result, the thickness of the positive electrode active material layer was 63 ⁇ m per side.
  • This heat treatment was performed in a nitrogen atmosphere by raising the temperature to 1000 ° C. in 12 hours and holding at that temperature for 5 hours. Then, after cooling to 60 degreeC by natural cooling, the composite carbon material 1b was taken out from the furnace. About the obtained composite carbon material 1b, the BET specific surface area and pore distribution were measured by the method similar to the above. As a result, the BET specific surface area was 6.1 m 2 / g, and the average particle size was 4.9 ⁇ m. Moreover, in the composite carbon material 1b, the mass ratio of the carbonaceous material derived from coal-based pitch to the activated carbon was 2.0%.
  • the initial charge capacity was measured by the following procedure using a charge / discharge device (TOSCAT-3100U) manufactured by Toyo System.
  • TOSCAT-3100U charge / discharge device manufactured by Toyo System.
  • the voltage value at a current value 0.5 mA / cm 2 was subjected to constant current charging until 0.01 V, further the current value reached 0.01 mA / cm 2 Until constant voltage charging.
  • the charging capacity at the time of constant current charging and constant voltage charging was evaluated as the initial charging capacity, it was 0.72 mAh, and the capacity per unit mass of the negative electrode 1 (lithium ion doping amount) was 550 mAh / g. .
  • EC ethylene carbonate
  • EMC ethylmethyl carbonate
  • LiN (SO 2 F) concentration ratio of 2 and LiPF 6 is the total electrolyte
  • the non-aqueous electrolyte solution 1 is obtained by dissolving each electrolyte salt so that the sum of the concentrations of 75:25 (molar ratio) and LiN (SO 2 F) 2 and LiPF 6 is 1.2 mol / L. It was.
  • the concentrations of LiN (SO 2 F) 2 and LiPF 6 in the electrolytic solution 1 were 0.9 mol / L and 0.3 mol / L, respectively.
  • the positive electrode precursor 1 one side is the positive electrode precursor 1 (single side), the positive electrode precursor, the separator, and the negative electrode in this order so that the positive electrode active material layer and the negative electrode active material layer face each other.
  • the positive electrode terminal and the negative electrode terminal were ultrasonically welded to the obtained electrode laminate, put into a container formed of an aluminum laminate packaging material, and three sides including the electrode terminal portion were sealed by heat sealing.
  • About 70 g of the non-aqueous electrolyte solution 1 is injected into the electrode laminate housed in the aluminum laminate packaging material at a temperature of 25 ° C. and a dew point of ⁇ 40 ° C. or less under an atmospheric pressure.
  • a water-based alkali metal ion capacitor was prepared.
  • the non-aqueous alkali metal ion capacitor was placed in a reduced pressure chamber, and the pressure was reduced from atmospheric pressure to -87 kPa, and then returned to atmospheric pressure and allowed to stand for 5 minutes. Thereafter, the process of reducing the pressure from atmospheric pressure to ⁇ 87 kPa and then returning to atmospheric pressure was repeated 4 times, and then allowed to stand for 15 minutes. Further, the pressure was reduced from atmospheric pressure to -91 kPa, and then returned to atmospheric pressure. Similarly, the process of reducing the pressure and returning to atmospheric pressure was repeated a total of 7 times (reduced pressure to -95, -96, -97, -81, -97, -97, and -97 kPa, respectively).
  • the electrode laminate was impregnated with the non-aqueous electrolyte solution 1. Thereafter, the non-aqueous alkali metal ion capacitor was placed in a vacuum sealing machine and sealed at 180 ° C. for 10 seconds at a pressure of 0.1 MPa with the pressure reduced to ⁇ 95 kPa, thereby sealing the aluminum laminate packaging material.
  • the obtained non-aqueous alkali metal ion capacitor was placed in an argon box having a temperature of 25 ° C., a dew point of ⁇ 60 ° C., and an oxygen concentration of 1 ppm.
  • the surplus portion of the aluminum laminate packaging material of the non-aqueous alkali metal ion capacitor is cut and opened, and a voltage of 4.5 V is reached at a current value of 50 mA using a power source (P4LT18-0.2) manufactured by Matsusada Precision Co., Ltd.
  • the non-aqueous alkali metal ion capacitor after alkali metal doping (lithium and potassium doping) is taken out from the argon box and discharged at a constant current of 50 mA at 25 mA in a 25 ° C. environment.
  • the voltage was adjusted to 3.0 V by performing current discharge for 1 hour.
  • the non-aqueous alkali metal ion capacitor was stored in a constant temperature bath at 60 ° C. for 48 hours.
  • a non-aqueous alkali metal ion capacitor was placed in a vacuum sealer, the pressure was reduced to ⁇ 90 kPa, and the aluminum laminate packaging material was sealed by sealing at 200 ° C. for 10 seconds with a pressure of 0.1 MPa.
  • the positive electrode was taken out, air-dried in an argon box for 5 minutes, immersed in 30 g of diethyl carbonate solvent newly prepared, and washed for 10 minutes in the same manner as described above. Subsequently, the positive electrode sample was vacuum-dried in a side box while maintaining a state where exposure to the atmosphere was not performed. The dried positive electrode body was transferred from the side box to the Ar box while being kept unexposed to the atmosphere, and immersed and extracted with heavy water to obtain a positive electrode body extract. The analysis of the extract was performed by ion chromatography (IC) and 1 H-NMR.
  • IC ion chromatography
  • 1 H-NMR 1 H-NMR
  • the positive electrode body extract is put into a 3 mm ⁇ NMR tube (PN-002 manufactured by Shigemi Co., Ltd.), and a 5 mm ⁇ NMR tube containing deuterated chloroform containing 1,2,4,5-tetrafluorobenzene (N, manufactured by Japan Precision Science Co., Ltd.). -5), and 1 H NMR measurement was performed by a double tube method. Normalization was performed with a signal of 1,2,4,5-tetrafluorobenzene of 7.1 ppm (m, 2H), and an integral value of each observed compound was obtained.
  • deuterated chloroform containing dimethyl sulfoxide of known concentration was put into a 3 mm ⁇ NMR tube (PN-002 manufactured by Shigemi Co., Ltd.), and the same deuterated chloroform containing 1,2,4,5-tetrafluorobenzene as above was added.
  • the sample was inserted into a 5 mm ⁇ NMR tube (N-5 manufactured by Japan Precision Science Co., Ltd.), and 1 H NMR measurement was performed by a double tube method.
  • the signal was normalized with 7.1 ppm (m, 2H) of 1,2,4,5-tetrafluorobenzene, and the integral value of 2.6 ppm (s, 6H) of dimethyl sulfoxide was obtained.
  • X is — (COO) n M or — (COO) n R 1, where M is an alkali metal selected from the group consisting of Li, Na, K, Rb, and Cs. ).
  • concentration W of XOCH 2 CH 2 OX contained in the positive electrode sample 1 is determined from the concentration of each compound obtained by the above analysis in the extract, the volume of heavy water used for extraction, and the active material mass of the positive electrode used for extraction. It was calculated to be 100.9 ⁇ 10 ⁇ 4 mol / g.
  • the positive electrode sample 1 was cut into a size of 5 cm ⁇ 5 cm (weight: 0.275 g), immersed in 20 g of ethanol in a container, and the container was covered and allowed to stand in a 25 ° C. environment for 3 days. Then, the positive electrode was taken out from the container and vacuum-dried for 10 hours under the conditions of 120 ° C. and 5 kPa.
  • the positive electrode weight M 0 at this time is 0.252 g, and GC / MS is measured under the conditions in which a calibration curve is prepared in advance for the ethanol solution after washing, and the presence of diethyl carbonate is less than 1%. confirmed.
  • the positive electrode was impregnated with 25.20 g of distilled water in another container, and the container was covered and allowed to stand in a 45 ° C. environment for 3 days. Since the weight of distilled water after standing for 3 days was 25.02 g, 0.18 g of distilled water was added. Thereafter, the positive electrode was taken out from the container and vacuum-dried for 12 hours at 150 ° C. and 3 kPa. At this time, the weight M 1 of the positive electrode was 0.238 g, and GC / MS was measured under the conditions in which a calibration curve was prepared in advance for distilled water after washing, and it was confirmed that the amount of ethanol present was less than 1%. did.
  • the active material layer on the positive electrode current collector was removed using a spatula, brush, or brush, and the weight M 2 of the positive electrode current collector was measured to be 0.099 g.
  • the total amount Z of lithium carbonate and potassium carbonate in the positive electrode was determined in accordance with the above formula (6), and it was 9.2% by mass.
  • a non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 1 except that lithium and potassium doping was performed.
  • a non-aqueous alkali metal ion capacitor was prepared by this method.
  • Example 5> Except that lithium carbonate and potassium carbonate were cooled to ⁇ 196 ° C. with liquid nitrogen and then pulverized at a peripheral speed of 10.0 m / s for 5 minutes using ⁇ 1.0 mm zirconia beads.
  • a non-aqueous alkali metal ion capacitor was prepared by this method.
  • Example 6> Except that lithium carbonate and potassium carbonate were cooled to ⁇ 196 ° C. with liquid nitrogen and then pulverized at a peripheral speed of 10.0 m / s for 3 minutes using ⁇ 1.0 mm zirconia beads, the same as in Example 1.
  • a non-aqueous alkali metal ion capacitor was prepared by this method.
  • Example 7 Lithium carbonate and potassium carbonate were cooled to ⁇ 196 ° C. with liquid nitrogen, then pulverized at a peripheral speed of 10.0 m / s for 20 minutes using ⁇ 1.0 mm zirconia beads, and a non-aqueous alkali metal ion capacitor Initial charging was performed by a method in which constant current charging was performed in a 45 ° C. environment until a voltage of 4.5 V was reached at a current value of 200 mA, followed by 4.5 V constant voltage charging for 20 hours. A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 1 except that potassium doping was performed.
  • Example 9 The initial charge of the non-aqueous alkali metal ion capacitor is performed by a method in which a constant current charge is performed until the voltage reaches 4.3 V at a current value of 200 mA, and then a 4.5 V constant voltage charge is continuously performed for 5 hours.
  • a non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 7 except that lithium and potassium were doped.
  • Example 10 Except that lithium carbonate and potassium carbonate were cooled to ⁇ 196 ° C. with liquid nitrogen and then pulverized at a peripheral speed of 10.0 m / s for 5 minutes using ⁇ 1.0 mm zirconia beads, the same as in Example 7. A non-aqueous alkali metal ion capacitor was prepared by this method.
  • Example 11 The initial charge of the non-aqueous alkali metal ion capacitor is carried out by a constant current charge until reaching a voltage of 4.3 V at a current value of 200 mA, followed by a method of continuing 4.3 V constant voltage charge for 2 hours.
  • a nonaqueous alkali metal ion capacitor was produced in the same manner as in Example 10 except that lithium and potassium doping was performed.
  • Example 12 The initial charge of the non-aqueous alkali metal ion capacitor was performed by a constant current charge until reaching a voltage of 4.5 V at a current value of 200 mA, followed by a method of continuing 4.5 V constant voltage charge for 6 hours, A nonaqueous alkali metal ion capacitor was produced in the same manner as in Example 10 except that lithium and potassium doping was performed.
  • Example 13 The initial charge of the non-aqueous alkali metal ion capacitor was performed by a constant current charge until reaching a voltage of 4.5 V at a current value of 200 mA, followed by a method of continuing 4.5 V constant voltage charge for 1 hour, A nonaqueous alkali metal ion capacitor was produced in the same manner as in Example 10 except that lithium and potassium doping was performed.
  • Example 14 The initial charge of the non-aqueous alkali metal ion capacitor was performed by a constant current charge until reaching a voltage of 4.2 V at a current value of 100 mA, followed by a method of continuing 4.2 V constant voltage charge for 1 hour, A nonaqueous alkali metal ion capacitor was produced in the same manner as in Example 10 except that lithium and potassium doping was performed.
  • Non-aqueous alkali metal ions in the same manner as in Example 1 except that lithium carbonate and potassium carbonate were pulverized at a peripheral speed of 10.0 m / s for 5 minutes using ⁇ 1.0 mm zirconia beads in a 25 ° C. environment. A capacitor was produced.
  • Non-aqueous alkali metal ions in the same manner as in Example 1 except that lithium carbonate and potassium carbonate were pulverized for 2 minutes at a peripheral speed of 10.0 m / s using zirconia beads of ⁇ 1.0 mm in an environment of 25 ° C. A capacitor was produced.
  • ⁇ Comparative Example 7> A method in which the initial charging of the non-aqueous alkali metal ion capacitor is performed under constant current charging until reaching a voltage of 4.5 V at a current value of 200 mA in a 45 ° C. environment, and then 4.5 V constant voltage charging is continued for 20 hours.
  • a non-aqueous alkali metal ion capacitor was produced in the same manner as in Comparative Example 1 except that the negative electrode was doped with lithium and potassium.
  • ⁇ Comparative Example 10> A method in which the initial charge of the non-aqueous alkali metal ion capacitor is performed at a constant current until the voltage reaches 4.5 V at a current value of 200 mA in an environment of 0 ° C., and then the 4.5 V constant voltage charge is continued for 20 hours.
  • a non-aqueous alkali metal ion capacitor was produced in the same manner as in Comparative Example 1 except that the negative electrode was doped with lithium and potassium.
  • ⁇ Comparative example 14> A method in which the initial charging of the non-aqueous alkali metal ion capacitor is performed at a current value of 200 mA until the voltage reaches 5.0 V in a 45 ° C. environment, and then 5.0 V constant voltage charging is continued for 72 hours.
  • a non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 1 except that the negative electrode was doped with lithium and potassium.
  • ⁇ Comparative Example 15> A method in which the initial charging of the non-aqueous alkali metal ion capacitor is performed under constant current charging until reaching a voltage of 5.0 V at a current value of 200 mA in a 45 ° C. environment, and then 5.0 V constant voltage charging is continued for 96 hours.
  • a non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 1 except that the negative electrode was doped with lithium and potassium.
  • Table 1 shows the evaluation results of the non-aqueous alkali metal ion capacitors of Examples 1 to 14 and Comparative Examples 1 to 15.
  • the viscosity ( ⁇ b) and TI value of the obtained coating solution were measured using an E-type viscometer TVE-35H manufactured by Toki Sangyo Co., Ltd. As a result, the viscosity ( ⁇ b) was 2,370 mPa ⁇ s, and the TI value was 3.8. Further, the degree of dispersion of the obtained coating solution was measured using a grain gauge manufactured by Yoshimitsu Seiki Co., Ltd. As a result, the particle size was 37 ⁇ m.
  • the coating solution is applied to one or both sides of a 15 ⁇ m thick aluminum foil using a die coater manufactured by Toray Engineering Co., Ltd. under a coating speed of 1 m / s, and dried at a drying temperature of 120 ° C.
  • Precursor 2 (single side) and positive electrode precursor 2 (both sides) were obtained.
  • the obtained positive electrode precursor 2 (single side) and positive electrode precursor 2 (both sides) were pressed using a roll press machine under conditions of a pressure of 6 kN / cm and a surface temperature of the press part of 25 ° C.
  • the thickness of the positive electrode precursor 2 (single side) and the positive electrode active material layer of the positive electrode precursor 2 (both sides) obtained above was determined using a thickness gauge Linear Gauge Sensor GS-551 manufactured by Ono Keiki Co., Ltd. 2 was obtained by subtracting the thickness of the aluminum foil from the average value of the thicknesses measured at any one of 10 locations. As a result, the thickness of the positive electrode active material layer was 63 ⁇ m per side.
  • 300 g of this coconut shell activated carbon is put in a stainless steel mesh basket, placed on a stainless steel bat containing 540 g of a coal-based pitch (softening point: 50 ° C.), and both are placed in an electric furnace (effective size in the furnace 300 mm ⁇ 300 mm ⁇
  • the composite porous carbon material 1a was obtained by installing in 300mm) and performing a thermal reaction. This heat treatment was performed in a nitrogen atmosphere by raising the temperature to 600 ° C. in 8 hours and holding at that temperature for 4 hours. Then, after cooling to 60 degreeC by natural cooling, the composite carbon material 1a was taken out from the furnace. About the obtained composite carbon material 1a, the BET specific surface area and pore distribution were measured by the method similar to the above.
  • the BET specific surface area was 262 m 2 / g
  • the mesopore volume (V m1 ) was 0.186 cc / g
  • the micropore volume (V m2 ) was 0.082 cc / g
  • V m1 / V m2 2.27. there were.
  • the mass ratio of the carbonaceous material derived from the coal-based pitch to the activated carbon was 78%.
  • Example 19 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 15 except that the compounding ratio of lithium carbonate 1 and sodium carbonate 1 in the positive electrode precursor was changed to 10:90.
  • Example 20 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 15 except that the compounding ratio of lithium carbonate 1 and sodium carbonate 1 in the positive electrode precursor was changed to 2:98.
  • Example 21 Example 1 except that lithium carbonate 1 (compound 1) and sodium hydroxide (compound 2) pulverized in the same manner as in Example 1 were used as the alkali metal compounds, and the respective compounding ratios were changed to 90:10. 15 was used to produce a non-aqueous alkali metal ion capacitor.
  • Example 15 except that lithium carbonate 1 (compound 1) and sodium oxide (compound 2) pulverized by the same method as in Example 1 were used as the alkali metal compound, and the respective compounding ratios were changed to 90:10.
  • a non-aqueous alkali metal ion capacitor was produced in the same manner as described above.
  • Example 25 A non-aqueous alkali metal was used in the same manner as in Example 15 except that lithium carbonate 1 (compound 1) and potassium carbonate 1 (compound 2) were used as the alkali metal compounds, and the respective compounding ratios were changed to 2:98. An ion capacitor was produced.
  • Example 15 except that lithium carbonate 1 (compound 1) and rubidium carbonate (compound 2) pulverized in the same manner as in Example 1 were used as the alkali metal compound, and the blending ratio was changed to 70:30.
  • a non-aqueous alkali metal ion capacitor was produced in the same manner as described above.
  • Example 16 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 15 except that lithium carbonate 1 (compound 1 only) was used as the alkali metal compound.
  • Example 17 A nonaqueous alkali metal was prepared in the same manner as in Example 15 except that the compounding ratio of lithium carbonate 1 (compound 1) and sodium carbonate 1 (compound 2) in the positive electrode precursor was changed to 99.5: 0.5. An ion capacitor was produced.
  • Example 18 A nonaqueous alkali metal was prepared in the same manner as in Example 15 except that the compounding ratio of lithium carbonate 1 (compound 1) and potassium carbonate 1 (compound 2) in the positive electrode precursor was changed to 99.5: 0.5. An ion capacitor was produced.
  • Example 28 A nonaqueous alkali metal ion capacitor was produced in the same manner as in Example 15 except that the compounding ratio of sodium carbonate 1 (compound 1) and potassium carbonate 1 (compound 2) in the positive electrode precursor was changed to 70:30. did.
  • Example 15 except that sodium carbonate 1 (compound 1) and rubidium carbonate (compound 2) pulverized in the same manner as in Example 1 were used as the alkali metal compound, and the blending ratio was changed to 70:30.
  • a non-aqueous alkali metal ion capacitor was produced in the same manner as described above.
  • Example 30 Example 15 except that sodium carbonate 1 (compound 1) and cesium carbonate (compound 2) pulverized in the same manner as in Example 1 were used as the alkali metal compound, and the respective compounding ratios were changed to 70:30.
  • a non-aqueous alkali metal ion capacitor was produced in the same manner as described above.
  • Example 22 A nonaqueous alkali metal was prepared in the same manner as in Example 15 except that the compounding ratio of sodium carbonate 1 (compound 1) and potassium carbonate 1 (compound 2) in the positive electrode precursor was changed to 99.5: 0.5. An ion capacitor was produced.
  • Example 31 Using lithium hydroxide (compound 1) crushed by the same method as in Example 1 and sodium hydroxide (compound 2) crushed by the same method as in Example 1, the mixing ratio was 70:30. A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 15 except for the change.
  • Example 32 Using lithium oxide (compound 1) crushed by the same method as in Example 1 and sodium oxide (compound 2) crushed by the same method as in Example 1, each compounding ratio was changed to 70:30. A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 15 except that.
  • Example 23 A nonaqueous alkali metal ion capacitor was produced in the same manner as in Example 15 except that lithium hydroxide (compound 1 only) pulverized by the same method as in Example 1 was used.
  • Example 24 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 15 except that lithium oxide (compound 1 only) pulverized by the same method as in Example 1 was used.
  • Example 33 The same as Example 15 except that the compounding ratio of lithium carbonate 1 (compound 1), sodium carbonate 1 (compound 2), and potassium carbonate 1 (compound 3) in the positive electrode precursor was changed to 96: 3: 1. A non-aqueous alkali metal ion capacitor was produced by this method.
  • Example 34 The same as Example 15 except that the compounding ratio of lithium carbonate 1 (compound 1), sodium carbonate 1 (compound 2), and potassium carbonate 1 (compound 3) in the positive electrode precursor was changed to 80: 15: 5. A non-aqueous alkali metal ion capacitor was produced by this method.
  • Example 35 The same as Example 15 except that the compounding ratio of lithium carbonate 1 (compound 1), sodium carbonate 1 (compound 2), and potassium carbonate 1 (compound 3) in the positive electrode precursor was changed to 70:20:10. A non-aqueous alkali metal ion capacitor was produced by this method.
  • Example 36 The same as Example 15 except that the compounding ratio of lithium carbonate 1 (compound 1), sodium carbonate 1 (compound 2), and potassium carbonate 1 (compound 3) in the positive electrode precursor was changed to 3: 96: 1.
  • a non-aqueous alkali metal ion capacitor was produced by this method.
  • Example 37 The same as Example 15 except that the compounding ratio of lithium carbonate 1 (compound 1), sodium carbonate 1 (compound 2), and potassium carbonate 1 (compound 3) in the positive electrode precursor was changed to 3: 1: 96. A non-aqueous alkali metal ion capacitor was produced by this method.
  • Example 38 Mixing ratio of lithium carbonate 1 (compound 1), sodium carbonate 1 (compound 2), potassium carbonate 1 (compound 3), and rubidium carbonate (compound 4) pulverized in the same manner as in Example 1 in the positive electrode precursor was changed to 85: 5: 5: 5 in the same manner as in Example 15 to produce a non-aqueous alkali metal ion capacitor.
  • Example 39 Mixing ratio of lithium carbonate 1 (compound 1), sodium carbonate 1 (compound 2), potassium carbonate 1 (compound 3), and cesium carbonate (compound 4) pulverized in the same manner as in Example 1 in the positive electrode precursor was changed to 85: 5: 5: 5 in the same manner as in Example 15 to produce a non-aqueous alkali metal ion capacitor.
  • Table 2 shows the evaluation results of the non-aqueous alkali metal ion capacitors of Examples 15 to 39 and Comparative Examples 16 to 28 and the substance amount ratio of alkali metal ions in the electrolytic solution.
  • Example 40> ⁇ Preparation of positive electrode active material>
  • Preparation Example 1b The crushed coconut shell carbide was put into a small carbonization furnace and carbonized at 500 ° C. for 3 hours under a nitrogen atmosphere to obtain a carbide. The obtained carbide was put in an activation furnace, steam heated in a preheating furnace was introduced into the activation furnace at 1 kg / h, and the temperature was increased to 900 ° C. over 8 hours for activation. The activated carbide was taken out and cooled in a nitrogen atmosphere to obtain activated activated carbon. The activated carbon thus obtained was washed with water for 10 hours, drained, dried in an electric dryer maintained at 115 ° C.
  • activated carbon 1b The average particle diameter of the activated carbon 1b was measured using a laser diffraction particle size distribution analyzer (SALD-2000J) manufactured by Shimadzu Corporation, and the result was 4.2 ⁇ m. Further, the pore distribution of the activated carbon 1b was measured using a pore distribution measuring device (AUTOSORB-1 AS-1-MP) manufactured by Yuasa Ionics.
  • SALD-2000J laser diffraction particle size distribution analyzer
  • AUTOSORB-1 AS-1-MP pore distribution measuring device manufactured by Yuasa Ionics.
  • the BET specific surface area was 2360 m 2 / g
  • the mesopore volume (V 1 ) was 0.52 cc / g
  • the micropore volume (V 2 ) was 0.88 cc / g
  • V 1 / V 2 0.59. there were.
  • Preparation Example 2b The phenol resin was placed in a firing furnace, carbonized at 600 ° C. for 2 hours in a nitrogen atmosphere, pulverized with a ball mill, and classified to obtain a carbide having an average particle diameter of 7 ⁇ m.
  • the obtained carbide and KOH were mixed at a mass ratio of 1: 5, put into a firing furnace, and activated by heating at 800 ° C. for 1 hour in a nitrogen atmosphere.
  • the activated carbide was taken out, washed with stirring in dilute hydrochloric acid adjusted to a concentration of 2 mol / L for 1 hour, boiled and washed with distilled water until it became stable between pH 5 and 6, and then dried to obtain activated carbon 2b.
  • a positive electrode precursor was manufactured using activated carbon 2b as a positive electrode active material. 54.5 parts by mass of activated carbon 2b, 33.0 parts by mass of carbonate mixture 1, 3.0 parts by mass of ketjen black, 1.5 parts by mass of PVP (polyvinylpyrrolidone), and PVDF (polyvinylidene fluoride) 8.0 parts by mass and a 99: 1 mixed solvent of NMP (N-methylpyrrolidone) and pure water were mixed, and the mixture was mixed with PRIMIX, a thin film swirl type high-speed mixer film mix, and the peripheral speed was 17 m / The coating liquid was obtained by dispersing under the conditions of s.
  • the viscosity ( ⁇ b) and TI value of the obtained coating solution were measured using an E-type viscometer TVE-35H manufactured by Toki Sangyo Co., Ltd. As a result, the viscosity ( ⁇ b) was 2,820 mPa ⁇ s, and the TI value was 4.1. Moreover, the dispersion degree of the obtained coating liquid was measured using the grain gauge made from Yoshimitsu Seiki. As a result, the particle size was 33 ⁇ m. Using a die coater manufactured by Toray Engineering Co., Ltd., the coating solution is applied to one or both sides of an aluminum foil having a thickness of 15 ⁇ m at a coating speed of 1 m / s and dried at a drying temperature of 120 ° C.
  • the body 3 (single side) and the positive electrode precursor 3 (both sides) were obtained.
  • the obtained positive electrode precursor 3 (single side) and positive electrode precursor 3 (both sides) were pressed using a roll press machine under conditions of a pressure of 6 kN / cm and a surface temperature of the pressed part of 25 ° C.
  • the total thickness of the pressed positive electrode precursor 3 (single side) and the positive electrode precursor 3 (both sides) was measured using a thickness gauge Linear Gauge Sensor GS-551 manufactured by Ono Keiki Co., Ltd. Measurements were made at any 10 points on the body 3 (both sides).
  • the thickness of the aluminum foil was subtracted from the average value of the measured total thicknesses to determine the film thicknesses of the positive electrode active material layers of the positive electrode precursor 3 (single side) and the positive electrode precursor 3 (both sides). As a result, the film thickness of the positive electrode active material layer was 58 ⁇ m per side.
  • this artificial graphite is placed in a stainless steel mesh cage and placed on a stainless steel bat containing 30 g of a coal-based pitch (softening point: 50 ° C.). ).
  • Artificial graphite and coal-based pitch were heated to 1000 ° C. in a nitrogen atmosphere in 12 hours and held at the same temperature for 5 hours to cause a thermal reaction to obtain a composite porous carbon material 1b.
  • the obtained composite porous carbon material 1b was cooled to 60 ° C. by natural cooling and taken out from the electric furnace.
  • the BET specific surface area and pore distribution were measured by the method similar to the above.
  • the BET specific surface area was 6.1 m 2 / g
  • the average particle size was 4.9 ⁇ m.
  • the mass ratio with respect to activated carbon of the carbonaceous material derived from coal-type pitch in the composite porous carbon material 1b was 2.0%.
  • a negative electrode was produced using the composite porous carbon material 1b as a negative electrode active material. 84 parts by mass of composite porous carbon material 1b, 10 parts by mass of acetylene black, 6 parts by mass of PVdF (polyvinylidene fluoride), and NMP (N-methylpyrrolidone) were mixed, and the mixture was a thin film made by PRIMIX. Using a swirl type high-speed mixer film mix, dispersion was performed under the condition of a peripheral speed of 17 m / s to obtain a coating solution.
  • PVdF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • the viscosity ( ⁇ b) and TI value of the obtained coating solution were measured using an E-type viscometer TVE-35H manufactured by Toki Sangyo Co., Ltd. As a result, the viscosity ( ⁇ b) was 2,310 mPa ⁇ s, and the TI value was 2.9.
  • the coating liquid was applied to both surfaces of an electrolytic copper foil having a thickness of 10 ⁇ m at a coating speed of 2 m / s and dried at a drying temperature of 120 ° C. Obtained.
  • the obtained negative electrode 3 was pressed under the conditions of a pressure of 5 kN / cm and a surface temperature of the pressing part of 25 ° C.
  • the film thickness of the negative electrode active material layer was 31 ⁇ m per side.
  • the initial charge capacity was measured by the following procedure using a charge / discharge device (TOSCAT-3100U) manufactured by Toyo System.
  • TOSCAT-3100U charge / discharge device manufactured by Toyo System.
  • the voltage value at a current value 0.5 mA / cm 2 was subjected to constant current charging until 0.01 V, further the current value reached 0.01 mA / cm 2 Until constant voltage charging.
  • the charge capacity at the time of constant current charge and constant voltage charge was evaluated as the initial charge capacity, it was 0.74 mAh, and the capacity per unit mass of the negative electrode 3 (lithium ion doping amount) was 545 mAh / g. .
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • the obtained positive electrode precursor 3 is composed of two positive electrode precursors 3 (one side) and positive electrode precursor 3 (both sides) so that the positive electrode active material layer has a size of 10.0 cm ⁇ 10.0 cm (100 cm 2 ). 19 sheets were cut out. Subsequently, 20 negative electrodes 3 were cut out so that the negative electrode active material layer had a size of 10.1 cm ⁇ 10.1 cm (102 cm 2 ). In addition, 40 separators made of polyethylene of 10.3 cm ⁇ 10.3 cm (106 cm 2 ) (manufactured by Asahi Kasei Corporation, thickness 10 ⁇ m) were prepared.
  • the non-aqueous electrolyte solution 2 was injected into the electrode laminate housed in the aluminum laminate packaging material in a dry air environment at a temperature of 25 ° C. and a dew point of ⁇ 40 ° C. or less under atmospheric pressure. Subsequently, the aluminum laminate packaging material containing the electrode laminate and the non-aqueous electrolyte was placed in a vacuum chamber, depressurized from atmospheric pressure to -87 kPa, then returned to atmospheric pressure and allowed to stand for 5 minutes. Thereafter, the process of reducing the packaging material in the chamber from atmospheric pressure to ⁇ 87 kPa and then returning to atmospheric pressure was repeated 4 times, and then allowed to stand for 15 minutes.
  • the pressure in the chamber was reduced from atmospheric pressure to ⁇ 91 kPa, and then returned to atmospheric pressure.
  • the process of depressurizing and returning to atmospheric pressure was repeated a total of 7 times (reduced pressure from atmospheric pressure to ⁇ 95, ⁇ 96, ⁇ 97, ⁇ 81, ⁇ 97, ⁇ 97, and ⁇ 97 kPa, respectively).
  • the electrode laminate was impregnated with the non-aqueous electrolyte solution 2.
  • the electrode laminate impregnated with the non-aqueous electrolyte solution 1 is put into a vacuum sealing machine and sealed at 180 ° C. for 10 seconds at a pressure of 0.1 MPa in a state where the pressure is reduced to ⁇ 95 kPa, whereby an aluminum laminate packaging material is obtained. Sealed.
  • Pre-doping process The electrode laminate obtained after sealing was placed in an argon box having a temperature of 25 ° C., a dew point of ⁇ 60 ° C., and an oxygen concentration of 1 ppm. The surplus portion of the aluminum laminate packaging material was cut and opened, and constant current charging was performed using a power source (P4LT18-0.2) manufactured by Matsusada Precision Co., Ltd. until the voltage reached 4.5 V at a current value of 100 mA. Thereafter, initial charging was performed by a method of continuing 4.5 V constant voltage charging for 72 hours, and the negative electrode was pre-doped. After completion of pre-doping, the aluminum laminate was sealed using a heat sealing machine (FA-300) manufactured by Fuji Impulse.
  • FA-300 heat sealing machine manufactured by Fuji Impulse.
  • the electrode laminate after pre-doping is taken out from the argon box, subjected to constant current discharge in a 25 ° C. environment at 100 mA until reaching a voltage of 3.8 V, and then subjected to 3.8 V constant current discharge for 1 hour, whereby the voltage is reduced. Adjusted to 3.8V. Subsequently, the electrode laminate was stored in a constant temperature bath at 60 ° C. for 48 hours.
  • the positive electrode was taken out from the solvent, air-dried in an argon box for 5 minutes, the positive electrode was immersed in 30 g of diethyl carbonate solvent newly prepared, and washed for 10 minutes in the same manner as described above.
  • the washed positive electrode was taken out from the argon box and dried for 20 hours under the conditions of a temperature of 25 ° C. and a pressure of 1 kPa using a vacuum dryer (manufactured by Yamato Kagaku, DP33), and two positive electrode samples 2 were obtained.
  • the obtained oxygen mapping and fluorine mapping were binarized using image analysis software (ImageJ) based on the average luminance value. At this time, the area of oxygen mapping was 15.4% with respect to all images, and the area of fluorine mapping was 31.4%.
  • Example 41 In the initial charging of the non-aqueous alkali metal ion capacitor in the pre-doping process, by performing constant current charging until the voltage reaches 4.5 V at a current value of 100 mA, and subsequently continuing 4.5 V constant voltage charging for 36 hours, A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 40 except that the negative electrode was pre-doped.
  • Example 42 In the initial charging of the non-aqueous alkali metal ion capacitor in the pre-doping process, by performing constant current charging until the voltage reaches 4.5 V at a current value of 100 mA, and subsequently continuing 4.5 V constant voltage charging for 12 hours, A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 40 except that the negative electrode was pre-doped.
  • Example 43 In the initial charging of the non-aqueous alkali metal ion capacitor in the pre-doping process, by performing constant current charging until reaching a voltage of 4.6 V at a current value of 100 mA, subsequently continuing 4.6 V constant voltage charging for 72 hours, A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 40 except that the negative electrode was pre-doped.
  • Example 44 In the initial charging of the non-aqueous alkali metal ion capacitor in the pre-doping process, by performing constant current charging until reaching a voltage of 4.6 V at a current value of 100 mA, and subsequently continuing 4.6 V constant voltage charging for 36 hours, A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 43 except that the negative electrode was pre-doped.
  • Example 45 In the initial charging of the non-aqueous alkali metal ion capacitor in the pre-doping step, by performing constant current charging until reaching a voltage of 4.6 V at a current value of 100 mA, and subsequently continuing 4.6 V constant voltage charging for 12 hours, A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 43 except that the negative electrode was pre-doped.
  • Example 46 In the initial charging of the non-aqueous alkali metal ion capacitor in the pre-doping process, by performing constant current charging until reaching a voltage of 4.3 V at a current value of 100 mA, subsequently continuing 4.3 V constant voltage charging for 72 hours, A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 40 except that the negative electrode was pre-doped.
  • Example 47 In the initial charging of the non-aqueous alkali metal ion capacitor in the pre-doping process, by performing constant current charging until reaching a voltage of 4.3 V at a current value of 100 mA, subsequently continuing 4.3 V constant voltage charging for 36 hours, A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 46 except that the negative electrode was pre-doped.
  • Example 48 In the initial charging of the non-aqueous alkali metal ion capacitor in the pre-doping process, by performing constant current charging until reaching a voltage of 4.3 V at a current value of 100 mA, and subsequently continuing 4.3 V constant voltage charging for 12 hours, A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 46 except that the negative electrode was pre-doped.
  • Example 49 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 40 except that a carbonate mixture was prepared using 150 g of lithium carbonate and 50 g of calcium carbonate.
  • Example 50 In the initial charging of the non-aqueous alkali metal ion capacitor in the pre-doping process, by performing constant current charging until the voltage reaches 4.5 V at a current value of 100 mA, and subsequently continuing 4.5 V constant voltage charging for 36 hours, A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 49 except that the negative electrode was pre-doped.
  • Example 51 In the initial charging of the non-aqueous alkali metal ion capacitor in the pre-doping process, by performing constant current charging until the voltage reaches 4.5 V at a current value of 100 mA, and subsequently continuing 4.5 V constant voltage charging for 12 hours, A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 49 except that the negative electrode was pre-doped.
  • Example 52> A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 40 except that a carbonate mixture was prepared using 75 g of lithium carbonate and 125 g of calcium carbonate.
  • Example 53 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 40 except that 30 g of lithium carbonate and 170 g of calcium carbonate were used to prepare a carbonate mixture.
  • Example 54 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 40 except that a carbonate mixture was prepared using 10 g of lithium carbonate and 190 g of calcium carbonate.
  • Example 55 A nonaqueous alkali metal ion capacitor was produced in the same manner as in Example 40 except that a carbonate mixture was prepared using 200 g of calcium carbonate.
  • Example 56 In the initial charging of the non-aqueous alkali metal ion capacitor in the pre-doping process, by performing constant current charging until the voltage reaches 4.5 V at a current value of 100 mA, and subsequently continuing 4.5 V constant voltage charging for 36 hours, A nonaqueous alkali metal ion capacitor was produced in the same manner as in Example 55 except that the negative electrode was pre-doped.
  • Example 57 In the initial charging of the non-aqueous alkali metal ion capacitor in the pre-doping process, by performing constant current charging until the voltage reaches 4.5 V at a current value of 100 mA, and subsequently continuing 4.5 V constant voltage charging for 12 hours, A nonaqueous alkali metal ion capacitor was produced in the same manner as in Example 55 except that the negative electrode was pre-doped.
  • Example 29 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 40 except that a carbonate mixture was prepared using only 200 g of lithium carbonate instead of 100 g of lithium carbonate and 100 g of calcium carbonate.
  • a non-aqueous alkaline earth metal was prepared in the same manner as in Example 40, except that a non-aqueous electrolyte solution in which an electrolyte salt was dissolved so that the concentration of Ca (PF 6 ) 2 was 0.6 mol / L was used as the mixed solvent.
  • a storage element was produced.
  • a carbonate mixture is prepared using 10 g of lithium carbonate and 190 g of calcium carbonate.
  • EMC ethylene carbonate
  • a non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 40 except that a non-aqueous electrolyte solution in which an electrolyte salt was dissolved so that the concentration of 2 was 0.6 mol / L was used.
  • Example 38 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 40 except that a carbonate mixture was prepared using 190 g of lithium carbonate and 10 g of calcium carbonate.
  • ⁇ Comparative Example 45 Calcium carbonate was pulverized for 5 minutes at a peripheral speed of 10.0 m / s using zirconia beads of ⁇ 1.0 mm in an environment of 25 ° C., and a coating solution was prepared with a 100% solvent of NMP (N-methylpyrrolidone) A non-aqueous alkaline earth metal energy storage device was produced in the same manner as in Comparative Example 33 except that this was used.
  • NMP N-methylpyrrolidone
  • Example 61 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that 100 g of cesium carbonate and 100 g of calcium carbonate were used to prepare a carbonate mixture.
  • Example 64 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that a carbonate mixture was prepared using 100 g of lithium carbonate and 100 g of strontium carbonate.
  • Example 67 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that a carbonate mixture was prepared using 100 g of lithium hydroxide and 100 g of calcium carbonate.
  • Example 68 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58, except that a carbonate mixture was prepared using 50 g of lithium hydroxide, 50 g of lithium oxide, and 100 g of calcium carbonate.
  • Example 71 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that a carbonate mixture was prepared using 100 g of lithium carbonate and 100 g of magnesium oxide.
  • Example 72 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that a carbonate mixture was prepared using 100 g of lithium carbonate and 100 g of magnesium hydroxide.
  • Example 73 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that a carbonate mixture was prepared using 100 g of lithium oxide and 100 g of calcium oxide.
  • Example 74 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that a carbonate mixture was prepared using 100 g of lithium oxide and 100 g of calcium hydroxide.
  • Example 75 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that a carbonate mixture was prepared using 100 g of sodium oxide and 100 g of calcium oxide.
  • Example 76 A nonaqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that a carbonate mixture was prepared using 100 g of sodium oxide and 100 g of calcium hydroxide.
  • Example 47 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that a carbonate mixture was prepared using only 200 g of sodium carbonate instead of 100 g of sodium carbonate and 100 g of calcium carbonate.
  • Example 48 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that a carbonate mixture was prepared using only 200 g of potassium carbonate instead of 100 g of sodium carbonate and 100 g of calcium carbonate.
  • Example 49 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that a carbonate mixture was prepared using only 200 g of rubidium carbonate instead of 100 g of sodium carbonate and 100 g of calcium carbonate.
  • Example 51 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that the carbonate mixture 2 was replaced with a pulverized product containing only 200 g of sodium oxide.
  • Example 52 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that the carbonate mixture 2 was replaced with a pulverized product containing only 200 g of potassium oxide.
  • Example 53 A non-aqueous alkali metal ion capacitor was produced in the same manner as in Example 58 except that the carbonate mixture 2 was replaced with a pulverized product containing only 200 g of sodium hydroxide.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • a non-aqueous alkaline earth metal storage element was produced in the same manner as in Example 58 except that a non-aqueous electrolyte solution in which an electrolyte salt was dissolved so that the concentration of 2 was 0.6 mol / L was used.
  • Table 4 shows the evaluation results of Examples 58 to 76 and Comparative Examples 47 to 58.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

Le présent condensateur à ions de métal alcalin non aqueux comprend une électrode positive contenant du charbon actif, une électrode négative, un séparateur et une solution électrolytique non aqueuse contenant au moins deux sortes de cations. Au moins un des deux types ou plus de cations est constitué d'ions de métal alcalin ; et un composé contenant au moins deux éléments correspondant aux deux types ou plus de cations est contenu dans l'électrode positive dans une proportion de 1,0 % en masse à 25,0 % en masse (inclus).
PCT/JP2017/028303 2016-08-08 2017-08-03 Condensateur à ions de métal alcalin non aqueux WO2018030280A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018532990A JP6705899B2 (ja) 2016-08-08 2017-08-03 非水系アルカリ金属イオンキャパシタ

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2016155931 2016-08-08
JP2016-155931 2016-08-08
JP2016-192471 2016-09-30
JP2016192471 2016-09-30

Publications (1)

Publication Number Publication Date
WO2018030280A1 true WO2018030280A1 (fr) 2018-02-15

Family

ID=61162186

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/028303 WO2018030280A1 (fr) 2016-08-08 2017-08-03 Condensateur à ions de métal alcalin non aqueux

Country Status (3)

Country Link
JP (1) JP6705899B2 (fr)
TW (1) TWI660912B (fr)
WO (1) WO2018030280A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3951937A4 (fr) * 2019-03-29 2022-06-01 Asahi Kasei Kabushiki Kaisha Procédé de production d'un élément de stockage d'électricité en métal alcalin non aqueux
JP7481707B2 (ja) 2020-11-30 2024-05-13 旭化成株式会社 非水系アルカリ金属蓄電素子

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110921646B (zh) * 2019-12-06 2022-01-07 大连理工大学 基于重质芳烃分的硬炭材料的类石墨微晶尺寸和层间距的选择性调控方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006261516A (ja) * 2005-03-18 2006-09-28 Honda Motor Co Ltd 電気二重層キャパシタ
WO2011102171A1 (fr) * 2010-02-19 2011-08-25 日本電気株式会社 Batterie secondaire
JP2012049304A (ja) * 2010-08-26 2012-03-08 Daihatsu Motor Co Ltd 電気化学キャパシタ
JP2012212629A (ja) * 2011-03-31 2012-11-01 Fuji Heavy Ind Ltd リチウムイオン蓄電デバイスの製造方法
JP2012219010A (ja) * 2011-04-06 2012-11-12 Samsung Electro-Mechanics Co Ltd ナノ複合素材及びその製造方法並びにこれを含むエネルギ貯藏装置
JP2015095339A (ja) * 2013-11-12 2015-05-18 株式会社豊田自動織機 蓄電装置用電極に添加される添加剤粒子
WO2016006632A1 (fr) * 2014-07-09 2016-01-14 旭化成株式会社 Élément de stockage au lithium non aqueux

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6361486B2 (ja) * 2014-12-01 2018-07-25 セントラル硝子株式会社 非水電解液電池用電解液、及びこれを用いた非水電解液電池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006261516A (ja) * 2005-03-18 2006-09-28 Honda Motor Co Ltd 電気二重層キャパシタ
WO2011102171A1 (fr) * 2010-02-19 2011-08-25 日本電気株式会社 Batterie secondaire
JP2012049304A (ja) * 2010-08-26 2012-03-08 Daihatsu Motor Co Ltd 電気化学キャパシタ
JP2012212629A (ja) * 2011-03-31 2012-11-01 Fuji Heavy Ind Ltd リチウムイオン蓄電デバイスの製造方法
JP2012219010A (ja) * 2011-04-06 2012-11-12 Samsung Electro-Mechanics Co Ltd ナノ複合素材及びその製造方法並びにこれを含むエネルギ貯藏装置
JP2015095339A (ja) * 2013-11-12 2015-05-18 株式会社豊田自動織機 蓄電装置用電極に添加される添加剤粒子
WO2016006632A1 (fr) * 2014-07-09 2016-01-14 旭化成株式会社 Élément de stockage au lithium non aqueux

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3951937A4 (fr) * 2019-03-29 2022-06-01 Asahi Kasei Kabushiki Kaisha Procédé de production d'un élément de stockage d'électricité en métal alcalin non aqueux
JP7481707B2 (ja) 2020-11-30 2024-05-13 旭化成株式会社 非水系アルカリ金属蓄電素子

Also Published As

Publication number Publication date
TWI660912B (zh) 2019-06-01
JP6705899B2 (ja) 2020-06-03
JPWO2018030280A1 (ja) 2019-02-21
TW201815675A (zh) 2018-05-01

Similar Documents

Publication Publication Date Title
JP6714566B2 (ja) 非水系リチウム型蓄電素子の製造方法
JP6227839B1 (ja) 非水系リチウム蓄電素子
WO2017126691A1 (fr) Élément de stockage de type au lithium non aqueux
JP6262402B2 (ja) 非水系リチウム蓄電素子
JP6957250B2 (ja) 非水系リチウム型蓄電素子
JP6705899B2 (ja) 非水系アルカリ金属イオンキャパシタ
JP6914015B2 (ja) 非水系アルカリ金属型蓄電素子
JP6815126B2 (ja) 非水系リチウム型蓄電素子
JP6815150B2 (ja) 非水系リチウム型蓄電素子
JP2018061022A (ja) 非水系リチウム型蓄電素子
JP2018056427A (ja) 非水系リチウム型蓄電素子
JP6792978B2 (ja) 非水系アルカリ金属型蓄電素子
JP6815148B2 (ja) 非水系リチウム型蓄電素子
JP6698493B2 (ja) 非水系リチウム蓄電素子
JP6829573B2 (ja) 捲回式非水系リチウム型蓄電素子
JP6754260B2 (ja) 非水系リチウム型蓄電素子
JP2018026408A (ja) 非水系アルカリ土類金属型蓄電素子
JP2019021783A (ja) 正極前駆体、及びそれを用いた非水系リチウム型蓄電素子
JP6815147B2 (ja) 非水系リチウム型蓄電素子
JP2018056434A (ja) 非水系リチウム型蓄電素子
JP6815151B2 (ja) 非水系リチウム型蓄電素子
JP6754655B2 (ja) 非水系リチウム型蓄電素子
JP6754659B2 (ja) 非水系リチウム型蓄電素子
JP6815146B2 (ja) 非水系リチウム型蓄電素子
JP2018056430A (ja) 非水系リチウム型蓄電素子

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018532990

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17839351

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17839351

Country of ref document: EP

Kind code of ref document: A1