WO2019156090A1 - 非水系リチウム蓄電素子 - Google Patents

非水系リチウム蓄電素子 Download PDF

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Publication number
WO2019156090A1
WO2019156090A1 PCT/JP2019/004111 JP2019004111W WO2019156090A1 WO 2019156090 A1 WO2019156090 A1 WO 2019156090A1 JP 2019004111 W JP2019004111 W JP 2019004111W WO 2019156090 A1 WO2019156090 A1 WO 2019156090A1
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Prior art keywords
positive electrode
active material
lithium
electrode active
less
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PCT/JP2019/004111
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English (en)
French (fr)
Japanese (ja)
Inventor
和照 梅津
啓太 楠坂
維摩 木村
森田　均
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旭化成株式会社
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Priority to JP2019570760A priority Critical patent/JPWO2019156090A1/ja
Publication of WO2019156090A1 publication Critical patent/WO2019156090A1/ja

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    • H—ELECTRICITY
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K6/00—Arrangement or mounting of plural diverse prime-movers for mutual or common propulsion, e.g. hybrid propulsion systems comprising electric motors and internal combustion engines ; Control systems therefor, i.e. systems controlling two or more prime movers, or controlling one of these prime movers and any of the transmission, drive or drive units Informative references: mechanical gearings with secondary electric drive F16H3/72; arrangements for handling mechanical energy structurally associated with the dynamo-electric machine H02K7/00; machines comprising structurally interrelated motor and generator parts H02K51/00; dynamo-electric machines not otherwise provided for in H02K see H02K99/00
    • B60K6/20—Arrangement or mounting of plural diverse prime-movers for mutual or common propulsion, e.g. hybrid propulsion systems comprising electric motors and internal combustion engines ; Control systems therefor, i.e. systems controlling two or more prime movers, or controlling one of these prime movers and any of the transmission, drive or drive units Informative references: mechanical gearings with secondary electric drive F16H3/72; arrangements for handling mechanical energy structurally associated with the dynamo-electric machine H02K7/00; machines comprising structurally interrelated motor and generator parts H02K51/00; dynamo-electric machines not otherwise provided for in H02K see H02K99/00 the prime-movers consisting of electric motors and internal combustion engines, e.g. HEVs
    • B60K6/22—Arrangement or mounting of plural diverse prime-movers for mutual or common propulsion, e.g. hybrid propulsion systems comprising electric motors and internal combustion engines ; Control systems therefor, i.e. systems controlling two or more prime movers, or controlling one of these prime movers and any of the transmission, drive or drive units Informative references: mechanical gearings with secondary electric drive F16H3/72; arrangements for handling mechanical energy structurally associated with the dynamo-electric machine H02K7/00; machines comprising structurally interrelated motor and generator parts H02K51/00; dynamo-electric machines not otherwise provided for in H02K see H02K99/00 the prime-movers consisting of electric motors and internal combustion engines, e.g. HEVs characterised by apparatus, components or means specially adapted for HEVs
    • B60K6/28—Arrangement or mounting of plural diverse prime-movers for mutual or common propulsion, e.g. hybrid propulsion systems comprising electric motors and internal combustion engines ; Control systems therefor, i.e. systems controlling two or more prime movers, or controlling one of these prime movers and any of the transmission, drive or drive units Informative references: mechanical gearings with secondary electric drive F16H3/72; arrangements for handling mechanical energy structurally associated with the dynamo-electric machine H02K7/00; machines comprising structurally interrelated motor and generator parts H02K51/00; dynamo-electric machines not otherwise provided for in H02K see H02K99/00 the prime-movers consisting of electric motors and internal combustion engines, e.g. HEVs characterised by apparatus, components or means specially adapted for HEVs characterised by the electric energy storing means, e.g. batteries or capacitors
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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    • H01G11/04—Hybrid capacitors
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    • 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
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Definitions

  • the positive electrode active material is made of a lithium transition metal composite oxide, and the viscosity change rate represented by the viscosity ratio after 30 minutes and 2 hours after the homogenization treatment is small and stable for a lithium secondary battery.
  • a positive electrode composition is disclosed.
  • Patent Document 7 discloses a method for producing a high-power lithium ion battery using an aluminum current collector.
  • Patent Document 8 discloses a non-aqueous system that ensures the electron conductivity between a plurality of positive electrode active materials by controlling the average particle size of the lithium compound contained in the positive electrode and the average particle size of the plurality of positive electrode active materials. It has been proposed to increase the output and energy density of a lithium storage element.
  • the positive electrode coating solution is selected from the group consisting of carboxymethylcellulose, methylcellulose, ethylcellulose, cellulose acetate phthalate, hydroxymethylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose phthalate, polyvinylpyrrolidone, polyvinyl alcohol, and polyvinyl acetal. 32.
  • the non-aqueous electrolyte solution is a non-aqueous lithium battery element including an organic solvent and a lithium salt electrolyte having an imide structure.
  • a non-aqueous lithium storage element comprising a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte solution,
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer on one or both sides of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material and a lithium compound other than the positive electrode active material.
  • the non-aqueous lithium electrical storage element which has a high capacity
  • the non-aqueous lithium storage element of this embodiment includes a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte solution.
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer on one or both sides of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material and a lithium compound other than the positive electrode active material.
  • the binder contains a polymer having a RED value greater than 1 based on a Hansen solubility parameter for the non-aqueous electrolyte
  • the negative electrode has a negative electrode current collector and a negative electrode active material layer on one or both sides of the negative electrode current collector, and the negative electrode active material layer contains a negative electrode active material capable of inserting and extracting lithium ions.
  • the said non-aqueous electrolyte solution contains an organic solvent and lithium salt electrolyte.
  • a battery element is assembled using a positive electrode precursor containing an alkali metal compound, a negative electrode, a separator, an exterior body, and a non-aqueous electrolyte, and then a voltage is applied between the positive electrode precursor and the negative electrode.
  • the alkali metal compound may be contained in any form in the positive electrode precursor.
  • the alkali metal compound may be present between the positive electrode current collector and the positive electrode active material layer, or may be present on the surface of the positive electrode active material layer.
  • the alkali metal compound is preferably contained in the positive electrode active material layer formed on the positive electrode current collector of the positive electrode precursor.
  • 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 combination of the lower limit and the upper limit is arbitrary.
  • the ratio of meso Anaryou V 1 relative to the micropore volume V 2 of activated carbon 1 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. Is preferred. More preferred V 1 / V 2 range 0.4 ⁇ V 1 / V 2 ⁇ 0.7, further preferred V 1 / V 2 range is 0.55 ⁇ V 1 / V 2 ⁇ 0.7.
  • the combination of the lower limit and the upper limit is arbitrary.
  • 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-product, bagasse, molasses, 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.
  • a gas activation method in which firing is performed using an activation gas such as water vapor, carbon dioxide, or oxygen is preferably used.
  • an activation gas such as water vapor, carbon dioxide, or oxygen
  • a method using water vapor or carbon dioxide as the activation gas is preferable.
  • the activated carbon 1 having the above-described characteristics can be produced by appropriately combining the firing temperature and firing time in the carbonization method with the activation gas supply amount, the heating rate and the maximum activation temperature in the activation method.
  • the average particle diameter of the activated carbon 1 is preferably 2 to 20 ⁇ m.
  • the average particle diameter is 2 ⁇ m or more, the density per volume of the electrode tends to increase because the density of the active material layer is high.
  • the average particle diameter is 2 ⁇ m or more, it is easy to ensure the durability of the positive electrode active material layer.
  • the average particle diameter is more preferably 2 to 15 ⁇ m, still more preferably 3 to 10 ⁇ m.
  • the upper and lower limits of the average particle diameter range can be arbitrarily combined.
  • 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 incorporated in the energy storage device.
  • V 1 is preferably 2.5 cc / g or less from the viewpoint of suppressing a reduction in the capacity of the power storage element.
  • V 1 is more preferably from 1.00 cc / g to 2.0 cc / g, and still more preferably from 1.2 cc / g to 1.8 cc / g.
  • the activated carbon 2 having the above-described mesopore size and micropore size has a higher BET specific surface area than activated carbon used for conventional electric double layer capacitors or lithium ion capacitors.
  • the specific value of the BET specific surface area of the activated carbon 2 is preferably 2,300 m 2 / g or more and 4,000 m 2 / g or less.
  • the lower limit of the BET specific surface area is more preferably 3,000 m 2 / g or more, and further preferably 3,200 m 2 / g or more.
  • the upper limit of the BET specific surface area is more preferably 3,800 m 2 / g or less.
  • the BET specific surface area is 2,300 m 2 / g or more, a good energy density is easily obtained.
  • the BET specific surface area is 4,000 m 2 / g or less, a binder is used to maintain the strength of the electrode. Since it is not necessary to add a large amount, the performance per electrode volume is increased.
  • V 1 , V 2 and BET specific surface area of the activated carbon 2 the upper limit and the lower limit of the preferred ranges described above can be arbitrarily combined.
  • the activated carbon 2 having the characteristics as described above can be obtained using, for example, the raw materials and the processing method described below.
  • the carbon source 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.
  • plant raw materials such as wood, wood flour, and coconut shells; petroleum pitch, coke And various synthetic resins such as phenol resin, furan resin, vinyl chloride resin, vinyl acetate resin, melamine resin, urea resin, resorcinol resin, and the like.
  • 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 preferably 400 to 700 ° C, the lower limit is preferably 450 ° C or higher, more preferably 500 ° C or higher, and the upper limit is preferably 650 ° C or lower.
  • the firing time is preferably 0.5 to 10 hours.
  • a method for activating the carbide after carbonization treatment there are 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 having a high specific surface area.
  • the mass ratio of carbide to an alkali metal compound such as potassium hydroxide (KOH) or sodium hydroxide (NaOH) is 1: 1 or more (that is, the amount of the alkali metal compound is the amount of the carbide).
  • KOH potassium hydroxide
  • NaOH sodium hydroxide
  • an inert gas atmosphere preferably in the range of 600 to 900 ° C., more preferably in the range of 650 ° C. to 850 ° C., preferably 0.5 to Heating is performed for 5 hours, and then the alkali metal compound is washed and removed with an acid and water, followed by drying.
  • the mass ratio of the carbide and the alkali metal compound increases as the amount of the alkali metal compound increases, but the mass ratio is preferably 1: 5.5 or less in consideration of the subsequent processing efficiency such as washing.
  • 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 activated carbon 2 (for example, activated carbon not having the specific V 1 and / or V 2 described above, or a material other than activated carbon (such as a conductive polymer). ) May be included.
  • the content of activated carbon is preferably 40% by mass or more and 95% by mass or less, more preferably 50% by mass or more and 90% by mass. It is below mass%.
  • the lithium transition metal oxide includes a transition metal oxide capable of inserting and extracting lithium. There is no restriction
  • the lithium transition metal oxide include an oxide containing lithium and at least one element selected from the group consisting of cobalt, nickel, manganese, iron, vanadium, and chromium.
  • the lithium transition metal oxide the following formula: Li x CoO 2 ⁇ wherein x satisfies 0 ⁇ x ⁇ 1. ⁇ , Li x NiO 2 ⁇ wherein x satisfies 0 ⁇ x ⁇ 1.
  • ⁇ -Li x FeO 2 wherein x satisfies 0 ⁇ x ⁇ 1.
  • Li x VO 2 ⁇ wherein x satisfies 0 ⁇ x ⁇ 1.
  • Li x CrO 2 ⁇ wherein x satisfies 0 ⁇ x ⁇ 1.
  • Li x FePO 4 ⁇ wherein x satisfies 0 ⁇ x ⁇ 1.
  • Li x MnPO 4 ⁇ wherein x satisfies 0 ⁇ x ⁇ 1.
  • Li z V 2 (PO 4 ) 3 ⁇ wherein z satisfies 0 ⁇ z ⁇ 3.
  • Li x Mn 2 O 4 ⁇ wherein x satisfies 0 ⁇ x ⁇ 1.
  • Li x Ni a Co b Al (1-ab) 2 O 3 2 Li x Ni c Co d Mn (1-cd) O 2 , Li x CoO 2 , Li x Mn 2 O 4 , Li x FePO 4 , Li x MnPO 4 , or Li z V 2 (PO 4 )
  • the compound represented by 3 is preferable.
  • the average particle size of the lithium transition metal oxide is preferably 0.1 to 20 ⁇ m.
  • the average particle size is 0.1 ⁇ m or more, the capacity per electrode volume tends to increase because the density of the positive electrode active material layer is high. If the average particle size is small, there may be a drawback that the durability is low, but if the average particle size is 0.1 ⁇ m or more, such a defect is difficult to occur. 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 of the lithium transition metal oxide is more preferably 0.5 to 15 ⁇ m, and further preferably 1 to 10 ⁇ m.
  • the average particle diameter of a lithium transition metal oxide is smaller than the average particle diameter of the carbon material demonstrated above. If the average particle diameter of the lithium transition metal oxide is small, the lithium transition metal oxide can be disposed in the void formed by the carbon material having a large average particle diameter, and the resistance can be reduced.
  • the lithium transition metal oxide is preferably at least one selected from the group consisting of a layered compound, a spinel compound, and an olivine compound.
  • the positive electrode active material may include a material other than the lithium transition metal oxide (for example, a conductive polymer).
  • K 2 is less 35 mass% to 5 mass%, or less preferably from 30 mass% to 10 mass% It is.
  • the content of the activated carbon 1 in the positive electrode active material layer that is, when the mass ratio of the carbon material of the positive electrode active material layer and A 1, also, the positive electrode conductive filler in the precursor, the binder, when containing the dispersion stabilizer and the like, when the total amount of the carbon material and these materials and a 1, a 1 is 65 wt% or less than 15 wt% It is preferable that it is 20 mass% or more and 50 mass% or less more preferably.
  • a 1 is 15% by mass or more, the contact area between the carbon material having high electrical conductivity and the alkali metal compound increases, so that the oxidation reaction of the alkali metal compound is promoted in the pre-doping step, and the pre-doping can be performed in a short time. it can.
  • a 1 is 65 wt% or less, higher capacity increased bulk density of the positive electrode active material layer.
  • a 2 is preferably 5% by mass or more and 35% by mass or less, more preferably 10% by mass or more and 30% by mass or less. is there. If A 2 is 5 wt% or more, higher capacity increased bulk density of the positive electrode active material layer.
  • a 2 is 35% by mass or less, the contact area between the carbon material having a high electrical conductivity and the alkali metal compound increases, so that the oxidation reaction of the alkali metal compound is promoted in the pre-doping step, and the pre-doping can be performed in a short time. it can.
  • 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 80 mass% or less. By setting the content ratio in this range, more suitable charge / discharge characteristics are exhibited.
  • the ratio K 2 / K 1 between the lithium transition metal oxide content K 2 and the carbon material content K 1 in the positive electrode coating solution is 0.1 or more and 2.0 or less, preferably It is 0.2 or more and 1.2 or less.
  • K 2 / K 1 is 0.1 or more, the bulk density of the positive electrode active material layer can be increased and the capacity can be increased.
  • K 2 / K 1 is 2.0 or less, the electron conduction between the activated carbons is increased, so that the resistance can be reduced, and the contact area between the activated carbon and the alkali metal compound is increased, so that the decomposition of the alkali metal compound can be promoted.
  • the ratio A 2 / A 1 between the content A 2 of the lithium transition metal oxide and the content A 1 of the carbon material is 0. .10 or more and 2.00 or less, preferably 0.20 or more and 1.20 or less, and more preferably 0.20 or more and 1.10 or less.
  • a 2 / A 1 is 0.10 or more, the bulk density of the positive electrode active material layer can be increased and the capacity can be increased.
  • a 2 / A 1 is 2.00 or less, the electron conduction between the activated carbons is increased, so that the resistance can be reduced, and the contact area between the activated carbons and the alkali metal compounds is increased, so that the decomposition of the alkali metal compounds can be promoted.
  • alkali metal compound examples include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium oxide, and lithium hydroxide, and decomposes in the positive electrode precursor to release a cation,
  • One or more alkali metal carbonates selected from the group consisting of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate, which can be pre-doped by reduction at the negative electrode, are preferably used.
  • Lithium carbonate, sodium carbonate or potassium carbonate is more preferably used, and lithium carbonate is more preferably used from the viewpoint of high capacity per unit weight.
  • the alkali metal compound contained in the positive electrode coating solution may be one kind or may contain two or more kinds of alkali metal compounds.
  • the positive-electrode coating formulation according to the present embodiment it is sufficient at least one alkali metal compound, an M Li, Na, K, Rb, as one or more selected from Cs, M 2 O Including one or more carboxylates such as oxides such as MOH, hydroxides such as MOH, halides such as MF and MCl, and RCOOM (wherein R is H, an alkyl group, or an aryl group). Also good.
  • alkali metal compound according to the present embodiment BeCO 3, MgCO 3, CaCO 3, SrCO 3, and alkaline earth metal carbonate selected from the group consisting of BaCO 3, alkaline earth metal oxides, alkaline earth One or more metal hydroxides, alkaline earth metal halides, or alkaline earth metal carboxylates may be included.
  • the weight ratio X 3 of the alkali metal compound to the total solid content of the Seikyokunuriko solution is more than 10 wt% 50 wt% or less.
  • X 3 is able to pre-doping a sufficient amount of alkali metal ions in the negative electrode as long as 10 mass% or more, increasing the capacity of the non-aqueous lithium storage element is. If X 3 is 50 or less, it is possible to enhance the electron conductivity of the positive electrode precursor, it is possible to efficiently decompose the alkali metal compound.
  • the positive electrode coating solution contains two or more alkali metal compounds or alkaline earth metal compounds in addition to the alkali metal compound, the total amount of the alkali metal compound and alkaline earth metal compound is the positive electrode coating solution. It is preferable to prepare the positive electrode coating solution so as to be contained at a ratio of 10% by mass or more and 50% by mass or less with respect to the total solid content.
  • Mass ratio A 3 of the alkali metal compound contained in the positive electrode active material layer of the positive electrode precursor it is preferable to produce a positive electrode precursor such that at least 10 wt% 50 wt% or less.
  • a 3 is able to pre-doping a sufficient amount of alkali metal ions in the negative electrode as long as 10 mass% or more, increasing the capacity of the non-aqueous lithium storage element is. If A 3 is less than 50 wt%, it is possible to enhance the electron conductivity of the positive electrode precursor, it is possible to efficiently decompose the alkali metal compound.
  • the positive electrode precursor contains two or more alkali metal compounds or alkaline earth metal compounds in addition to the alkali metal compound, the total amount of the alkali metal compound and the alkaline earth metal compound per one surface of the positive electrode precursor It is preferable to prepare the positive electrode precursor so that the ratio is 10% by mass or more and 50% by mass or less in the positive electrode active material layer.
  • the alkali metal compound contained in the positive electrode precursor is oxidatively decomposed by applying a high voltage when a non-aqueous lithium electricity storage element is formed to release alkali metal ions, and pre-doping proceeds by reduction at the negative electrode. Therefore, the pre-dope process can be performed in a short time by promoting the oxidation reaction.
  • an alkali metal compound that is an insulator is brought into contact with the positive electrode active material to ensure electron conduction, and a cation released by the reaction is diffused in the electrolytic solution. is important. Therefore, it is important that the surface of the positive electrode active material is appropriately covered with an alkali metal compound.
  • a pulverizer such as a ball mill, a bead mill, a ring mill, a jet mill, or a rod mill can be used.
  • the quantification of the alkali metal element and alkaline earth metal element can be calculated by ICP-AES, atomic absorption analysis, fluorescent X-ray analysis, neutron activation analysis, ICP-MS, or the like.
  • the average particle diameter of an alkali metal compound is 0.1 micrometer or more and 10 micrometers or less. When the average particle size is 0.1 ⁇ m or more, the dispersibility in the positive electrode precursor is excellent.
  • the positive electrode active material layer of the positive electrode of this embodiment contains a lithium compound other than the positive electrode active material.
  • Such a lithium compound is decomposed by the application of a voltage, functions as a lithium-doped dopant source for the negative electrode, and forms vacancies in the positive electrode active material layer, so that it has excellent electrolyte retention and ion conductivity. Can be formed.
  • the average particle size of the lithium compound is 0.1 ⁇ m or more, the vacancies remaining after the oxidation reaction of the lithium compound in the positive electrode have a sufficient volume to hold the electrolytic solution. improves.
  • the average particle size of the lithium compound is 100 ⁇ m or less, the surface area of the lithium compound does not become excessively small, so that the speed of the oxidation reaction of the lithium compound can be ensured.
  • the upper limit and the lower limit of the range of the average particle diameter of the lithium compound can be arbitrarily combined.
  • pulverizer such as a ball mill, a bead mill, a ring mill, a jet mill, or a rod mill can be used.
  • the content ratio of the lithium compound in the positive electrode active material layer of the positive electrode precursor is preferably 5% by mass or more and 60% by mass or less, preferably 10% by mass or more and 50% by mass or less, based on the total mass of the positive electrode active material layer in the positive electrode precursor. It is more preferable that the amount is not more than mass%.
  • the lithium compound other than the positive electrode active material contained in the positive electrode is preferably 1% by mass or more and 50% by mass or less, more preferably 2.5% by mass or more and 25% by mass based on the total mass of the positive electrode active material layer in the positive electrode. It is as follows. When the amount of the lithium compound is 1% by mass or more, the lithium carbonate suppresses the decomposition reaction of the electrolyte solvent on the positive electrode in a high temperature environment, so that the high temperature durability is improved. Becomes prominent.
  • the amount of the lithium compound is 50% by mass or less, the electron conductivity between the positive electrode active materials is relatively less disturbed by the lithium compound, and thus exhibits high input / output characteristics, and when it is 25% by mass or less, In particular, it is particularly preferable from the viewpoint of improving input / output characteristics.
  • the combination of the lower limit and the upper limit is arbitrary.
  • the identification method of lithium compounds other than the positive electrode active material contained in a positive electrode is not specifically limited, For example, it can identify by the following method.
  • For identification of lithium compounds SEM-EDX, Raman, X-ray photoelectron spectroscopy (XPS), solid 7 Li-NMR, XRD (X-ray diffraction), TOF-SIMS (time-of-flight secondary ion mass spectrometry), AES ( It is preferable to identify by combining a plurality of analysis methods selected from Auger electron spectroscopy), TPD / MS (heat generation gas mass spectrometry), DSC (differential scanning calorimetry) and the like.
  • the positive electrode coating liquid in the present embodiment and the positive electrode active material layer of the positive electrode precursor contain a polyacrylic acid compound as a binder in addition to the positive electrode active material and the alkali metal compound, and if necessary, a conductive filler And optional components such as a dispersant and a pH adjuster may be contained.
  • the conductive filler include a conductive carbonaceous material having higher conductivity than the positive electrode active material.
  • a conductive filler for example, ketjen black, acetylene black, vapor-grown carbon fiber, graphite, flake graphite, carbon nanotube, graphene, a mixture thereof, and the like are preferable.
  • the mixing amount of the conductive filler in the positive electrode active material layer of the positive electrode coating liquid and the positive electrode precursor 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 decreases, and therefore the energy density per volume of the positive electrode active material layer decreases, which is not preferable.
  • the binder according to the positive electrode coating liquid and the positive electrode precursor of this embodiment is characterized by containing a polyacrylic acid compound.
  • a polyacrylic acid compound for example, polyacrylic acid; Sodium polyacrylate or potassium polyacrylate by which the acidic functional group was neutralized; Maleic acid, a sulfonic acid, methacrylic acid etc., and an acrylic acid monomer Examples thereof include a copolymer or a sodium or potassium salt thereof.
  • polyacrylic acid in which some of the carboxyl groups are alkylated may be used, or fluorine-substituted alkylated polyacrylic acid may be used.
  • the average molecular weight of the polyacrylic acid compound is not particularly limited, but is preferably in the range of 5,000 to 1,000,000, more preferably 10,000 to 500,000. If the average molecular weight is 5,000 or more, the peel strength of the electrode can be increased. When the average molecular weight is 1,000,000 or less, the diffusion of ions in the electrode is improved and the input / output characteristics are enhanced.
  • the binder in the positive electrode coating liquid and the positive electrode precursor of the present embodiment only needs to contain a polyacrylic acid compound.
  • 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 part 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 hindering the entry / exit and diffusion of ions to / from the positive electrode active material.
  • the dispersant is not particularly limited, and examples thereof include carboxymethyl cellulose, methyl cellulose, ethyl cellulose, cellulose acetate phthalate, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose phthalate, polyvinyl pyrrolidone, polyvinyl alcohol, and At least one selected from the group consisting of polyvinyl acetals can be used.
  • the amount of the dispersant used is preferably 0 parts by mass or more and 10 parts by mass or less, more preferably more than 0 parts by mass and 10 parts by mass or less with respect to 100 parts by mass of the positive electrode active material. When the amount of the dispersant is 10 parts by mass or less, high input / output characteristics are exhibited without hindering the entry and exit of ions into and diffusion of the positive electrode active material.
  • dispersion solvent for the positive electrode coating liquid examples include water, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, dioxane, tetrahydrofuran, dimethylformamide, dimethylacetamide, tetramethylurea, dimethylsulfoxide, phosphorus Acid trimethyl, alcohol, acetone, toluene, xylene, normal hexane, cyclohexane, and a mixture thereof can be used.
  • the amount of water contained in the dispersion solvent is preferably 0% by mass or more and 10% by mass or less. If the water content is 0% by mass or more, the alkali metal compound dissolves in a very small amount, so that the contact between the positive electrode active material or the conductive material and the alkali metal compound is increased, and pre-doping is promoted. If the water content is 10% by mass or less, the basicity of the coating solution does not become too high, and denaturation of the binder can be suppressed. Examples of the method for suppressing the contained water content to 10% by mass or less include a method of adding a dehydrating agent such as magnesium sulfate or zeolite.
  • a dehydrating agent such as magnesium sulfate or zeolite.
  • the positive electrode active material layer in the non-aqueous lithium storage element of this embodiment contains a binder in addition to the positive electrode active material and the lithium compound other than the positive electrode active material.
  • the binder includes a polymer having a RED value greater than 1 based on the Hansen solubility parameter for the non-aqueous electrolyte.
  • a polymer having a RED value greater than 1 based on the Hansen solubility parameter for the non-aqueous electrolyte Specifically, PVdF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), polyacrylic acid, polyimide, latex, styrene-butadiene copolymer, fluororubber, acrylic copolymer, acrylate polymer, etc. Polyacrylic acid is preferable.
  • acids polyacrylic acid in which some of the carboxyl groups are fluorine-substituted alkylated, and the like.
  • the average molecular weight of the polyacrylic acid is not particularly limited, but is preferably in the range of 5,000 to 1,000,000, and more preferably 10,000 to 500,000. If the average molecular weight is 5,000 or more, the peel strength of the electrode can be increased. When the average molecular weight is 1,000,000 or less, the diffusion of ions in the electrode is improved and the input / output characteristics are enhanced.
  • Polyacrylic acid may be used alone or in combination of two or more.
  • 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 and 25 parts by mass or less with respect to 100 parts by mass of the positive electrode active material. Or less. If the usage-amount of a binder is 1 mass part or more, sufficient electrode intensity
  • the positive electrode active material layer in the present embodiment includes optional components such as a conductive filler, a binder, and a dispersion stabilizer in addition to the positive electrode active material, the lithium compound other than the positive electrode active material, and the binder. May be included.
  • the dispersion stabilizer is not particularly limited, and for example, PVP (polyvinyl pyrrolidone), PVA (polyvinyl alcohol), cellulose derivatives and the like can be used.
  • the amount of the dispersion stabilizer used is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the positive electrode active material. When the amount of the dispersion stabilizer used is 10 parts by mass or less, high input / output characteristics are exhibited without impeding ion entry and exit and diffusion into the positive electrode active material.
  • the coating solution may become basic by adding a lithium compound, so a pH adjuster may be added to the coating solution as necessary.
  • a pH adjuster For example, hydrogen halides, such as hydrogen fluoride, hydrogen chloride, and hydrogen bromide; Halogen oxo acids, such as hypochlorous acid, chlorous acid, and chloric acid; Formic acid Carboxylic acids such as acetic acid, citric acid, oxalic acid, lactic acid, maleic acid and fumaric acid; sulfonic acids such as methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; nitric acid, sulfuric acid, phosphoric acid, boric acid and dioxide Other acids such as carbon can be used.
  • the material constituting the positive electrode current collector in the present embodiment is not particularly limited as long as it is a material that has high electron conductivity and is unlikely to 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 lithium storage element of the present embodiment.
  • the metal foil may be a metal foil having no irregularities, through-holes, etc., or may be a metal foil having irregularities subjected to embossing, chemical etching, electrolytic deposition, blasting, etc., expanded metal, punching metal, 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.
  • an anchor layer containing a conductive material such as graphite, scaly graphite, carbon nanotube, graphene, ketjen black, acetylene black, or vapor grown carbon fiber may be provided on the surface of the metal foil.
  • a conductive material such as graphite, scaly graphite, carbon nanotube, graphene, ketjen black, acetylene black, or vapor grown carbon fiber.
  • the positive electrode coating liquid of the non-aqueous lithium storage element can be manufactured by a manufacturing technique of a coating liquid in a known lithium ion battery, electric double layer capacitor, or the like.
  • a slurry-like coating liquid may be prepared by dispersing or dissolving a positive electrode active material, an alkali metal compound, and other optional components used as necessary in water or an organic solvent in any order. it can.
  • the method for producing a positive electrode coating liquid according to the present embodiment is obtained by dry-mixing a carbon material and, if desired, a solid content including a lithium transition metal oxide and an alkali metal compound, and then dry-mixing. Mixing the solid content and the dispersion solvent to disperse the solid content. More specifically, for example, part or all of the solid content including the carbon material, the lithium transition metal oxide, and the alkali metal compound is dry-mixed (also referred to as “dry blend”), and then the dispersion solvent.
  • the carbon material and the alkali metal compound may be dry-mixed, and then the other solid content and the dispersion solvent may be mixed and dispersed by an arbitrary procedure. According to this procedure, the carbon material and the alkali metal compound are more closely mixed, whereby the electron conduction of the alkali metal compound can be increased and the alkali metal compound is easily decomposed in the pre-doping step, which is preferable. More specifically, for example, part or all of the carbon material and the alkali metal compound are dry-mixed, then lithium transition metal oxide is added and dry-mixed, and then the dispersion solvent and / or the dispersion solvent are mixed with the polycrystal.
  • a positive electrode coating solution may be prepared by adding a liquid or slurry substance in which an acrylic acid compound, a dispersant or a pH adjuster is dissolved or dispersed.
  • a carbon material and an alkali metal compound that are dry-mixed in advance in a liquid or slurry substance in which a polyacrylic acid compound, a dispersant or a pH adjuster is dissolved or dispersed in a dispersion solvent, and a lithium transition metal oxide, etc. May be prepared by adding by any procedure.
  • the method for dry mixing is not limited, but for example, a ball mill can be used.
  • the conductive material and the alkali metal compound may be dry mixed, and then the other solid content and the dispersion solvent may be mixed and dispersed by an arbitrary procedure.
  • a conductive material is coated on a low-conductivity alkali metal compound, whereby electronic conductivity of the alkali metal compound can be increased, and the alkali metal compound is easily decomposed in the pre-doping step, which is preferable. More specifically, for example, part or all of the conductive material and the alkali metal compound are dry-mixed, then the carbon material and the lithium transition metal oxide are added and dry-mixed, and then the dispersion solvent and / or the dispersion are mixed.
  • a positive electrode coating solution may be prepared by adding a liquid or slurry substance in which a polyacrylic acid compound, a dispersant or a pH adjuster is dissolved or dispersed in a solvent.
  • a conductive material and an alkali metal compound, and a carbon material and a lithium transition metal which are previously dry-mixed in a liquid or slurry substance in which a polyacrylic acid compound, a dispersant or a pH adjuster is dissolved or dispersed in a dispersion solvent.
  • You may add and prepare an oxide etc. by arbitrary procedures.
  • the method for dry mixing is not limited, but for example, a ball mill can be used.
  • the solid content of the positive electrode coating solution is preferably 15% or more and 60% or less. If the solid content is 15% or more, it can be dried under mild conditions during coating. If the solid content is 60% or less, the occurrence of coating streaks or cracks during coating can be suppressed.
  • the solid content rate is the ratio of the total weight of solids such as carbon material, polyacrylic acid compound, alkali metal compound, and other lithium transition metal oxides or conductive materials in the total weight of the coating liquid.
  • the dispersion method in the preparation of the positive electrode coating liquid is not particularly limited, but is preferably a bead mill, ball mill, jet mill, homogenizer, emulsifier / disperser, autorotation / revolution mixer, homodisper, multiaxial disperser, planetar.
  • Dispersers such as a Lee mixer and a thin film swirl type high-speed mixer can be used. It is also possible to disperse a plurality of these dispersers in combination.
  • a peripheral speed of 1 m / s to 50 m / s it is preferable to disperse at a peripheral speed of 1 m / s to 50 m / s.
  • a peripheral speed of 1 m / s or more is preferable because various materials can be dissolved or dispersed well.
  • a peripheral speed of 50 m / s or less is preferable because various materials are not destroyed by heat or shear force due to dispersion and reaggregation does not occur.
  • the dispersion degree of the coating solution is preferably such that the particle size measured with a particle gauge is 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. If the particle size is less than 0.1 ⁇ m, it is not preferable because the particle size is not more than the particle size of various material powders including the positive electrode active material, and the material is crushed during preparation of the coating liquid.
  • the particle size is 100 ⁇ m or less, coating can be performed stably without clogging during coating liquid discharge or generation of streaks in the coating film.
  • an edge part thinner than a center part in the TD direction of a positive electrode active material layer it is preferable to make an edge part thinner than a center part in the TD direction of a positive electrode active material layer.
  • stress is applied in a portion near the terminal portion, so that the positive electrode active material layer is easily lost. Therefore, by reducing the thickness of the positive electrode active material layer at the end, stress can be relieved and the loss of the positive electrode active material layer can be suppressed.
  • the thickness of the positive electrode active material layer in the range to 10% from the edge part of the longest line segment of a positive electrode active material layer to the center side is followed along the TD direction of a positive electrode active material layer.
  • the thickness of the positive electrode active material layer at the midpoint of the longest line segment of the positive electrode active material layer is more preferably 90% or more and less than 100%.
  • 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. If the coating speed is 100 m / min or less, sufficient coating accuracy can be secured.
  • the method for drying the coating film of the positive electrode precursor is not particularly limited, and drying methods such as hot air drying and 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.
  • the coating film may be dried by combining a plurality of 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 still more 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. When the drying temperature is 200 ° C.
  • the moisture contained in the positive electrode precursor after drying is preferably 0.1% or more and 10% or less, with the mass of the positive electrode active material layer being 100%.
  • the moisture contained in the positive electrode precursor can be measured, for example, by the Karl Fischer titration method (JIS 0068 (2001) “Method for measuring moisture in chemical products”).
  • the method for pressing the positive electrode precursor is not particularly limited, and a press machine such as a hydraulic press machine or a vacuum press machine can be preferably used.
  • a press machine such as a hydraulic press machine or a vacuum press machine can be preferably used.
  • the thickness, bulk density, and electrode strength of the positive electrode active material layer can be adjusted by the press pressure, the gap, and the 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. When the pressing pressure is 20 kN / cm or less, the positive electrode precursor is less likely to bend or wrinkle, and can be adjusted to the desired thickness and bulk density of the positive electrode active material layer.
  • Those skilled in the art can set an arbitrary value according to the thickness of the positive electrode precursor after drying so that the gap between the press rolls has a desired thickness and bulk density of the positive electrode active material layer.
  • a person skilled in the art can set the press speed to an arbitrary speed at which bending and wrinkle hardly occur in the positive electrode precursor.
  • the surface temperature of the press part may be room temperature, or the press part 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 of the binder used minus 60 ° C. or more, more preferably the melting point of the binder minus 45 ° C. or more, more preferably the melting point of the binder minus 30. It is above °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 the melting point plus 30 ° C. or less, and more preferably the melting point of the binder plus 20 ° C. or less. .
  • the surface temperature of the press part is preferably 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. It is not lower than 170 ° C.
  • the surface temperature of the press part is preferably 40 ° C. or higher and 150 ° C. or lower, more preferably 55 ° C. or higher and 130 ° C. or lower, and further preferably 70 ° C. It is at least 120 ° C.
  • stress is applied to the current collector portion where the positive electrode active material layer is not applied, and wrinkles are formed. Further, the positive electrode precursor can be slit again after pressing.
  • 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.
  • the thickness of the positive electrode active material layer is more preferably 25 ⁇ m or more and 100 ⁇ m or less, more preferably 30 ⁇ m or more and 80 ⁇ m or less per side. If this thickness is 20 ⁇ m or more, sufficient charge / discharge capacity can be exhibited. If this thickness is 200 ⁇ m or less, the ion diffusion resistance in the electrode can be kept low. Therefore, sufficient output characteristics can be obtained, the cell volume can be reduced, and therefore the energy density can be increased.
  • the upper limit and the lower limit of the thickness range of the positive electrode active material layer can be arbitrarily combined.
  • the thickness of the positive electrode active material layer in the case where the current collector has through-holes or irregularities refers to the average value of the thickness per side of the portion of the current collector that does not have through-holes or irregularities.
  • each X 0 and Y 0 is defined as the average particle diameter X 1 and Y 1 .
  • the amount of the lithium compound other than the positive electrode active material contained in the positive electrode after lithium doping is preferably 1% by mass or more and 50% by mass or less, more preferably 2.5% by mass, based on the total mass of the positive electrode active material layer in the positive electrode. % To 25% by mass.
  • the amount of the lithium compound is 1% by mass or more, since the lithium compound other than the positive electrode active material suppresses the decomposition reaction of the electrolytic solution solvent on the positive electrode in a high temperature environment, the high temperature durability is improved, and 2.5% by mass. The effect becomes remarkable at more than%.
  • the amount of the lithium compound other than the positive electrode active material is 50% by mass or less, the electron conductivity between the positive electrode active materials is relatively less likely to be inhibited by the lithium compound other than the positive electrode active material, and thus exhibits high input / output characteristics. 25 mass% or less is particularly preferable from the viewpoint of input / output characteristics.
  • the combination of the lower limit and the upper limit is arbitrary.
  • heat treatment is performed in a state where one or more carbon materials (hereinafter also referred to as “base material”) and a carbonaceous material precursor coexist.
  • a composite carbon material obtained by combining a carbonaceous material derived from a carbonaceous material precursor is preferable.
  • the substrate and the carbonaceous material precursor may be mixed at a temperature higher than the melting point of the carbonaceous material precursor.
  • the heat treatment temperature may be a temperature at which a component generated by volatilization or thermal decomposition of the carbonaceous material precursor to be used becomes a carbonaceous material, preferably 400 ° C. or higher and 2,500 ° C. or lower, more preferably 500 ° C. or higher. It is 2,000 ° C. or lower, more preferably 550 ° C. or higher and 1,500 ° C. or lower.
  • the atmosphere in which the heat treatment is performed is not particularly limited, but a non-oxidizing atmosphere is preferable.
  • composite carbon material is composite carbon materials 1 and 2 described later. Either of these may be selected and used, or both of these may be used in combination.
  • the composite carbon material 1 is a composite carbon material using as a base material one or more carbon materials having a BET specific surface area of 100 m 2 / g or more and 3,000 m 2 / g or less.
  • the substrate 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 BET specific surface area of the composite carbon material 1 is preferably 100 m 2 / g or more and 1,500 m 2 / g or less, more preferably 150 m 2 / g or more and 1,100 m 2 / g or less, and further preferably 180 m 2 / g or more and 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 the lithium ion diffusion becomes good, so that high input / output characteristics can be exhibited. By being 1,500 m ⁇ 2 > / g or less, since the charging / discharging efficiency of lithium ion improves, cycle durability is not impaired.
  • the upper limit and the lower limit of the above range of the BET specific surface area of the composite carbon material 1 can be arbitrarily combined.
  • the mass ratio of the carbonaceous material to the base material in the composite carbon material 1 is preferably 10% by mass to 200% by mass, more preferably 12% by mass to 180% by mass, and still more preferably 15% by mass to 160% by mass. Especially preferably, it is 18 mass% or more and 150 mass% or less. If the mass ratio of the carbonaceous material is 10% by mass or more, the micropores that the base material has can be appropriately filled with the carbonaceous material, and the charge / discharge efficiency of lithium ions is improved. It can show durability. If the mass ratio of the carbonaceous material is 200% by mass or less, the pores can be appropriately maintained and lithium ion diffusion is improved, and thus high input / output characteristics can be exhibited.
  • the dope amount of lithium ions per unit mass of the composite carbon material 1 is 530 mAh / g or more and 2500 mAh / g or less. More preferably, it is 620 mAh / g or more and 2,100 mAh / g or less, More preferably, it is 760 mAh / g or more and 1,700 mAh / g or less, Most preferably, it is 840 mAh / g or more and 1,500 mAh / g or less.
  • the upper limit and the lower limit of the numerical range of the lithium ion doping amount can be arbitrarily combined.
  • the negative electrode potential is lowered by doping lithium ions. Therefore, when the negative electrode containing the composite carbon material 1 doped with lithium ions is combined with the positive electrode, the voltage of the non-aqueous lithium storage element is increased and the utilization capacity of the positive electrode is increased. Therefore, the capacity and energy density of the obtained non-aqueous lithium storage element are increased.
  • a composite carbon material 1a using activated carbon as a base material will be described.
  • the mesopore amount V m1 is 0.300 cc / g or less, the BET specific surface area can be increased, the lithium ion doping amount can be increased, and the bulk density of the negative electrode can be increased. As a result, the negative electrode can be thinned.
  • the micropore amount V m2 is 0.650 cc / g or less, high charge / discharge efficiency for lithium ions can be maintained. If the mesopore volume V m1 and the micropore volume V m2 are equal to or higher than the lower limit (0.010 ⁇ V m1 , 0.001 ⁇ V m2 ), high input / output characteristics can be obtained.
  • 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 achieving high input / output characteristics. From the viewpoint of high energy density, the average pore diameter is preferably 65 mm or less, and 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 1a has a (002) plane spacing d002 of 3.60 to 4.00 and the crystallite size in the c-axis direction obtained from the half width of this peak.
  • Lc is preferably 8.0 to 20.0 ⁇
  • d002 is 3.60 to 3.75 ⁇
  • the crystallite size Lc in the c-axis direction obtained from the half width of this peak is 11.0 ⁇ . More preferably, it is 16.0 mm or less.
  • 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 of the activated carbon powder is preferably 1 ⁇ m or more and 15 ⁇ m or less, more preferably 2 ⁇ m or more and 10 ⁇ m or less.
  • the pore distribution of the activated carbon used for the base material is important.
  • 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 used.
  • V 2 (cc / g) 0.050 ⁇ V 1 ⁇ 0.500, 0.005 ⁇ V 2 ⁇ 1.000, and 0.2 ⁇ V 1 / V 2 ⁇ 20.0. It is preferable.
  • the meso Anaryou V 1 more preferably 0.050 ⁇ V 1 ⁇ 0.350, 0.100 ⁇ V 1 ⁇ 0.300 is more preferable.
  • the micropore amount V 2 is more preferably 0.005 ⁇ V 2 ⁇ 0.850, and further preferably 0.100 ⁇ V 2 ⁇ 0.800.
  • the ratio of mesopore amount / micropore amount is more preferably 0.22 ⁇ V 1 / V 2 ⁇ 15.0, and further preferably 0.25 ⁇ V 1 / V 2 ⁇ 10.0.
  • the mesopore volume V 1 of the activated carbon is 0.050 or more
  • the micropore volume V 2 is 0.005 or more
  • V 1 / V 2 is 0.2 or more
  • V 1 / V 2 The pore structure of the composite carbon material 1a can be easily obtained even when is 20.0 or less.
  • the carbonaceous material precursor used as a raw material for the composite carbon material 1a is preferably an organic material that can be deposited on the activated carbon by being heat-treated, and that can be dissolved in a solid, liquid, or solvent.
  • the carbonaceous material precursor include pitch, mesocarbon microbeads, coke, and synthetic resins such as furfuryl alcohol resin and phenol resin.
  • Pitch is roughly divided into petroleum pitch and coal pitch.
  • Examples of 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 is heat-treated in the presence of activated carbon, and the carbonaceous material is deposited on the activated carbon by thermally reacting the volatile component or pyrolyzed component of the pitch on the surface of the activated carbon. 1a is obtained.
  • the deposition of pitch volatile components or pyrolysis components into the activated carbon pores proceeds, and at 400 ° C. or higher, the reaction that the deposited components become carbonaceous materials proceeds.
  • 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 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 a hydrocarbon gas volatilized from a carbonaceous material precursor, and the carbonaceous material is deposited in a gas phase.
  • a method 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 and then heat-treated is also possible.
  • the mass ratio of the carbonaceous material to the activated carbon in the composite carbon material 1a is preferably 10% by mass to 100% by mass, and more preferably 15% by mass to 80% by mass. If the mass ratio of the carbonaceous material is 10% by mass or more, the micropores that the activated carbon has can be appropriately filled with the carbonaceous material, and the charge / discharge efficiency of lithium ions is improved. Less likely to be damaged. If the mass ratio of the carbonaceous material is 100% by mass or less, the pores of the composite carbon material 1a are appropriately maintained and maintained with a large specific surface area. Therefore, from the result that the doping amount of lithium ions can be increased, high output density and high durability can be maintained even if the negative electrode is thinned.
  • the composite carbon material 2 is a composite carbon material using, as a base material, 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.
  • 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 2 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 this BET specific surface area is 1 m 2 / g or more, a sufficient reaction field with lithium ions can be secured, and thus high input / output characteristics can be exhibited.
  • the mass ratio of the carbonaceous material to the base material in the composite carbon material 2 is preferably 1% by mass or more and 30% by mass or less, more preferably 1.2% by mass or more and 25% by mass or less, and further preferably 1.5% by mass or more. It is 20 mass% or less. If the mass ratio of the carbonaceous material is 1% or more by mass, the carbonaceous material can sufficiently increase the reaction site with lithium ions and facilitates the desolvation of lithium ions. be able to. If the mass ratio of the carbonaceous material is 20% by mass or less, the diffusion of lithium ions between the carbonaceous material and the base material in the solid can be satisfactorily maintained, and thus high input / output characteristics can be exhibited. Since the charge / discharge efficiency of lithium ions can be improved, high cycle durability can be exhibited.
  • the negative electrode potential is lowered by doping lithium ions. Therefore, when the negative electrode including the composite carbon material 2 doped with lithium ions is combined with the positive electrode, the voltage of the nonaqueous lithium storage element is increased and the capacity of the positive electrode is increased. Therefore, the capacity and energy density of the obtained non-aqueous lithium storage element are increased.
  • a composite carbon material 2a using a graphite material as a base material will be described.
  • the average particle diameter of the composite carbon material 2a is preferably 1 ⁇ m or more and 10 ⁇ m or less, 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 lithium ions can be improved, and thus high cycle durability can be exhibited. If it is 10 micrometers or less, since the reaction area of the composite carbon material 2a and a non-aqueous electrolyte solution will increase, a high input / output characteristic can be shown.
  • the carbonaceous material precursor used as a raw material of the composite carbon material 2a is preferably an organic material that can be combined with the graphite material by heat treatment and can be dissolved in a solid, liquid, or solvent.
  • the carbonaceous material precursor include pitch, mesocarbon microbeads, coke, and synthetic resins such as furfuryl alcohol resin and 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 2a is preferably 1% by mass or more and 10% by mass or less, more preferably 1.2% by mass or more and 8% by mass or less, and further preferably 1.5% by mass or more. It is 6 mass% or less, Most preferably, it is 2 mass% or more and 5 mass% or less. If the mass ratio of the carbonaceous material is 1% by mass or more, the carbonaceous material can sufficiently increase the reaction sites with lithium ions, and the desolvation of lithium ions is facilitated, so that high input / output characteristics are exhibited. be able to.
  • the initial charge capacity is 300 mAh / g or more, the pre-doping amount of alkali metal ions can be sufficiently increased, so that even when the negative electrode active material layer is thinned, high output characteristics can be obtained. Further, if the initial charge capacity is 1,600 mAh / g or less, the swelling / shrinkage of the composite carbon material when the composite carbon material is doped / undoped with alkali metal ions is reduced, and the strength of the negative electrode is maintained. Be drunk.
  • the composite carbon material 1c described above is particularly preferably a composite porous material satisfying the following conditions (1) and (2) from the viewpoint of obtaining a good internal resistance value.
  • (1) Mesopore volume (amount of pores having a diameter of 2 nm to 50 nm) Vm 1 (cc / g) calculated by the BJH method is 0.01 ⁇ Vm 1 ⁇ 0.10. Fulfill.
  • (2) The amount of micropores (amount of pores having a diameter of less than 2 nm) Vm 2 (cc / g) calculated by the above-described MP method satisfies the condition of 0.01 ⁇ Vm 2 ⁇ 0.30.
  • the negative electrode active material is preferably particulate.
  • the silicon, silicon oxide, silicon alloy and silicon compound, and tin and tin compound preferably have a particle size of 0.1 ⁇ m or more and 30 ⁇ m or less. If the particle diameter is 0.1 ⁇ m or more, the contact area with the electrolytic solution increases, so the resistance of the non-aqueous lithium storage element can be lowered. Moreover, if this particle diameter is 30 ⁇ m or less, swelling and shrinkage of the negative electrode due to doping and dedoping of alkali metal ions to the negative electrode accompanying charge / discharge are reduced, and the strength of the negative electrode is maintained.
  • the silicon, silicon oxide, silicon alloy and silicon compound, and tin and tin compound can be formed into fine particles by pulverization using a jet mill with a built-in classifier, a stirring ball mill, or the like.
  • the pulverizer is equipped with a centrifugal classifier, and fine particles pulverized in an inert gas environment such as nitrogen and argon can be collected by a cyclone or a dust collector.
  • the content ratio of the negative electrode active material in the negative electrode active material layer of the negative electrode precursor is preferably 70% by mass or more and more preferably 80% by mass or more based on the total mass of the negative electrode active material layer.
  • the conductive filler is preferably mixed with the negative electrode active material layer from the viewpoint of high input.
  • the amount of the binder used in the negative electrode active material layer is preferably 3 to 25 parts by mass and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the negative electrode active material.
  • the amount of the binder is less than 3 parts by mass, sufficient adhesion cannot be secured between the current collector and the negative electrode active material layer in the negative electrode (precursor), and the current collector and the active material layer And the interface resistance increases.
  • the amount of the binder is larger than 25 parts by mass, the binder covers the active material surface of the negative electrode (precursor) excessively, and the diffusion resistance of ions in the active material pores increases. .
  • the material constituting the negative electrode current collector in this embodiment is preferably a metal foil that has high electron conductivity and is unlikely to deteriorate due to elution into a non-aqueous electrolyte and reaction with an electrolyte or ions.
  • a metal foil that has high electron conductivity and is unlikely to deteriorate due to elution into a non-aqueous electrolyte and reaction with an electrolyte or ions.
  • metal foil For example, aluminum foil, copper foil, nickel foil, stainless steel foil, etc. are mentioned.
  • a copper foil is preferable.
  • the metal foil may be a metal foil having no irregularities, through-holes, etc., or may be a metal foil having irregularities subjected to embossing, chemical etching, electrolytic deposition, blasting, etc., expanded metal, punching metal, A metal foil having a through hole such as an etching foil may be used.
  • the negative electrode current collector in the present embodiment is preferably a metal foil having no through holes. Without the through-hole, the manufacturing cost is low, the thinning is easy, it can contribute to high energy density, and the current collecting resistance can be lowered, so that high input / output characteristics can be obtained.
  • 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 the 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.
  • various materials including a negative electrode active material are dispersed or dissolved in water or an organic solvent to prepare a slurry-like negative electrode coating liquid, and this negative electrode coating liquid is applied to one or both surfaces on the 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 thickness or bulk density of the negative electrode active material layer.
  • the preparation of the negative electrode coating liquid, the formation of the negative electrode coating film, and the drying, and the optional press are as described above as the preparation of the positive electrode coating liquid, the formation of the positive electrode coating film, the drying, and the press, respectively.
  • the present invention can be carried out in the same manner as described above, or with appropriate modifications made by those skilled in the art.
  • the viscosity ( ⁇ b), thixotropy index (TI) value, and the like of the negative electrode coating liquid may be the same as those of the positive electrode coating liquid.
  • the thickness of the negative electrode active material layer is preferably 5 ⁇ m or more and 100 ⁇ m or less per side, the lower limit is more preferably 7 ⁇ m or more, still more preferably 10 ⁇ m or more, and the upper limit is more preferably 80 ⁇ m or less, still more preferably 60 ⁇ m. It is as follows. When the thickness of the negative electrode active material layer is 5 ⁇ m or more per side, streaks or the like hardly occur when the negative electrode active material layer is applied, and the coating property is excellent. When the thickness of the negative electrode active material layer is 100 ⁇ m or less per side, a high energy density can be expressed by reducing the cell volume.
  • the thickness of the negative electrode active material layer in the case where the negative electrode current collector has through holes, irregularities, and the like refers to the average value of the thickness per side of the portion of the negative electrode current collector that does not have through holes and irregularities.
  • the electrolytic solution is a non-aqueous electrolytic solution. That is, this electrolytic solution contains an organic solvent (nonaqueous solvent).
  • the non-aqueous electrolyte contains a lithium salt electrolyte. That is, the nonaqueous electrolytic solution contains lithium ions derived from this lithium salt electrolyte as an electrolyte.
  • the maximum response current value in the voltage range of 4.8 V (vs. Li / Li + ) or less is 0.010 mA / cm 2 or less with respect to the area of the aluminum foil. This value is preferably 0.008mA / cm 2 or less, more preferably 0.005 mA / cm 2 or less, more preferably 0.003mA / cm 2 or less.
  • the present embodiment it is preferable to dope lithium into the negative electrode by applying a voltage between the positive electrode precursor and the negative electrode to decompose the lithium compound in the positive electrode precursor.
  • a voltage between the positive electrode precursor and the negative electrode to decompose the lithium compound in the positive electrode precursor.
  • the aluminum foil of the positive electrode current collector is oxidized and eluted by applying a high voltage to the positive electrode precursor, and in particular, the positive electrode active material layer is applied.
  • Unexposed aluminum foil may corrode.
  • the positive electrode current collector is broken and cannot be formed as a power storage element.
  • the elution reaction of the positive electrode current collector depends on the composition of the non-aqueous electrolyte solution.
  • the positive electrode current collector Since corrosion due to elution of the body, resulting increase in resistance, disconnection of the current collector, and the like can be suppressed, high input / output characteristics can be obtained and high-temperature durability is also excellent.
  • lithium salt examples include a lithium salt having an imide structure and other lithium salts.
  • a lithium salt electrolyte having an imide structure for example, lithium bis (fluorosulfonyl) imide [LiN (SO 2 F) 2 , abbreviation: LiFSI], lithium bis (trifluoromethanesulfonyl) imide [LiN (SO 2 CF 3 ) 2 , Abbreviation: LiTFSI], lithium bis (pentafluoroethanesulfonyl) imide [LiN (SO 2 C 2 F 5 ) 2 , abbreviation: LiBETI], LiN (SO 2 CF 3 ) (SO 2 C 2 F 5 ), LiN ( SO 2 CF 3) (SO 2 C 2 F 4 H) and the like:
  • LiC (SO 2 F) 3 LiC (SO 2 CF 3 ) 3
  • lithium salts having an imide structure when used alone, the corrosiveness to a positive electrode current collector such as an aluminum foil is high and the withstand voltage is low (maximum voltage range of 3.8V to 4.8V). There is also a lithium salt (which increases the response current value). In such a case, it is preferable to use a lithium salt (for example, LiF 2 BC 2 O 4 ) that easily generates a fluoride ion by decomposition and easily forms a film on the surface of the aluminum foil, an additive described later, and the like.
  • a lithium salt for example, LiF 2 BC 2 O 4
  • the total concentration of the lithium salt electrolyte in the non-aqueous electrolyte is preferably 0.5 mol / L or more, based on the total amount of the non-aqueous electrolyte, and is in the range of 0.5 mol / L to 2.0 mol / L. Is more preferable. If the concentration of the lithium salt electrolyte is 0.5 mol / L or more, since the anion is sufficiently present, the capacity of the electricity storage device can be sufficiently increased. When the concentration of the lithium salt electrolyte is 2.0 mol / L or less, it is possible to prevent undissolved lithium salt from precipitating in the nonaqueous electrolytic solution and the viscosity of the electrolytic solution to be too high, and the conductivity is lowered. And output characteristics are not deteriorated.
  • non-aqueous solvent contained in the non-aqueous electrolyte solution in the present embodiment examples include cyclic carbonates and chain carbonates.
  • examples of 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.
  • dimethyl carbonate having a low boiling point and inferior heat resistance it is preferable not to use dimethyl carbonate having a low boiling point and inferior heat resistance.
  • Ethylene carbonate is preferable because it forms a protective film on the negative electrode surface after reductive decomposition, and a non-aqueous lithium electricity storage device having excellent durability at high temperatures and high voltages can be obtained.
  • Propylene carbonate is preferred because it has a low melting point, and is less likely to cause solidification of the non-aqueous electrolyte solution or precipitation of the non-aqueous solvent component in a low-temperature environment.
  • ethylene carbonate is contained more than propylene carbonate in order to effectively exhibit the ability to form a protective film on the negative electrode surface of ethylene carbonate.
  • the non-aqueous solvent in this embodiment preferably contains both a cyclic carbonate and a chain carbonate.
  • the nonaqueous electrolytic solution containing a cyclic carbonate and a chain carbonate is advantageous in that a lithium salt having a desired concentration is dissolved and a high lithium ion conductivity is exhibited.
  • 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, preferably 95% by mass or less, more preferably, based on the total mass of the nonaqueous electrolytic solution. 90% by mass or less.
  • the total content of the cyclic carbonate and the chain carbonate is 50% by mass or more, it is easy to dissolve a lithium salt having a desired concentration, and high lithium ion conductivity can be expressed, and 95% by mass or less. If it is, it will become easy that electrolyte solution further contains the additive mentioned later.
  • the upper and lower limits of the total concentration range can be arbitrarily combined.
  • acyclic fluorine-containing ethers, cyclic fluorine-containing carbonates, and cyclic fluorine-containing phosphazenes which are fluorine-containing compounds, generate fluoride ions due to decomposition and easily form a film on the surface of the aluminum foil. Since corrosion can be suppressed, it is preferable.
  • Examples of the acyclic fluorine-containing ether 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 can be 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 mass 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 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 non-cyclic fluorine-containing ether may be used alone or in combination of two or more.
  • the cyclic fluorine-containing carbonate is preferably at least one selected from the group consisting of fluoroethylene carbonate (FEC) and difluoroethylene carbonate (dFEC) from the viewpoint of compatibility with other non-aqueous solvents.
  • FEC fluoroethylene carbonate
  • dFEC difluoroethylene carbonate
  • the content of the cyclic fluorine-containing 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 mass of the nonaqueous electrolytic solution. If the content of the cyclic fluorinated carbonate 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 electrolytic 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, and thus high input / output characteristics. Can be expressed.
  • the cyclic fluorine-containing carbonate may be used alone or in combination of two or more.
  • cyclic fluorine-containing phosphazene examples include ethoxypentafluorocyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene and the like, and one or more selected from these are preferable.
  • the electrolytic solution containing an alkali metal salt in the present embodiment is a non-aqueous electrolytic solution. That is, this electrolytic solution contains a nonaqueous solvent.
  • the non-aqueous electrolyte contains 0.5 mol / L or more alkali metal salt based on the total amount of the non-aqueous electrolyte. That is, the nonaqueous electrolytic solution contains an alkali metal salt as an electrolyte.
  • non-aqueous solvent contained in the non-aqueous electrolyte examples include cyclic carbonates typified by ethylene carbonate and propylene carbonate, and chain carbonates typified by dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. From the viewpoint of suppressing an increase in resistance under an environment of 85 ° C. or higher, it is preferable that the Hansen solubility parameter RED value for the binder is greater than 1.
  • the electrolyte salt containing an alkali metal ion dissolved in the non-aqueous solvent as described above for example, MFSI, MBF 4 , MPF 6 , MClO 4 or the like is used where M is Li, Na, K, Rb or Cs.
  • a method of containing at least one salt, and an alkaline earth metal oxide, alkaline earth metal hydroxide, alkaline earth metal halide, and alkaline earth metal carboxylate, and decomposing in a pre-doping step described later Is mentioned.
  • the electrolyte salt concentration in the electrolytic solution is preferably in the range of 0.5 to 2.0 mol / L.
  • anions are sufficiently present, and the capacity of the non-aqueous lithium storage element is maintained.
  • an electrolyte salt concentration of 2.0 mol / L or less the salt is sufficiently dissolved in the electrolytic solution, and appropriate viscosity and conductivity of the electrolytic solution are maintained.
  • the total value of these salt concentrations should be 0.5 mol / L or more. Is preferable, and the range of 0.5 to 2.0 mol / L is more preferable.
  • the positive electrode precursor and the negative electrode are laminated via a separator, or are laminated and wound to form an electrode laminate or an electrode winding body having a positive electrode precursor, a separator, and a negative electrode.
  • a separator the separator used for a lithium ion secondary battery, an electric double layer capacitor, a lithium ion capacitor etc. can be used conveniently.
  • the shrinkage ratio (L1-L2) / L1 of the separator is preferably 0.08 or less, more preferably 0.06 or less, and still more preferably 0.04 or less.
  • the shrinkage rate of the separator can be measured by the method shown in the examples described later.
  • the separator used in the present embodiment preferably has a high liquid retainability of the non-aqueous electrolyte.
  • the separator in order to develop these physical properties even under high temperature conditions (for example, 85 ° C. or higher), it is preferable that the separator is not clogged even after holding at 120 ° C. for 1 hour and the liquid retaining property is maintained.
  • the air permeability P of the separator after being held for 1 hour in an environment of 120 ° C. is preferably 5 seconds / 100 mL or more and 300 seconds / 100 mL or less.
  • the air permeability P of the separator is more preferably 7 seconds / 100 mL or more and 250 seconds / 100 mL or less, more preferably 15 seconds / 100 mL or more and 200 seconds / 100 mL or less, and particularly preferably 50 seconds / 100 mL or more. 150 seconds / 100 mL or less.
  • This air permeability P can be measured by the method shown in the examples described later.
  • the separator in the present embodiment is preferably a separator including at least one selected from the group consisting of polyolefin, cellulose, and aramid resin.
  • the separator containing the coating layer containing an aramid resin or inorganic fine particles is preferable.
  • the separator containing these materials is less likely to shrink even when held at a high temperature (for example, 85 ° C. or higher), can maintain the liquid retainability of the non-aqueous electrolyte, and has low resistance of the non-aqueous lithium storage element. Can be maintained, which is preferable.
  • the separator production method in the present embodiment is preferably a polymer (typically polyolefin) and a plasticizer, or a polymer and a plasticizer, from the viewpoint of appropriately controlling the physical property balance between the permeability and membrane strength of the separator. Forming by melting and kneading the agent and filler; stretching; extracting the plasticizer (and filler if necessary); and heat setting.
  • the plasticizer used in the kneading in step 1 may be those conventionally used in the production of polyolefin microporous membranes.
  • the plasticizer include phthalic acid esters such as dioctyl phthalate ("DOP"), diheptyl phthalate and dibutyl phthalate; organic acid esters other than phthalic acid esters such as adipic acid ester and glyceric acid ester; and trioctyl phosphate. Examples thereof include phosphate ester, liquid paraffin, solid wax, mineral oil, etc. These may be used alone or in combination of two or more, and among these, compatibility with polyethylene Phthalate is particularly preferred.
  • DOP dioctyl phthalate
  • organic acid esters other than phthalic acid esters such as adipic acid ester and glyceric acid ester
  • trioctyl phosphate examples thereof include phosphate ester, liquid paraffin, solid wax, mineral oil, etc. These may be used
  • polyolefin and a plasticizer may be kneaded to form a kneaded product, or a polyolefin, a plasticizer, and a filler may be kneaded to form a kneaded product.
  • a filler used in the latter case, at least one of organic fine particles and inorganic fine particles can be used.
  • organic fine particles examples include modified polystyrene fine particles and modified acrylic resin particles.
  • Examples of the material constituting the inorganic fine particles include alumina, silica (silicon oxide), titania, zirconia, magnesia, ceria, yttria, zinc oxide, iron oxide, and other oxide ceramics; silicon nitride, titanium nitride, boron nitride Nitride ceramics such as silicon carbide, calcium carbonate, aluminum sulfate, aluminum hydroxide, potassium titanate, talc, kaolin clay, kaolinite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amesite, bentonite, Other ceramics such as asbestos, zeolite, calcium silicate, magnesium silicate, diatomaceous earth, and silica sand; glass fiber and the like.
  • silica silicon oxide
  • titania titanium nitride
  • boron nitride Nitride ceramics such as silicon carbide, calcium carbonate, aluminum sulfate, aluminum hydrox
  • the blend ratio of polyolefin, plasticizer, and filler used as necessary in the kneading in step 1 is not particularly limited.
  • the proportion of the polyolefin in the kneaded product is preferably 25 to 50% by mass based on the total mass of the kneaded product from the viewpoint of the strength and film-forming property of the separator obtained.
  • the proportion of the plasticizer in the kneaded product is preferably 30 to 60% by mass based on the total mass of the kneaded product from the viewpoint of obtaining a viscosity suitable for extrusion.
  • the kneading method in the kneading in step 1 is not particularly limited, and a conventionally used kneading method may be appropriately selected and employed.
  • a polyolefin, a plasticizer, and a mixture of some of the fillers used as necessary are mixed in advance using a general mixer such as a Henschel mixer, a V-blender, a pro shear mixer, or a ribbon blender. After mixing, the remaining raw materials may be further kneaded, or all of the raw materials may be kneaded simultaneously.
  • the apparatus used for kneading is not particularly limited, and can be kneaded using a melt kneading apparatus such as an extruder or a kneader.
  • the formation of the sheet in step 2 includes, for example, extruding the kneaded material obtained in step 1 into a sheet shape through, for example, a T-die, and bringing the extrudate into contact with a heat conductor to cool and solidify.
  • a heat conductor for example, metal, water, air, plasticizer itself, and the like can be used.
  • the stretching in step 3 includes stretching the sheet (sheet-like formed body) obtained in step 2 to obtain a stretched sheet.
  • Examples of the sheet stretching method in stretching include MD uniaxial stretching by a roll stretching machine; TD uniaxial stretching by a tenter; sequential biaxial stretching by a combination of a roll stretching machine and a tenter, or a combination of a tenter and a tenter; simultaneous biaxial And simultaneous biaxial stretching by tenter or inflation molding. From the viewpoint of obtaining a more uniform film, the sheet stretching method is preferably simultaneous biaxial stretching.
  • the total surface magnification at the time of stretching is preferably 8 times or more, more preferably 15 times or more, from the viewpoint of the uniformity of the thickness of the sheet and the balance of tensile elongation, porosity, and average pore diameter, 30 More than double is more preferable. When the total surface magnification is 30 times or more, a high-strength separator is easily obtained.
  • the stretching temperature is preferably 121 ° C. or higher from the viewpoint of imparting high permeability and high temperature and low shrinkage, and is preferably 135 ° C. or lower from the viewpoint of film strength.
  • Examples of the extraction method optionally performed prior to the stretching in Step 3 include a method of immersing the sheet or the stretched sheet in an extraction solvent, a method of showering the extraction solvent on the sheet or the stretched sheet, and the like.
  • the extraction solvent is preferably a poor solvent for polyolefin and a good solvent for plasticizer and filler, and preferably has a boiling point lower than the melting point of polyolefin.
  • Examples of the heat treatment method in step 4 include a heat setting method in which the stretched sheet obtained in step 3 is stretched and / or relaxed at a predetermined temperature using a tenter and / or a roll stretching machine.
  • the relaxation operation is the MD of the film (the traveling direction when winding the separator formed into a sheet shape on a roll, also referred to as “longitudinal direction”) and / or TD (the direction orthogonal to the MD direction) (Referred to as “width direction” or “short direction”) is a reduction operation performed at a predetermined relaxation rate.
  • the stretched sheet obtained in step 3 is preferably stretched 1.5 times or more to TD, and may be stretched 1.8 times or more to TD. More preferred.
  • the TD stretching ratio of the stretched sheet is preferably 6.0 times or less, and more preferably 4.0 times or less from the viewpoint of maintaining the balance between the film strength and the permeability.
  • the predetermined relaxation rate is preferably 0.9 times or less from the viewpoint of suppression of heat shrinkage, and is preferably 0.6 times or more from the viewpoint of preventing wrinkle generation, porosity, and permeability.
  • the relaxation operation may be performed in both directions of MD and TD, but may be a relaxation operation of only one of MD and TD. Even if the relaxation operation is performed on only one of MD and TD, it is possible to reduce the thermal contraction rate not only in the operation direction but also in the other direction.
  • the extraction optionally performed prior to the heat setting in step 4 may be performed by the same method as the extraction optionally performed prior to the stretching in step 3.
  • the shrinkage ratio of the separator in this embodiment is, for example, the concentration of polyolefin during extrusion, the blending ratio of various polyolefins in the polyolefin, the molecular weight of the polyolefin, the stretching ratio in step 3 and / or the heat setting in step 4, It can be adjusted by appropriately changing the stretching temperature and the like.
  • a metal can, a laminate packaging material, or the like can be used as the exterior body.
  • the metal can is preferably made of aluminum.
  • the laminate packaging material a film in which a metal foil and a resin film are laminated is preferable, and 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 non-aqueous electrolyte contained therein and melts and seals the exterior body during heat sealing. Polyolefin, acid-modified polyolefin, and the like can be suitably used.
  • the non-aqueous lithium storage element of the present embodiment includes, for example, an electrode laminate or an electrode winding body together with a non-aqueous electrolyte solution, and then sequentially performs lithium doping, aging, and degassing. Can be manufactured.
  • an exemplary manufacturing method of the non-aqueous lithium storage element will be described.
  • the method for connecting the electrode laminate or the electrode winding body to the positive electrode terminal and the negative electrode terminal is not particularly limited, and can be performed by a method such as resistance welding or ultrasonic welding.
  • the drying method is not limited, and it can be dried by vacuum drying or the like.
  • the residual solvent is preferably 1.5% by mass or less per mass of the positive electrode active material layer or the negative electrode active material layer. If the residual solvent is 1.5% by mass or less, the self-discharge characteristic or the cycle characteristic is hardly deteriorated, which is preferable.
  • a non-aqueous electrolyte solution is injected into the exterior body in which the dried electrode laminate or electrode winding body is accommodated. It is desirable that the positive electrode precursor, the negative electrode, and the separator be sufficiently impregnated with a nonaqueous electrolytic solution after the injection. In a state where the non-aqueous electrolyte solution is not immersed in at least a part of the positive electrode precursor, the negative electrode, and the separator, since the dope proceeds non-uniformly in lithium doping described later, the resistance of the obtained non-aqueous lithium storage element is It may increase or durability may decrease.
  • the impregnation method is not particularly limited.
  • the nonaqueous lithium storage element after injection is placed in a decompression chamber with the exterior body opened, the inside of the chamber is decompressed using a vacuum pump, and again A method of returning to atmospheric pressure can be used. After the impregnation, the opened exterior body is sealed while being decompressed.
  • the alkali metal to be used is lithium
  • the “alkali metal doping step” is referred to as “lithium doping step”.
  • the organic solvent in the non-aqueous electrolyte solution is decomposed at the negative electrode, and a lithium ion permeable solid polymer film is formed on the negative electrode surface.
  • ⁇ gas releasing> It is preferable to further degas after aging to reliably remove the gas remaining in the non-aqueous electrolyte, the positive electrode, and the negative electrode.
  • gas remains in at least a part of the non-aqueous electrolyte, the positive electrode, and the negative electrode, ion conduction is inhibited, and thus the resistance of the obtained non-aqueous lithium storage element increases.
  • the degassing method is not particularly limited, and for example, a method in which a nonaqueous lithium electricity storage element is installed in a decompression chamber with the exterior body opened, and the chamber is decompressed using a vacuum pump, or the like is used. be able to.
  • a carbonate solvent such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, or the like can be suitably used because the lithium salt electrolyte attached to the separator surface may be washed away.
  • a cleaning method for example, the separator is immersed in a carbonate solvent 50 to 100 times the mass of the separator for 10 minutes or more, and then the solvent is changed and the separator is immersed again. Thereafter, the separator is taken out of the carbonate solvent and dried in a vacuum, for example.
  • the conditions for vacuum drying can be, for example, temperature: 0 to 100 ° C., pressure: 0 to 20 kPa, and time: 1 to 40 hours. It is preferable to set the temperature at such a level that the shape of the separator does not change during vacuum drying.
  • the shrinkage ratio (L1-L2) / L1 the shrinkage ratio (L1-L2) / L1
  • the air permeability P the air permeability P
  • the withstand voltage can be measured by the method described in the examples.
  • the C rate of current in the following refers to a relative value with 1C being a current value at which discharge is completed in one hour when performing constant current discharge from the upper limit voltage to the lower limit voltage.
  • the upper limit voltage Vmax and the lower limit voltage Vmin are different depending on the examples and comparative examples, they are defined individually in each of the examples and comparative examples.
  • the discharge capacity Q is a value obtained by the following method. First, constant-current charging is performed in a thermostatic chamber in which a cell corresponding to the nonaqueous lithium storage element is set to 25 ° C. until reaching Vmax at a current value of 20 C, and then constant-voltage charging in which a constant voltage of Vmax is applied. For a total of 30 minutes. Thereafter, constant current discharge is performed at a current value of 2 C up to Vmin. The discharge capacity at this time is defined as a discharge capacity Q (mAh) in the present embodiment.
  • the room temperature discharge internal resistance Ra ( ⁇ ) is a value obtained by the following method. First, constant-current charging in which a cell corresponding to a non-aqueous lithium storage element and a cell corresponding to a non-aqueous lithium storage element are set to 25 ° C. until reaching Vmax at a current value of 20 C, followed by constant-voltage charging in which a constant voltage of Vmax is applied. Perform a total of 30 minutes. Subsequently, the sampling interval is set to 0.05 seconds, and a constant current discharge is performed up to Vmin at a current value of 20 C to obtain a discharge curve (time-voltage).
  • the electric energy E (Wh) is a value obtained by the following method. Using the capacitance F (F) calculated by the method described above, A value calculated by F ⁇ (Vmax 2 ⁇ Vmin 2 ) / 2 / 3,600.
  • volume The volume V (L) of the electricity storage element refers to the volume of the portion of the exterior body in which the electrode laminate or the electrode winding body is accommodated.
  • the room temperature discharge internal resistance increase rate after the high temperature storage test 1 is measured by the following method.
  • the normal temperature discharge internal resistance after the high temperature storage test is Rb
  • the normal temperature before the start of the high temperature storage test The rate of increase in internal resistance after the high temperature storage test 1 with respect to the discharge internal resistance Ra is calculated by Rb / Ra.
  • the initial room temperature discharge internal resistance is Ra ( ⁇ )
  • the room temperature discharge internal resistance after storage for 1,000 hours at a cell voltage of 4.0 V and an environmental temperature of 85 ° C. is Rb ( ⁇ )
  • the rate of increase in internal resistance represented by the ratio Rb / Ra of both can be 3.0 or less.
  • Rb / Ra is preferably 3.0 or less, more preferably 2 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. .5 or less, more preferably 2.0 or less. If Rb / Ra is less than or equal to the above upper limit value, excellent output characteristics can be obtained stably over a long period of time, leading to a longer life of the device.
  • the internal resistance increase rate Rb / Ra can be set to 3.0 or less, further 2.5 or less, and particularly 2.0 or less. It can be 5 or less, 1.4 or less, 1.3 or less, or 1.12 or less.
  • the non-aqueous lithium electricity storage device includes the following (c): (C) It is preferable that Rb / Ra satisfies 3.0 or less.
  • the resistance change rate Rb / Ra after the high-temperature storage test 2 is preferably 3.0 or less, more preferably 2.5 or less, and still more preferably 2.0 or less. If the rate of increase in resistance after the high-temperature storage test is 3.0 or less, excellent input / output characteristics can be obtained stably for a long period of time, leading to a longer life of the non-aqueous lithium storage element.
  • the lower limit value of Rb / Ra is preferably 0.9 or more.
  • Rb / Ra be the resistance change rate after the high-temperature storage test.
  • the resistance change rate Rb / Ra after the high temperature storage test 3 is preferably 2.0 or less, more preferably 1.7 or less, and still more preferably 1.5 or less. If the rate of increase in resistance after the high-temperature storage test is 2.0 or less, the characteristics under a high-temperature environment of 85 ° C. or more are maintained. Therefore, excellent input / output characteristics can be obtained stably for a long period of time, leading to a long life of the non-aqueous lithium storage element.
  • the lower limit value of Rb / Ra is preferably 0.9 or more.
  • Rd / Ra is 3.0 or less, a sufficient discharge capacity can be obtained even at a low temperature of ⁇ 30 ° C. Therefore, for example, in an electric vehicle, it can be used for peak assist applications such as a starter even at a low temperature of ⁇ 30 ° C.
  • the non-aqueous lithium electricity storage device includes the following conditions (a) and (b): (A) The product Ra ⁇ F of Ra and F is 0.3 to 3.0; and (b) E / V is 15 to 80; It is preferable to satisfy.
  • Ra ⁇ F is a product of the initial internal resistance Ra and the electrostatic capacity F at 3.8 V, and from the viewpoint of developing sufficient charging capacity and discharging capacity for a large current, Preferably it is 3.0 or less, More preferably, it is 2.5 or less, More preferably, it is 2.0 or less.
  • Ra ⁇ F is 3.0 or less, an energy storage device having excellent input / output characteristics can be obtained. Therefore, it is preferable to combine a power storage system using a power storage element with, for example, a high-efficiency engine, sufficiently withstanding a high load applied to the power storage element.
  • Ra ⁇ F is preferably 0.3 or more, 0.4 or more, or 0.5 or more from the viewpoint of maintaining the characteristics of the electricity storage device.
  • the fine short circuit of a non-aqueous lithium electrical storage element is judged with the following method.
  • the electrode body was discharged at a constant current to 2.5 V at a current value of 100 mA, and then charged at a current value of 100 mA to a voltage of 3.5 V, followed by 3.5 V constant voltage charging for 2 hours. Is adjusted to 3.5V.
  • the electrode body was left to stand for one week in a state of being pressurized at a pressure of 10 kPa.
  • Mass ratio A 1 of the carbon material contained in the positive electrode active material layer, the mass ratio A 2 of the lithium transition metal oxides, and quantitative methods of mass ratio A 3 of the alkali metal compound is not particularly limited, for example, the following method Can be quantified.
  • Area of measurement for the positive electrode precursor is not particularly limited, but 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. If the area is 200 cm 2 or less, the sample is easy to handle. First, the positive electrode precursor is cut into the above area and vacuum dried.
  • the conditions for vacuum drying are preferably, for example, such that the residual moisture content in the positive electrode precursor is 1% by mass or less in the range of temperature: 100 to 200 ° C., pressure: 0 to 10 kPa, and time: 5 to 20 hours.
  • the residual amount of moisture can be quantified by the Karl Fischer method.
  • the weight (M 0 ) of the positive electrode precursor obtained after vacuum drying is measured.
  • the alkali metal compound is eluted in water by immersing in distilled water 100 to 150 times the weight of the positive electrode precursor for 3 days or more. It is preferable to cover the container so that distilled water does not volatilize during the immersion.
  • the mass of the obtained TG curve at 25 ° C. is defined as M 3, and the mass at the first temperature at which the mass reduction rate becomes M 3 ⁇ 0.01 / min or less at a temperature of 500 ° C. or higher is defined as M 4 .
  • All the carbon materials are oxidized and burned by heating at a temperature of 500 ° C. or lower in an oxygen-containing atmosphere (for example, an air atmosphere).
  • an oxygen-containing atmosphere for example, an air atmosphere.
  • the mass of the lithium transition metal oxide does not decrease even in an oxygen-containing atmosphere up to the temperature of the melting point of the lithium transition metal oxide minus 50 ° C. Therefore, the content A 2 of the lithium transition metal oxide in the positive electrode active material layer can be calculated by the following formula (2).
  • a 1 ⁇ (M 3 ⁇ M 4 ) / M 3 ⁇ ⁇ ⁇ 1 ⁇ (M 0 ⁇ M 1 ) / (M 0 ⁇ M 2 ) ⁇ ⁇ 100 (3)
  • M in the following formula is one or more selected from Na, K, Rb, and Cs, an oxide such as M 2 O, and a hydroxide such as MOH A halide such as MF, MCl, an oxalate such as M 2 (CO 2 ) 2 , a carboxylate such as RCOOM (wherein R is H, an alkyl group, or an aryl group); and a positive electrode active material layer, BeCO 3, MgCO 3, CaCO 3, SrCO 3, and alkaline earth metal carbonates selected from BaCO 3, or alkaline earth metal oxides, alkaline earth metal hydroxides, alkaline earth metal Halide, alkaline earth Genus
  • analysis method fails to identify the alkali metal compound, other analysis methods include 7 Li-solid NMR, XRD (X-ray diffraction), TOF-SIMS (time-of-flight secondary ion mass spectrometry), AES (Auger)
  • An alkali metal compound can also be identified by using electron spectroscopy, TPD / MS (heat generation gas mass spectrometry), DSC (differential scanning calorimetry), or the like.
  • Alkali metal carbonates and positive electrode active materials can be identified by Raman imaging of carbonate ions on the surface of the positive electrode precursor measured at an observation magnification of 1000 to 4000 times.
  • the excitation light is 532 nm
  • the excitation light intensity is 1%
  • the long operation of the objective lens is 50 times
  • the diffraction grating is 1800 gr / mm
  • the mapping method is point scanning (slit 65 mm, binning 5 pix), 1 mm step
  • the exposure time per point can be measured for 3 seconds
  • the number of integrations is 1, and measurement can be performed with a noise filter.
  • the primary particle diameter is 2,000 to 3,000 by using a fully automatic image processing apparatus and the like by taking a few field images of the powder with an electron microscope. It can be obtained by a method of measuring the degree and making the arithmetic average of these values the primary particle diameter.
  • the dispersity is a value determined by a dispersity evaluation test using a grain gauge specified in JIS K5600. That is, a sufficient amount of sample is poured into the deeper end of the groove and slightly overflows from the groove gauge having a groove with a desired depth according to the size of the grain. Place the scraper's long side parallel to the gauge width direction and place the blade tip in contact with the deep tip of the groove of the grain gauge. The surface of the gauge is pulled at a uniform speed to the groove depth of 0 to 1 second for 1 to 2 seconds, and within 3 seconds after the pulling is finished, light is applied at an angle of 20 ° to 30 ° and observed. Read the depth at which the grain appears in the groove of the grain gauge.
  • the viscosity ( ⁇ b) and the TI value are values obtained by the following methods, respectively.
  • a stable viscosity ( ⁇ a) after measurement for 2 minutes or more under conditions of a temperature of 25 ° C. and a shear rate of 2 s ⁇ 1 is obtained using an E-type viscometer.
  • the viscosity ( ⁇ b) measured under the same conditions as described above is obtained except that the shear rate is changed to 20 s ⁇ 1 .
  • shear rate When increasing the shear rate from 2 s ⁇ 1 to 20 s ⁇ 1 , it may be increased in one step, or the shear rate is increased in a multistage manner within the above range, and increased while obtaining the viscosity at that shear rate as appropriate. You may let them.
  • the non-aqueous lithium storage element is disassembled and the non-aqueous electrolyte solution is taken out.
  • a three-electrode cell is produced using an aluminum foil as a working electrode and lithium metal as a counter electrode and a reference electrode.
  • the separator is sandwiched between the working electrode and the counter electrode, and the reference electrode is arranged so as to be in liquid contact with the stacked body and accommodated in the laminate film.
  • the bottle container may be filled with a nonaqueous electrolytic solution, and the working electrode, the counter electrode, and the reference electrode may be immersed therein.
  • the aluminum foil used for the working electrode is not particularly limited, but from the viewpoint of easy handling, the thickness is preferably 10 to 100 ⁇ m and the area is preferably 1 to 100 cm 2 .
  • the above-mentioned triode cell is swept at a rate of 5 mV / sec from 3 V to 5 V in a constant temperature bath set at 25 ° C., and then is swept at a rate of 5 mV / sec from 5 V to 3 V. With this as one cycle, a total of 5 cycles are implemented to measure the current response.
  • the current response result of the fifth cycle is used, and the maximum response current in the voltage range of 3.8 V (vs. Li / Li + ) or more and 4.8 V (vs. Li / Li + ) or less is used. A value is obtained and evaluated as a value per aluminum foil area of the working electrode used.
  • a power storage module can be produced by connecting a plurality of non-aqueous lithium power storage elements according to this embodiment in series or in parallel. Further, since the non-aqueous lithium storage element and the storage module of the present embodiment can achieve both high input / output characteristics and high-temperature safety, a power regeneration assist system, a power load leveling system, an uninterruptible power supply system , Non-contact power feeding system, energy harvesting system, power storage system, electric power steering system, emergency power supply system, in-wheel motor system, idling stop system, quick charging system, smart grid system, etc.
  • the power storage system is preferably used for natural power generation such as solar power generation or wind power generation, the power load leveling system is used for a microgrid or the like, and the uninterruptible power supply system is preferably used for production facilities of a factory.
  • the non-contact power supply system the non-aqueous lithium storage element is used for leveling of voltage fluctuations such as microwave power transmission or electric field resonance and energy storage. In order to use the generated electric power, each is preferably used.
  • a power storage system as a cell stack, a plurality of non-aqueous lithium power storage elements are connected in series or in parallel, or a non-aqueous lithium power storage element, a lead battery, a nickel hydride battery, a lithium ion secondary battery, or a fuel cell Are connected in series or in parallel.
  • the non-aqueous lithium storage element according to the present embodiment can achieve both high input / output characteristics and high-temperature safety, for example, an electric vehicle, a plug-in hybrid vehicle, a hybrid vehicle, an electric motorcycle, etc. Can be mounted on a vehicle.
  • the above-described power regeneration assist system, electric power steering system, emergency power supply system, in-wheel motor system, idling stop system, or a combination thereof is suitably mounted on a vehicle.
  • Lithium carbonate was pulverized by brittle fracture while preventing thermal denaturation at a temperature of -196 ° C.
  • 200 g of lithium carbonate having an average particle size of 53 ⁇ m was cooled to ⁇ 196 ° C. with liquid nitrogen using a crusher (liquid nitrogen bead mill LNM) manufactured by Imex Co., Ltd., and then peripheral speed was 10.0 m / s using dry ice beads. For 9 minutes.
  • the average particle size of the obtained lithium carbonate was 2.26 ⁇ m.
  • the average particle diameter measured in the same manner as in activated carbon 1 was 7.1 ⁇ m
  • the BET specific surface area was 3,627 m 2 / g
  • the mesopore amount (V 1 ) was 1.50 cc / g
  • the amount of pores (V 2 ) was 2.28 cc / g
  • V 1 / V 2 0.66.
  • the obtained mixture was dispersed under the condition of a peripheral speed of 17.0 m / s using a thin film swirl type high-speed mixer “Filmix” manufactured by PRIMIX to obtain a positive electrode coating solution.
  • a thin film swirl type high-speed mixer “Filmix” manufactured by PRIMIX to obtain a positive electrode coating solution.
  • no lithium transition metal oxide was used in the preparation of the coating solution.
  • no lithium compound other than the positive electrode active material was used.
  • the positive electrode active material As the positive electrode active material, the types and amounts of carbon materials and lithium transition metal oxides described in Table 2 are used, and the lithium compounds other than the positive electrode active material, conductive filler, and binders of the types and amounts described in Table 2 are used. An agent, a dispersion stabilizer, and distilled water were further mixed to obtain a mixture having a solid mass ratio of 43.0%. The obtained mixture was dispersed for 3 minutes under the condition of a peripheral speed of 17 m / s using a thin film swirl type high-speed mixer “FILMIX (registered trademark)” manufactured by PRIMIX to prepare a coating solution.
  • FILMIX registered trademark
  • Lithium compounds other than positive electrode active materials Lithium carbonate: Lithium carbonate having an average particle size of 2.4 ⁇ m
  • Lithium oxide Lithium oxide having an average particle size of 2.4 ⁇ m
  • Lithium hydroxide Lithium hydroxide having an average particle size of 2.4 ⁇ m
  • LiFePO 4 average particle size 3.5
  • PAcNa Sodium polyacrylate
  • SBR Styrene butadiene rubber
  • CMC Carboxymethylcellulose “-” in Table 2 indicates that the component in the column was not used.
  • Non-aqueous electrolytes 1 to 3 were obtained by dissolving the lithium salt electrolytes shown in Table 5 in a mixed solvent composed of the organic solvents of the types and amounts shown in Table 5.
  • the outer package containing the electrode laminate impregnated with the non-aqueous electrolyte solution 1 is put into a vacuum sealer, and sealed at 10 ° C. at 180 ° C. and a pressure of 0.1 MPa for 10 seconds under reduced pressure to ⁇ 95 kPa.
  • a non-aqueous lithium storage element was obtained.
  • ⁇ RED value of non-aqueous electrolyte of polymer constituting binder The RED value of the sodium polyacrylate, which is a polymer constituting the binder in the positive electrode active material layer, with respect to the nonaqueous electrolytic solution 1 was 2.48. The RED value was determined by the method described in Patent Document 4. The obtained RED values are shown in Table 7.
  • non-aqueous lithium storage element in a vacuum sealer, depressurize to -90 kPa, and seal for 10 seconds at a temperature of 200 ° C and a pressure of 0.1 MPa to seal (reseal) the aluminum laminate packaging material did.
  • Examples 1-2 to 1-16 and Comparative Examples 1-1 to 1-6 A nonaqueous lithium storage element was produced in the same manner as in Example 1-1 except that the positive electrode precursor, the negative electrode, the separator, and the nonaqueous electrolyte were as shown in Table 7, and various evaluations were made. Went.
  • separators in Examples 1-2 to 1-7 and 1-14 to 1-16, and Comparative Examples 1-1 to 1-3 and 1-6, polyethylene microporous films having the thicknesses shown in Table 7 were used.
  • a separator having a two-layer structure in which a coat layer having the type and thickness described in Table 7 was formed was used.
  • the non-aqueous lithium storage element after lithium doping was subjected to constant current discharge at 25 A in an environment of 0.5 A until reaching a voltage of 3.5 V, and then the voltage was reduced by performing 3.5 V constant current discharge for 1 hour. Adjusted to 3.5V. Subsequently, the non-aqueous lithium electricity storage element was stored in a constant temperature bath at 60 ° C. for 60 hours and subjected to aging.
  • non-aqueous lithium storage element in a vacuum sealer, depressurize to -90 kPa, and seal for 10 seconds at a temperature of 200 ° C and a pressure of 0.1 MPa to seal (reseal) the aluminum laminate packaging material did.
  • the outer package containing the laminate impregnated with the non-aqueous electrolyte solution is put into a vacuum sealing machine, and sealed at a temperature of 180 ° C. and a pressure of 0.1 MPa for 10 seconds under a reduced pressure of ⁇ 95 kPa.
  • a triode cell for cyclic voltammogram measurement was obtained.
  • the positive electrode contains a lithium compound other than the positive electrode active material
  • the RED value of the polymer constituting the binder with respect to the non-aqueous electrolyte is greater than 1
  • the maximum response current value of the non-aqueous electrolyte is 0.
  • the electricity storage devices of Examples 2-1 to 2-20 that were 010 mA / cm 2 or less had small Ra ⁇ F and small Rb / Ra. These storage elements have low Ra ⁇ F, low internal resistance (that is, high input / output characteristics), and low Rb / Ra, so they have excellent durability even at high temperatures of 85 ° C or higher. I understand that there is.
  • the positive electrode precursor 18 was manufactured using the activated carbon 1 as a positive electrode active material. First, 4.0 parts by mass of ketjen black and 32.0 parts by mass of lithium carbonate were dry-mixed for 15 minutes at a speed of 20 rpm using a planetary mixer. 42.0 parts by mass of activated carbon 1 was added to the dry mixture, followed by dry mixing at a rate of 20 rpm for 15 minutes. Subsequently, 14.0 parts by mass of LiFePO 4 having an average particle size of 3.5 ⁇ m as a lithium transition metal oxide was added to the dry mixture, and dry mixed at a speed of 10 rpm for 5 minutes to obtain a powder mixture 1.
  • the viscosity ( ⁇ b 1 ) and TI 1 value of the obtained positive electrode coating solution were measured by the above-described method using an E-type viscometer TVE-35H manufactured by Toki Sangyo Co., Ltd. As a result, the viscosity ( ⁇ b 1 ) was 2,030 mPa ⁇ s, and the TI 1 value was 7.2.
  • the degree of dispersion of the obtained positive electrode coating liquid 1 was measured using a grain gauge manufactured by Yoshimitsu Seiki Co., Ltd. As a result, the particle size was 22 ⁇ m.
  • the obtained positive-electrode coating formulation 20g weighed into a closed container, 25 ° C. After standing for 24 hours under environment was measured again viscosity (? B 2) and TI 2 value, viscosity (? B 2) is 1, 670 mPa ⁇ s, TI 2 value was 6.0, TI 2 / TI 1 was 0.83, and ⁇ b 2 / ⁇ b 1 was 0.82.
  • ⁇ Production of positive electrode precursor> Using a double-sided die coater manufactured by Toray Engineering Co., Ltd., a positive electrode coating solution was applied to both sides of an aluminum foil having a thickness of 15 ⁇ m at a coating speed of 1 m / s. It adjusted in order of 90 degreeC and 110 degreeC, and dried with IR heater after that, and the positive electrode precursor 18 was obtained.
  • the obtained positive electrode precursor 18 was pressed using a roll press machine under conditions of a pressure of 6 kN / cm and a surface temperature of the pressing part of 25 ° C.
  • the total thickness of the positive electrode precursor 18 was measured at any 10 points of the positive electrode precursor 18 using a thickness gauge Linear Gauge Sensor GS-551 manufactured by Ono Keiki Co., Ltd. From the obtained measurement result, the film thickness per one side of the positive electrode active material layer of the positive electrode precursor 1 was 61 ⁇ m.
  • the positive electrode precursor 18 is cut into a width of 25 mm and a length of 120 mm (100 mm is a positive electrode active material layer, and the remaining 20 mm is an uncoated portion where the positive electrode active material layer is not applied).
  • ) (Nichiban CT405AP-24) was cut to a length of 100 mm and attached to the positive electrode active material layer.
  • Tensilon STB-1225S, manufactured by A & D Co., Ltd.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • concentration of LiFSI and LiBF 4 1: 3, for a total concentration of 1.2 mol / L.
  • the non-aqueous electrolyte solution 16 was obtained by dissolving the electrolyte salt so that the LiFSI was 0.3 mol / L and the LiBF 4 was 0.9 mol / L.
  • the negative electrode 7 is arrange
  • the positive electrode terminal and the negative electrode terminal were ultrasonically welded to the obtained electrode body, 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 75 g of the non-aqueous electrolyte solution 16 was injected into the electrode body 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.
  • 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 pressure in the chamber was reduced from atmospheric pressure to ⁇ 87 kPa, and then the process of returning to atmospheric pressure was repeated 4 times, and then allowed to stand for 15 minutes. Further, the pressure in the chamber was reduced from atmospheric pressure to ⁇ 91 kPa, and then returned to atmospheric pressure.
  • the process of depressurizing the packaging material and returning it 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 16.
  • the electrode laminate impregnated with the non-aqueous electrolyte solution 16 is put in 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, thereby forming an aluminum laminate packaging material. Sealed.
  • Alkali metal doping process The electrode body obtained after sealing was placed in a dry box having a temperature of 40 ° C. and a dew point of ⁇ 40 ° C. or less. After cutting and opening the surplus portion of the aluminum laminate packaging material, performing constant current charging until the voltage reaches 4.5 V at a current value of 500 mA, and then initializing by 4.5 V constant voltage charging for 10 hours. Charging was performed, and alkali metal doping was performed on the negative electrode. After the alkali metal doping, the aluminum laminate was sealed using a heat sealing machine (FA-300) manufactured by Fuji Impulse. [Aging process] By taking out the electrode body after doping with alkali metal from the dry box, performing a constant current discharge at 25 ° C.
  • Example 3-2 43.5 parts by mass of activated carbon 1, 14.0 parts by mass of LiFePO 4 having an average particle size of 3.5 ⁇ m as a lithium transition metal oxide, 32.0 parts by mass of lithium carbonate, and 4.0 parts by mass of Ketjen black
  • a nonaqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that 5.0 parts by mass of sodium polyacrylate and 1.5 parts by mass of CMC were used.
  • Example 3-3 45.0 parts by mass of activated carbon 1, 14.0 parts by mass of LiFePO 4 having an average particle size of 3.5 ⁇ m as a lithium transition metal oxide, 32.0 parts by mass of lithium carbonate, and 4.0 parts by mass of Ketjen black
  • a nonaqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that 4.0 parts by mass of sodium polyacrylate and 1.0 part by mass of CMC were used.
  • Example 3-4 46.5 parts by mass of activated carbon 1, 14.0 parts by mass of LiFePO 4 having an average particle size of 3.5 ⁇ m as a lithium transition metal oxide, 32.0 parts by mass of lithium carbonate, and 4.0 parts by mass of ketjen black
  • a nonaqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that 3.0 parts by mass of sodium polyacrylate and 0.5 parts by mass of CMC were used.
  • Example 3-6 41.0 parts by mass of activated carbon 1, 14.0 parts by mass of LiFePO 4 having a mean particle size of 3.5 ⁇ m as a lithium transition metal oxide, 32.0 parts by mass of lithium carbonate, and 4.0 parts by mass of Ketjen black
  • a nonaqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that 7.0 parts by mass of sodium polyacrylate and 2.0 parts by mass of CMC were used.
  • Example 3-9 40.0 parts by mass of activated carbon 1, 12.0 parts by mass of LiFePO 4 having an average particle size of 3.5 ⁇ m as a lithium transition metal oxide, 32.0 parts by mass of lithium carbonate, and 4.0 parts by mass of Ketjen black
  • a nonaqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that 10.0 parts by mass of sodium polyacrylate and 2.0 parts by mass of CMC were used.
  • a nonaqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that 11.0 parts by mass of sodium polyacrylate and 2.0 parts by mass of CMC were used.
  • Example 3-11> A non-aqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that CMC was not used in the production of the positive electrode coating solution.
  • the produced positive electrode precursor had cracks on the surface of the positive electrode active material layer.
  • ⁇ Comparative Example 3-1 38.5 parts by mass of activated carbon 1, 12.0 parts by mass of LiFePO 4 having an average particle size of 3.5 ⁇ m as a lithium transition metal oxide, 31.0 parts by mass of lithium carbonate, and 4.0 parts by mass of ketjen black
  • a nonaqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that 12.0 parts by mass of sodium polyacrylate and 2.5 parts by mass of CMC were used.
  • a nonaqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that 12.5 parts by mass of sodium polyacrylate and 2.5 parts by mass of CMC were used.
  • a non-aqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that 13.0 parts by mass of sodium polyacrylate and 3.0 parts by mass of CMC were used.
  • a nonaqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that 1.0 part by mass of sodium polyacrylate and 0.5 part by mass of CMC were used.
  • a nonaqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that 0.5 parts by mass of sodium polyacrylate and 0.5 parts by mass of CMC were used.
  • Example 3-10> A non-aqueous lithium storage element was produced in the same manner as in Example 3-1, except that styrene butadiene rubber was used instead of sodium polyacrylate as the binder.
  • Table 10 shows the results of Examples 3-1 to 3-11 and Comparative Examples 3-1 to 3-10.
  • Example 3-11 when sodium polyacrylate was not included as a binder, the resistance increase (Rb / Ra) after a high temperature storage test became large.
  • CMC was not added to the positive electrode coating solution and the positive electrode precursor, but in this case, TI 2 / TI 1 was 0.05 or more and 1.
  • TI 2 / TI 1 was 0.05 or more and 1.
  • ⁇ b2 / ⁇ b1 was greater than 1.3, and the viscosity was likely to increase due to long-term storage.
  • Example 3-11 since the fine short-circuit rate is relatively high, the cracked positive electrode active material layer may slide down in the cell, and the positive and negative electrodes may be electrically connected in some form. Was suggested.
  • Example 3-12> A non-aqueous lithium storage element was produced in the same manner as in Example 3-1, except that LiNi 0.80 Co 0.15 Al 0.05 O 2 was used instead of LiFePO 4 .
  • Example 3-13> A non-aqueous lithium storage element was produced in the same manner as in Example 3-1, except that LiNi 0.33 Co 0.33 Mn 0.33 O 2 was used instead of LiFePO 4 .
  • Example 3-14> A non-aqueous lithium storage element was produced in the same manner as in Example 3-1, except that LiCoO 2 was used instead of LiFePO 4 .
  • Example 3-15> A non-aqueous lithium storage element was produced in the same manner as in Example 3-1, except that LiMnPO 4 was used instead of LiFePO 4 .
  • Example 3-16> A non-aqueous lithium storage element was produced in the same manner as in Example 3-1, except that LiMn 2 O 4 was used instead of LiFePO 4 .
  • Example 3-17> A non-aqueous lithium storage element was produced in the same manner as in Example 3-1, except that Li 3 V 2 (PO 4 ) 3 was used instead of LiFePO 4 .
  • Example 3-18> A non-aqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that sodium carbonate was used instead of lithium carbonate.
  • Example 3-19> A non-aqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that potassium carbonate was used instead of lithium carbonate.
  • Example 3-20> A non-aqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that a mixture of sodium carbonate and lithium carbonate in a mass ratio of 1: 1 was used instead of lithium carbonate.
  • Example 3-21> A non-aqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that a mixture of potassium carbonate and lithium carbonate in a mass ratio of 1: 1 was used instead of lithium carbonate.
  • Example 3-22> A non-aqueous lithium storage element was produced in the same manner as in Example 3-1, except that LiFePO 4 was not used.
  • ⁇ Comparative Example 3-11> A non-aqueous lithium storage element was produced in the same manner as in Comparative Example 3-6, except that LiNi 0.80 Co 0.15 Al 0.05 O 2 was used instead of LiFePO 4 .
  • ⁇ Comparative Example 3-12> A non-aqueous lithium storage element was produced in the same manner as in Comparative Example 3-6, except that LiNi 0.33 Co 0.33 Mn 0.33 O 2 was used instead of LiFePO 4 .
  • ⁇ Comparative Example 3-13> A non-aqueous lithium electricity storage device was produced in the same manner as in Comparative Example 3-6, except that LiCoO 2 was used instead of LiFePO 4 .
  • ⁇ Comparative Example 3-14> A non-aqueous lithium storage element was produced in the same manner as in Comparative Example 3-6, except that LiMnPO 4 was used instead of LiFePO 4 .
  • ⁇ Comparative Example 3-15> A non-aqueous lithium electricity storage device was produced in the same manner as in Comparative Example 3-6 except that LiMn 2 O 4 was used instead of LiFePO 4 .
  • ⁇ Comparative Example 3-16> A non-aqueous lithium storage element was produced in the same manner as in Comparative Example 3-6, except that Li 3 V 2 (PO 4 ) 3 was used instead of LiFePO 4 .
  • ⁇ Comparative Example 3-17> A nonaqueous lithium electricity storage device was produced in the same manner as in Comparative Example 3-6, except that sodium carbonate was used instead of lithium carbonate.
  • ⁇ Comparative Example 3-18> A non-aqueous lithium storage element was produced in the same manner as in Comparative Example 3-6, except that potassium carbonate was used instead of lithium carbonate.
  • ⁇ Comparative Example 3-19> A non-aqueous lithium storage element was produced in the same manner as in Comparative Example 3-6, except that a mixture of sodium carbonate and lithium carbonate in a mass ratio of 1: 1 was used instead of lithium carbonate.
  • ⁇ Comparative Example 3-20> A non-aqueous lithium electricity storage device was produced in the same manner as in Comparative Example 3-6, except that a mixture of potassium carbonate and lithium carbonate in a mass ratio of 1: 1 was used instead of lithium carbonate.
  • Table 11 shows the evaluation results of Examples 3-12 to 3-22 and Comparative Examples 3-11 to 3-21.
  • the positive electrode precursor 18 was cut into a size of 12.0 cm ⁇ 210.0 cm (the size of the positive electrode active material layer was 10.0 cm ⁇ 210.0 cm, and the positive electrode active material layer was coated on the positive electrode current collector).
  • the uncoated positive electrode uncoated portion is 2.0 cm ⁇ 210.0 cm
  • the negative electrode 7 is cut into a size of 12.1 ⁇ 220.0 cm (the size of the negative electrode active material layer is 10.1 cm).
  • ⁇ 220.0 cm, and the negative electrode uncoated portion on which the negative electrode active material layer is not coated on the negative electrode current collector is 2.0 cm ⁇ 220.0 cm.)
  • the cut out positive electrode precursor and negative electrode was wound through a paper separator (thickness 20 ⁇ m) to prepare an electrode wound body.
  • a terminal was connected to the obtained electrode winding body, inserted into a metal square can made of aluminum, and sealed.
  • a non-aqueous electrolyte solution 16 was injected from the opening of the metal square can, and then a detachable check valve was attached.
  • the obtained device was put in a dry box having a temperature of 40 ° C. and a dew point of ⁇ 40 ° C. or less, pressurized at a pressure of 100 kPa, and charged with a constant current until a voltage of 4.5 V was reached at a current value of 500 mA.
  • Initial charging was performed by a method of continuing 4.5 V constant voltage charging for 10 hours, and alkali metal doping was performed on the negative electrode.
  • Example 3-1 aging was performed under the same conditions as in Example 3-1, and after removing the check valve, degassing was performed under the same conditions as in Example 3-1, thereby sealing the opening of the device.
  • the short-circuit rate was 0%
  • the capacity Q 910 mAh
  • the internal resistance Ra 1.18 m ⁇
  • the internal resistance Rb 1.71 m ⁇ after the high-temperature storage test
  • Rb / Ra 1.45.
  • Example 3-24> A nonaqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that an acrylic acid / maleic acid copolymer sodium salt was used instead of sodium polyacrylate.
  • Example 3-25> A non-aqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that sodium salt of acrylic acid / vinyl sulfonic acid copolymer was used instead of sodium polyacrylate.
  • Example 3-26> A non-aqueous lithium storage element was produced in the same manner as in Example 3-1, except that an acrylic acid / methacrylic acid copolymer sodium salt was used instead of sodium polyacrylate.
  • Example 3-27> A non-aqueous lithium storage element was produced in the same manner as in Example 3-1, except that methyl polyacrylate was used instead of sodium polyacrylate.
  • Example 3-28> A nonaqueous lithium electricity storage device was produced in the same manner as in Example 3-1, except that polyacrylic acid was used instead of sodium polyacrylate.
  • ⁇ Comparative Example 3-22> A non-aqueous lithium electricity storage device was produced in the same manner as in Comparative Example 3-6, except that acrylic acid / maleic acid copolymer sodium salt was used instead of sodium polyacrylate.
  • ⁇ Comparative Example 3-23> A non-aqueous lithium electricity storage device was produced in the same manner as in Comparative Example 3-6, except that sodium salt of acrylic acid / vinyl sulfonic acid copolymer was used instead of sodium polyacrylate.
  • ⁇ Comparative Example 3-24> A non-aqueous lithium electricity storage device was produced in the same manner as in Comparative Example 3-6, except that acrylic acid / methacrylic acid copolymer sodium salt was used instead of sodium polyacrylate.
  • ⁇ Comparative Example 3-25> A nonaqueous lithium electricity storage device was produced in the same manner as in Comparative Example 3-6, except that methyl polyacrylate was used instead of sodium polyacrylate.
  • ⁇ Comparative Example 3-26> A non-aqueous lithium electricity storage device was produced in the same manner as in Comparative Example 3-6, except that polyacrylic acid was used in place of sodium polyacrylate.
  • Table 12 shows the evaluation results of Examples 3-24 to 3-28 and Comparative Examples 3-22 to 3-26.
  • the non-aqueous lithium storage element of the present invention can be suitably used as a storage element in, for example, an instantaneous power peak assist application in a hybrid drive system of an automobile.
  • the non-aqueous lithium electricity storage device of the present invention is preferable because the effects of the present invention are maximized when applied as, for example, a lithium ion capacitor or a lithium ion secondary battery.

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CN112615051A (zh) * 2020-11-24 2021-04-06 北京理工大学 铝二次电池及其电解液
JPWO2019212041A1 (ja) * 2018-05-02 2021-05-13 株式会社ジェイテクト リチウムイオン二次電池
JPWO2019212040A1 (ja) * 2018-05-02 2021-05-13 株式会社ジェイテクト リチウムイオン二次電池
KR20230029985A (ko) 2020-10-21 2023-03-03 아사히 가세이 가부시키가이샤 비수계 알칼리 금속 축전 소자 및 정극 도공액

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JP2017017299A (ja) * 2015-04-23 2017-01-19 株式会社ジェイテクト リチウムイオンキャパシタ
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JPWO2019212041A1 (ja) * 2018-05-02 2021-05-13 株式会社ジェイテクト リチウムイオン二次電池
JPWO2019212040A1 (ja) * 2018-05-02 2021-05-13 株式会社ジェイテクト リチウムイオン二次電池
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JP7396271B2 (ja) 2018-05-02 2023-12-12 株式会社ジェイテクト リチウムイオン二次電池
KR20230029985A (ko) 2020-10-21 2023-03-03 아사히 가세이 가부시키가이샤 비수계 알칼리 금속 축전 소자 및 정극 도공액
CN112615051A (zh) * 2020-11-24 2021-04-06 北京理工大学 铝二次电池及其电解液
CN112615051B (zh) * 2020-11-24 2022-04-22 北京理工大学 铝二次电池及其电解液

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