WO2021131742A1 - Batterie secondaire - Google Patents

Batterie secondaire Download PDF

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Publication number
WO2021131742A1
WO2021131742A1 PCT/JP2020/046018 JP2020046018W WO2021131742A1 WO 2021131742 A1 WO2021131742 A1 WO 2021131742A1 JP 2020046018 W JP2020046018 W JP 2020046018W WO 2021131742 A1 WO2021131742 A1 WO 2021131742A1
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active material
acid anhydride
negative electrode
cyclic
positive electrode
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PCT/JP2020/046018
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English (en)
Japanese (ja)
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小谷　徹
永田　佳秀
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株式会社村田製作所
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Publication of WO2021131742A1 publication Critical patent/WO2021131742A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the content of cyclic acid anhydride in the electrolytic solution is 0.001% by weight or more and 1% by weight or less, and the ratio of the total area of the negative electrode active material layer to the total area of the positive electrode active material layer is 1.001 or more. It is 1.1 or less.
  • the entire positive electrode active material layer faces a part of the negative electrode active material layer
  • the electrolytic solution contains a cyclic acid anhydride such as a cyclic dicarboxylic acid anhydride.
  • the content of the cyclic acid anhydride in the electrolytic solution is 0.001% by weight or more and 1% by weight or less, and the ratio of the total area of the negative electrode active material layer to the total area of the positive electrode active material layer is 1. Since it is 001 or more and 1.1 or less, excellent swelling characteristics can be obtained.
  • FIG. 1 It is a perspective view which shows the structure of the secondary battery in one Embodiment of this technique. It is sectional drawing which shows the structure of the battery element shown in FIG. It is a top view which shows the structure of the main part of the battery element shown in FIG. It is a top view which shows the structure of the secondary battery of the modification. It is a block diagram which shows the structure of the application example (battery pack: cell) of a secondary battery. It is a block diagram which shows the structure of application example (battery pack: assembled battery) of a secondary battery. It is a block diagram which shows the structure of the application example (electric vehicle) of a secondary battery.
  • the secondary battery described here is a secondary battery in which the battery capacity can be obtained by using the occlusion and release of the electrode reactant, and includes an electrolytic solution together with the positive electrode and the negative electrode.
  • the charge capacity of the negative electrode is larger than the discharge capacity of the positive electrode in order to prevent the electrode reactant from being unintentionally deposited on the surface of the negative electrode during charging. That is, the electrochemical capacity per unit area of the negative electrode is set to be larger than the electrochemical capacity per unit area of the positive electrode.
  • the type of electrode reactant is not particularly limited, but specifically, it is a light metal such as an alkali metal and an alkaline earth metal.
  • Alkali metals include lithium, sodium and potassium, and alkaline earth metals include beryllium, magnesium and calcium.
  • a secondary battery whose battery capacity can be obtained by utilizing the storage and release of lithium is a so-called lithium ion secondary battery.
  • lithium ion secondary battery lithium is occluded and released in an ionic state.
  • FIG. 1 shows the perspective configuration of the secondary battery
  • FIG. 2 shows the cross-sectional configuration of the battery element 10 shown in FIG.
  • FIG. 1 shows a state in which the battery element 10 and the exterior film 20 are separated from each other
  • FIG. 2 shows only a part of the battery element 10 (positive electrode 11, negative electrode 12 and separator 13). There is.
  • this secondary battery includes a battery element 10, an exterior film 20, a positive electrode lead 14, and a negative electrode lead 15.
  • the battery element 10 is housed inside the exterior film 20, and each of the positive electrode lead 14 and the negative electrode lead 15 is led out from the inside of the exterior film 20 toward the outside in a common direction.
  • the secondary battery described here is a laminated film type secondary battery using a flexible (or flexible) exterior member (exterior film 20) as an exterior member for accommodating the battery element 10. ..
  • the exterior film 20 is a single film-like member, and can be folded in the direction of the arrow R (dashed line). Since the exterior film 20 houses the battery element 10 as described above, it houses the positive electrode 11, the negative electrode 12, and the electrolytic solution.
  • the exterior film 20 is provided with a recessed portion 20U (so-called deep drawing portion) for accommodating the battery element 10.
  • the exterior film 20 is a three-layer laminated film in which a fusion layer, a metal layer, and a surface protective layer are laminated in this order from the inside, and when the exterior film 20 is folded, they face each other.
  • the outer peripheral edges of the fused layer are fused to each other.
  • the fused layer contains a polymer compound such as polypropylene.
  • the metal layer contains a metallic material such as aluminum.
  • the surface protective layer contains a polymer compound such as nylon.
  • the structure (number of layers) of the exterior film 20 is not particularly limited, and may be one layer or two layers, or four or more layers.
  • the adhesion film 21 is inserted between the exterior film 20 and the positive electrode lead 14, and the adhesion film 22 is inserted between the exterior film 20 and the negative electrode lead 15.
  • Each of the adhesive films 21 and 22 is a member that prevents outside air from unintentionally invading the inside of the exterior film 20, such as polyolefin having adhesiveness to each of the positive electrode lead 14 and the negative electrode lead 15. It contains any one or more of the polymer compounds.
  • the polyolefins include polyethylene, polypropylene, modified polyethylene and modified polypropylene. However, one or both of the adhesive films 21 and 22 may be omitted.
  • the battery element 10 includes a positive electrode 11, a negative electrode 12, a separator 13, and an electrolytic solution (not shown) which is a liquid electrolyte.
  • the battery element 10 is a structure in which positive electrodes 11 and 12 are alternately laminated via a separator 13, and is a so-called laminated electrode body. That is, the positive electrode 11 and the negative electrode 12 face each other via the separator 13.
  • the electrolytic solution is impregnated in each of the positive electrode 11, the negative electrode 12, and the separator 13.
  • the positive electrode 11 includes a positive electrode current collector 11A and two positive electrode active material layers 11B provided on both sides of the positive electrode current collector 11A.
  • the positive electrode active material layer 11B may be provided on only one side of the positive electrode current collector 11A.
  • the positive electrode current collector 11A contains any one or more of conductive materials such as metal materials, and the metal materials are aluminum, nickel, stainless steel, and the like.
  • the positive electrode current collector 11A includes a protruding portion 11AT in which the positive electrode active material layer 11B is not formed. Therefore, when the battery element 10 includes a plurality of positive electrodes 11 (a plurality of positive electrode current collectors 11A), the battery element 10 includes a plurality of protrusions 11AT. The plurality of projecting portions 11AT are joined to each other to form one lead-shaped joining portion 11Z.
  • the positive electrode active material layer 11B contains any one or more of the positive electrode active materials capable of occluding and releasing lithium. However, the positive electrode active material layer 11B may further contain a positive electrode binder, a positive electrode conductive agent, and the like.
  • the type of positive electrode active material is not particularly limited, but specifically, it is a lithium-containing compound such as a lithium-containing transition metal compound.
  • This lithium-containing transition metal compound contains one or more kinds of transition metal elements together with lithium, and may further contain one kind or two or more kinds of other elements.
  • the type of the other element is not particularly limited as long as it is an arbitrary element other than the transition metal element, but specifically, it is an element belonging to groups 2 to 15 in the long periodic table.
  • the type of the lithium-containing transition metal compound is not particularly limited, but specifically, any of oxides, phosphoric acid compounds, silicic acid compounds, boric acid compounds and the like may be used.
  • oxides are LiNiO 2 , LiCoO 2 , LiCo 0.98 Al 0.01 Mg 0.01 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiNi 0.33 Co 0.33 Mn 0.33 O 2 , Li 1.2 Mn 0.52 Co 0.175 Ni 0.1 O 2 , Li 1.15 (Mn 0.65 Ni 0.22 Co 0.13 ) O 2 and Li Mn 2 O 4 .
  • Specific examples of the phosphoric acid compound include LiFePO 4 , LiMnPO 4 , LiFe 0.5 Mn 0.5 PO 4, and LiFe 0.3 Mn 0.7 PO 4 .
  • the positive electrode binder contains any one or more of synthetic rubber and polymer compounds.
  • Synthetic rubbers include styrene-butadiene rubbers, fluorine-based rubbers and ethylene propylene diene.
  • Polymer compounds include polyvinylidene fluoride, polyimide and carboxymethyl cellulose.
  • the positive electrode conductive agent contains any one or more of conductive materials such as carbon materials, and the carbon materials are graphite, carbon black, acetylene black, ketjen black and the like.
  • the conductive material may be a metal material, a polymer compound, or the like.
  • the negative electrode 12 includes a negative electrode current collector 12A and two negative electrode active material layers 12B provided on both sides of the negative electrode current collector 12A.
  • the negative electrode active material layer 12B may be provided on only one side of the negative electrode current collector 12A.
  • the negative electrode current collector 12A includes a protruding portion 12AT in which the negative electrode active material layer 12B is not formed, and the protruding portion 12AT is located at a position where it does not overlap with the protruding portion 11AT. Have been placed. Therefore, when the battery element 10 includes a plurality of negative electrodes 12 (a plurality of negative electrode current collectors 12A), the battery element 10 includes a plurality of protrusions 12AT. The plurality of projecting portions 12AT are joined to each other to form one lead-shaped joint portion 12Z.
  • the negative electrode active material layer 12B contains any one or more of the negative electrode active materials capable of occluding and releasing lithium. However, the negative electrode active material layer 12B may further contain a negative electrode binder, a negative electrode conductive agent, and the like. The details regarding the negative electrode binder are the same as the details regarding the positive electrode binder, and the details regarding the negative electrode conductive agent are the same as the details regarding the positive electrode conductive agent.
  • the type of negative electrode active material is not particularly limited, but specifically, it is a carbon material, a metal-based material, or the like.
  • the carbon material is graphitizable carbon, non-graphitizable carbon, graphite and the like, and the graphite is natural graphite and artificial graphite and the like.
  • the metal-based material is a material containing any one or more of metal elements and semi-metal elements capable of forming an alloy with lithium, and the metal elements and semi-metal elements are silicon and semi-metal elements. Such as tin.
  • the metal-based material may be a simple substance, an alloy, a compound, a mixture of two or more kinds thereof, or a material containing two or more kinds of phases thereof.
  • metallic materials include SiB 4 , SiB 6 , Mg 2 Si, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2 , CrSi 2 , Cu 5 Si, FeSi 2 , MnSi 2 , NbSi 2 , TaSi 2 , VSi 2 , WSi 2 , ZnSi 2 , SiC, Si 3 N 4 , Si 2 N 2 O, SiO v (0 ⁇ v ⁇ 2), LiSiO, SnO w (0 ⁇ w ⁇ 2), SnSiO 3 , LiSnO, Mg 2 Sn, and the like.
  • v of SiO v may satisfy 0.2 ⁇ v ⁇ 1.4.
  • the method for forming the negative electrode active material layer 12B is not particularly limited, but specifically, any one of a coating method, a gas phase method, a liquid phase method, a thermal spraying method, a firing method (sintering method), and the like, or There are two or more types.
  • the separator 13 is an insulating porous film interposed between the positive electrode 11 and the negative electrode 12, and lithium ions are emitted while preventing contact between the positive electrode 11 and the negative electrode 12. Let it pass.
  • the separator 13 contains any one or more of the polymer compounds, and the polymer compounds are polytetrafluoroethylene, polypropylene, polyethylene, and the like.
  • the separator 13 may be a single layer or a multi-layer.
  • the separator 13 may be a single-layer film composed of one type of porous film, or may be a multilayer film in which one type or two or more types of porous films are laminated on each other.
  • the electrolytic solution contains a cyclic acid anhydride, and the cyclic acid anhydride is one of a cyclic dicarboxylic acid anhydride, a cyclic disulfonic acid anhydride, a cyclic carboxylic acid sulfonic acid anhydride, and a cyclic phosphonic acid anhydride. Includes one or more types.
  • the cyclic acid anhydride may contain only one of cyclic dicarboxylic acid anhydride, cyclic disulfonic acid anhydride, cyclic carboxylic acid sulfonic acid anhydride, and cyclic phosphonic acid anhydride. Further, the cyclic acid anhydride may contain any two or more of cyclic dicarboxylic acid anhydride, cyclic disulfonic acid anhydride, cyclic carboxylic acid sulfonic acid anhydride and cyclic phosphonic acid anhydride.
  • the cyclic acid anhydride may contain all of the cyclic dicarboxylic acid anhydride, the cyclic disulfonic acid anhydride, the cyclic carboxylic acid sulfonic acid anhydride and the cyclic phosphonic acid anhydride.
  • Cyclic carboxylic acid sulfonic acid anhydride is a general term for cyclic compounds containing a group in which a carboxylic acid group and a sulfonic acid group are dehydrated and condensed.
  • the reason why the electrolytic solution contains cyclic acid anhydride is that the electrolytic solution contains cyclic acid anhydride when the entire positive electrode active material layer 11B faces a part of the negative electrode active material layer 12B, as will be described later. This is because the decomposition reaction of the electrolytic solution is specifically suppressed when the area ratio R is within a predetermined range, so that the secondary battery is less likely to swell. The details of the reason why the secondary battery described here is less likely to swell will be described later.
  • the cyclic dicarboxylic acid anhydride contains any one or more of the compounds represented by the formula (1).
  • the cyclic disulfonic acid anhydride contains any one or more of the compounds represented by the formula (2).
  • the cyclic carboxylic acid sulfonic acid anhydride contains any one or more of the compounds represented by the formula (3).
  • the cyclic phosphonic anhydride contains any one or more of the compounds represented by the formula (4).
  • Each of X1, X2 and X3 is one of a divalent hydrocarbon group, a divalent oxygen-containing hydrocarbon group, a divalent halogenated hydrocarbon group and a divalent halogenated oxygen-containing hydrocarbon group.
  • Each of R1, R2 and R3 is one of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group.
  • the divalent hydrocarbon group is a divalent group composed of carbon (C) and hydrogen (H), and may be linear or branched with one or more side chains. It may be cyclic, or two or more of them may be bonded to each other.
  • the divalent hydrocarbon group may or may not contain one or more carbon-carbon unsaturated bonds.
  • the divalent hydrocarbon group is an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, a divalent bonding group and the like.
  • This divalent bonding group is a divalent group in which two or more of an alkylene group, an alkaneylene group, an alkynylene group, a cycloalkylene group and an arylene group are bonded to each other.
  • the type of the alkylene group is not particularly limited, but specifically, it is a methylene group, an ethylene group, a propylene group, or the like.
  • the type of the alkenylene group is not particularly limited, and specific examples thereof include an ethenylene group, a propenylene group and a butenylene group.
  • the type of the alkynylene group is not particularly limited, and specific examples thereof include an ethynylene group, a propynylene group, and a butynylene group.
  • the type of the cycloalkylene group is not particularly limited, and specific examples thereof include a cyclopropylene group, a cyclobutylene group and a cyclohexylene group.
  • the type of the arylene group is not particularly limited, and specific examples thereof include a phenylene group and a naphthylene group.
  • the type of the divalent bonding group is not particularly limited, and is, for example, a group in which one hydrogen group is eliminated from the benzyl group.
  • the number of carbon atoms of the alkylene group is not particularly limited, but specifically, it is 1 to 4.
  • the carbon number of each of the alkenylene group and the alkynylene group is not particularly limited, but is specifically 2 to 4.
  • the number of carbon atoms of the cycloalkylene group is not particularly limited, but is specifically 3 to 6.
  • the carbon number of the arylene group is not particularly limited, but specifically, it is 6 to 14. This is because the solubility and compatibility of the cyclic acid anhydride are improved.
  • the divalent oxygen-containing hydrocarbon group is a group in which one or more ether bonds (-O-) are introduced into the above-mentioned divalent hydrocarbon group.
  • This ether bond may be introduced in the middle of the divalent hydrocarbon group or may be introduced at the end of the divalent hydrocarbon group. That is, for example, when the divalent hydrocarbon group is an ethylene group (-CH 2- CH 2- ), the group in which one ether bond is introduced into the ethylene group is -CH 2- O.
  • -CH 2 - may be the, -O-CH 2 -CH 2 - or -CH 2 -CH 2 -O- may be used.
  • the divalent halogenated hydrocarbon group is a group in which one or more hydrogen groups (-H) among the above-mentioned divalent hydrocarbon groups are substituted with halogen groups.
  • the halogen group includes a fluorine group (-F), a chlorine group (-Cl), a bromine group (-Br) and an iodine group (-I).
  • the type of the halogen group contained in the divalent halogenated hydrocarbon group may be only one type or two or more types.
  • the divalent oxygen-containing hydrocarbon group is a group in which one or more hydrogen groups among the above-mentioned divalent oxygen-containing hydrocarbon groups are substituted with a halogen group, and details regarding the halogen group. Is the same as the case described with respect to the divalent halogenated hydrocarbon group.
  • each of R1, R2 and R3 are as described below. However, each of R1, R2 and R3 may be the same group or different groups from each other. Also, only any two of R1, R2 and R3 may be the same group.
  • the monovalent hydrocarbon group is an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a monovalent bonding group and the like.
  • the monovalent group is a monovalent group in which two or more of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group and an aryl group are bonded to each other.
  • the type of alkyl group is not particularly limited, but specifically, it is a methyl group, an ethyl group, a propyl group, or the like.
  • the type of the alkenyl group is not particularly limited, and specific examples thereof include an ethenyl group, a propenyl group and a butenyl group.
  • the type of the alkynyl group is not particularly limited, and specific examples thereof include an ethynyl group, a propynyl group and a butynyl group.
  • the type of the cycloalkyl group is not particularly limited, and specific examples thereof include a cyclopropyl group, a cyclobutyl group and a cyclohexyl group.
  • the type of the aryl group is not particularly limited, and specific examples thereof include a phenyl group and a naphthyl group.
  • the type of the monovalent bonding group is not particularly limited, but specifically, it is a benzyl group or the like.
  • the number of carbon atoms of the alkyl group is not particularly limited, but specifically, it is 1 to 4.
  • the carbon number of each of the alkenyl group and the alkynyl group is not particularly limited, but is specifically 2 to 4.
  • the number of carbon atoms of the cycloalkyl group is not particularly limited, but is specifically 3 to 6.
  • the number of carbon atoms of the aryl group is not particularly limited, but specifically, it is 6 to 14. This is because the solubility and compatibility of the cyclic acid anhydride are improved.
  • the monovalent halogenated hydrocarbon group is a group in which one or more hydrogen groups among the above-mentioned monovalent hydrocarbon groups are substituted with a halogen group, and the details regarding the halogen group are divalent. It is the same as the case described about the halogenated hydrocarbon group of.
  • cyclic dicarboxylic acid anhydride examples are compounds represented by the formulas (1-1) to (1-9).
  • cyclic disulfonic acid anhydride examples are compounds represented by the formulas (2-1) to (2-9).
  • cyclic phosphonic anhydride examples are compounds represented by the formulas (4-1) to (4-7).
  • the content of the cyclic acid anhydride in the electrolytic solution is 0.001% by weight to 1% by weight. This is because the content of the cyclic acid anhydride in the electrolytic solution is optimized. As a result, when the entire positive electrode active material layer 11B faces a part of the negative electrode active material layer 12B and the area ratio R is within a predetermined range, the decomposition reaction of the electrolytic solution is sufficiently suppressed. This is because the secondary battery does not swell sufficiently.
  • the content of the cyclic acid anhydride in the electrolytic solution is preferably 0.01% by weight to 0.1% by weight. This is because the decomposition reaction of the electrolytic solution is more suppressed, so that the secondary battery is less likely to swell.
  • the content of the cyclic acid anhydride described here is the total content of each of the cyclic dicarboxylic acid anhydride, the cyclic disulfonic acid anhydride, the cyclic carboxylic acid sulfonic acid anhydride, and the cyclic phosphonic acid anhydride. That is, when the cyclic acid anhydride contains only one of cyclic dicarboxylic acid anhydride, cyclic disulfonic acid anhydride, cyclic carboxylic acid sulfonic acid anhydride and cyclic phosphonic acid anhydride, any one of them. The content of one type of cyclic acid anhydride.
  • the cyclic acid anhydride contains two or more of cyclic dicarboxylic acid anhydride, cyclic disulfonic acid anhydride, cyclic carboxylic acid sulfonic acid anhydride and cyclic phosphonic acid anhydride, the cyclic acid anhydride thereof.
  • the content of the substance is the sum of the contents of the two or more kinds of cyclic acid anhydrides.
  • the electrolytic solution may further contain a solvent and an electrolyte salt.
  • cyclic acid anhydrides cyclic dicarboxylic acid anhydride, cyclic disulfonic acid anhydride, cyclic carboxylic acid sulfonic acid anhydride and cyclic phosphonic acid anhydride
  • solvents described here are excluded from the solvents described here.
  • the solvent contains any one or more of non-aqueous solvents (organic solvents), and the electrolytic solution containing the non-aqueous solvent is a so-called non-aqueous electrolytic solution.
  • the non-aqueous solvent is an ester, an ether, or the like, and more specifically, a carbonic acid ester compound, a carboxylic acid ester compound, a lactone compound, or the like.
  • Carbonate ester compounds include cyclic carbonates and chain carbonates. Cyclic carbonates are ethylene carbonate, propylene carbonate and the like, and chain carbonates are dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate and the like. Carboxylate ester compounds include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate and ethyl trimethyl acetate. Lactone compounds include ⁇ -butyrolactone and ⁇ -valerolactone. Ethers include 1,2-dimethoxyethane, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane and the like, in addition to the above-mentioned lactone-based compounds.
  • the non-aqueous solvent is an unsaturated cyclic carbonate, a halogenated carbonate, a sulfonic acid ester, a phosphoric acid ester, a nitrile compound, an isocyanate compound, or the like. This is because the chemical stability of the electrolytic solution is improved.
  • unsaturated cyclic carbonates include vinylene carbonate (1,3-dioxolane-2-one), vinyl carbonate ethylene (4-vinyl-1,3-dioxolane-2-one) and methylene carbonate (4). -Methylene-1,3-dioxolane-2-one) and the like.
  • Halogenated carbonic acid esters include ethylene fluorocarbonate (4-fluoro-1,3-dioxolane-2-one) and ethylene difluorocarbonate (4,5-difluoro-1,3-dioxolane-2-one).
  • the sulfonic acid ester is 1,3-propane sultone or the like.
  • Phosphate esters include trimethyl phosphate and triethyl phosphate.
  • Nitrile compounds include acetonitrile, acrylonitrile, malononitrile, succinonitrile, glutaronitrile, adiponitrile, sebaconitrile, phthalonitrile and the like.
  • the isocyanate compound is hexamethylene diisocyanate or the like.
  • the electrolyte salt contains any one or more of light metal salts such as lithium salt.
  • This lithium salt includes lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), and bis (fluorosulfonyl) imide lithium (LiN (FSO)).
  • the content of the electrolyte salt is not particularly limited, but specifically, it is 0.3 mol / kg to 3.0 mol / kg with respect to the solvent. This is because high ionic conductivity can be obtained.
  • the positive electrode lead 14 contains any one or more of conductive materials such as aluminum, and the negative electrode lead 15 is any one of conductive materials such as copper, nickel and stainless steel. Includes type or two or more types.
  • the shape of each of the positive electrode lead 14 and the negative electrode lead 15 is a thin plate shape, a mesh shape, or the like.
  • FIG. 3 shows the planar configuration of the main parts (positive electrode active material layer 11B and negative electrode active material layer 12B) of the battery element 10 shown in FIG.
  • FIG. 3 shows only one positive electrode active material layer 11B and one negative electrode active material layer 12B, and is interposed between the positive electrode active material layer 11B and the negative electrode active material layer 12B.
  • the illustration of the separator 13 is omitted.
  • the positive electrode active material layer 11B is darkly shaded, and the negative electrode active material layer 12B is lightly shaded.
  • the planar shape of the battery element 10 (the shape of the surface along the XY surface) is rectangular as shown in FIG. Therefore, the planar shapes of the positive electrode 11 (positive electrode active material layer 11B) and the negative electrode 12 (negative electrode active material layer 12B) are rectangular as shown in FIGS. 1 and 3.
  • the positive electrode active material layer 11B has a length L1 (mm) and a width W1 (mm)
  • the negative electrode active material layer 12B has a length L2 (mm) and a width W2 (mm). ..
  • the entire positive electrode active material layer 11B faces a part of the negative electrode active material layer 12B. That is, the negative electrode active material layer 12B does not face a part of the positive electrode active material layer 11B, but faces the entire positive electrode active material layer 11B.
  • the entire positive electrode active material layer 11B faces a part of the negative electrode active material layer 12B between the positive electrode 11 (positive electrode active material layer 11B) and the negative electrode 12 (negative electrode active material layer 12B) during charging and discharging. This is to prevent unintentional precipitation of lithium when the lithium ions move in the water.
  • the total area of the positive electrode active material layer 11B on the side facing the negative electrode active material layer 12B is S1 and the total area of the negative electrode active material layer 12B on the side facing the positive electrode active material layer 11B is S2.
  • the area S2 is larger than the area S1.
  • the ratio of the area S2 to the area S1 is 1.001 to 1.1.
  • the value of this area ratio R shall be the value rounded to the fourth decimal place.
  • the area ratio R is within the above range when the entire positive electrode active material layer 11B faces a part of the negative electrode active material layer 12B and the electrolytic solution contains a cyclic acid anhydride. This is because the ratio R is optimized. As a result, as compared with the case where the area ratio R is outside the above range, the decomposition reaction of the electrolytic solution is suppressed as described above, so that the secondary battery is less likely to swell. The details of the reason why the secondary battery described here is less likely to swell will be described later.
  • the area ratio R is more preferably 1.004 to 1.06. This is because the decomposition reaction of the electrolytic solution is more suppressed, so that the secondary battery is less likely to swell.
  • the facing relationship between the positive electrode active material layer 11B and the negative electrode active material layer 12B, that is, the positive electrode active material layer 11B is the negative electrode active material. How it faces the material layer 12B is not particularly limited. In this case, the lengths L1 and L2 and the widths W1 and W2 can be set arbitrarily.
  • the entire positive electrode active material layer 11B faces the region inside the outer edge 12G of the negative electrode active material layer 12B. That is, since the position of the outer edge 11G of the positive electrode active material layer 11B does not match the position of the outer edge 12G of the negative electrode active material layer 12B, the negative electrode active material layer 12B faces the entire positive electrode active material layer 11B. It is preferable to include the region 12BX and the frame-shaped non-opposing region 12BY that surrounds the facing region 12BX from all sides (upward, downward, rightward and leftward).
  • a positive electrode 11 and a negative electrode 12 are prepared and an electrolytic solution is prepared according to the procedure described below, and then the secondary battery is manufactured using the positive electrode 11, the negative electrode 12 and the electrolytic solution. To do. In the following, the illustrated contents of FIGS. 1 to 3 already described will be quoted as needed.
  • the positive electrode active material is mixed with a positive electrode binder, a positive electrode conductive agent, and the like, if necessary, to obtain a positive electrode mixture.
  • a paste-like positive electrode mixture slurry is prepared by adding the positive electrode mixture to an organic solvent or the like.
  • the positive electrode active material layer 11B is formed by applying the positive electrode mixture slurry on both surfaces of the positive electrode current collector 11A including the protruding portion 11AT.
  • the positive electrode active material layer 11B may be compression-molded using a roll press or the like. In this case, the positive electrode active material layer 11B may be heated, or compression molding may be repeated a plurality of times. As a result, the positive electrode active material layers 11B are formed on both sides of the positive electrode current collector 11A, so that the positive electrode 11 is produced.
  • the negative electrode active material layers 12B are formed on both sides of the negative electrode current collector 12A by the same procedure as the procedure for producing the positive electrode 11 described above. Specifically, the negative electrode active material is mixed with a negative electrode binder, a negative electrode conductive agent, etc. as necessary to obtain a negative electrode mixture, and then the negative electrode mixture is added to an organic solvent or the like. Prepare a paste-like negative electrode mixture slurry. Subsequently, the negative electrode active material layer 12B is formed by applying the negative electrode mixture slurry to both surfaces of the negative electrode current collector 12A including the protruding portion 12AT. After that, the negative electrode active material layer 12B may be compression-molded. As a result, the negative electrode active material layers 12B are formed on both sides of the negative electrode current collector 12A, so that the negative electrode 12 is produced.
  • the magnitude relationship of the areas S1 and S2 is adjusted so that the area ratio R is 1.001 to 1.1 as described above.
  • the joint portion 11Z is formed by joining the plurality of projecting portions 11AT to each other by using a welding method or the like
  • the joining portion 12Z is formed by joining the plurality of protruding portions 12AT to each other by using a welding method or the like.
  • the positive electrode lead 14 is connected to the joint portion 11Z by a welding method or the like
  • the negative electrode lead 15 is connected to the joint portion 12Z by a welding method or the like.
  • the exterior film 20 is folded in the direction of the arrow R. Subsequently, the laminated body is stored inside the bag-shaped exterior film 20 by adhering the outer peripheral edges of the two sides of the exterior film 20 (fused layer) to each other by using a heat fusion method or the like. ..
  • the outer peripheral edges of the remaining one side of the exterior film 20 are bonded to each other by a heat fusion method or the like.
  • the adhesion film 21 is inserted between the exterior film 20 and the positive electrode lead 14, and the adhesion film 22 is inserted between the exterior film 20 and the negative electrode lead 15.
  • the laminated body is impregnated with the electrolytic solution, so that the battery element 10 which is a laminated electrode body is manufactured. Therefore, since the battery element 10 is enclosed inside the bag-shaped exterior film 20, the secondary battery is assembled.
  • the electrolytic solution contains a cyclic acid anhydride such as a cyclic dicarboxylic acid anhydride.
  • the content of the cyclic acid anhydride in the electrolytic solution is 0.001% by weight to 1% by weight, and the area ratio R is 1.001 to 1.1.
  • the content of the cyclic acid anhydride in the electrolytic solution is optimized and the area ratio R Is optimized, so that a stable film derived from the cyclic acid anhydride is formed on the surface of the negative electrode active material layer 12B (particularly, the surface of the non-opposite region 12BY) on the side facing the positive electrode active material layer 11B. ..
  • the electrolytic solution is injected into the laminate from the outside. Since the cyclic acid anhydride is easily arranged in the non-opposing region 12BY that does not face the positive electrode active material layer 11B, a film is easily formed on the surface of the non-opposing region 12BY.
  • the decomposition reaction of the electrolytic solution is specifically suppressed in the non-opposing region 12BY where the potential is high.
  • the generation of gas due to the decomposition reaction of the electrolytic solution is also suppressed.
  • the area ratio R is larger than 1 (the area S2 is larger than the area S1), lithium is less likely to precipitate during charging and discharging.
  • the secondary battery is less likely to swell during charging and discharging, so that excellent swelling characteristics can be obtained for the secondary battery.
  • the entire positive electrode active material layer 11B faces the region inside the outer edge 12G of the negative electrode active material layer 12B (opposing region 12BX), the decomposition reaction of the electrolytic solution is further suppressed. Therefore, the secondary battery is less likely to swell, and a higher effect can be obtained.
  • the cyclic dicarboxylic acid anhydride contains the compound represented by the formula (1)
  • the cyclic disulfonic acid anhydride contains the compound represented by the formula (2)
  • the cyclic dicarboxylic acid sulfonic acid anhydride contains the compound represented by the formula (2). If the compound shown in 3) is contained and the cyclic phosphonic acid anhydride contains the compound represented by the formula (4), the decomposition reaction of the electrolytic solution is sufficiently suppressed. Therefore, the secondary battery is sufficiently less likely to swell, and a higher effect can be obtained.
  • the content of the cyclic acid anhydride in the electrolytic solution is 0.01% by weight to 0.1% by weight, the decomposition reaction of the electrolytic solution is sufficiently suppressed. Therefore, the secondary battery is sufficiently less likely to swell, and a higher effect can be obtained.
  • the area ratio R is 1.004 to 1.06
  • the decomposition reaction of the electrolytic solution is sufficiently suppressed. Therefore, the secondary battery is sufficiently less likely to swell, and a higher effect can be obtained.
  • the secondary battery includes the positive electrode 11, the negative electrode 12, and the flexible exterior film 20 for accommodating the electrolytic solution, the exterior film 20 that is easily deformed due to the generation of gas is used, that is, the exterior. Even when the swelling of the secondary battery is likely to become apparent due to the flexibility of the film 20, the swelling of the secondary battery is effectively suppressed, so that a higher effect can be obtained.
  • the secondary battery is a lithium ion secondary battery, a higher effect can be obtained because a sufficient battery capacity can be stably obtained by utilizing the storage and release of lithium.
  • the negative electrode active material layer 12B is a frame type that surrounds the facing region 12BX facing the entire positive electrode active material layer 11B and the facing region 12BX from three sides (here, downward, right direction, and left direction). Includes the non-opposing region 12BY of.
  • the secondary battery is less likely to swell as the decomposition reaction of the electrolytic solution is further suppressed. Therefore, the same effect can be obtained.
  • the non-opposing region 12BY surrounds the facing region 12BX from the three directions of the downward direction, the right direction, and the left direction, but if the non-opposing region 12BY surrounds the facing region 12BX from the three sides, the positive electrode active material layer
  • the facing relationship between 11B and the negative electrode active material layer 12B is not particularly limited.
  • the non-opposing region 12BY may surround the facing region 12BX from three directions of upward, right and left directions, and may surround the opposing region 12BX from three directions of upward, downward and right directions.
  • the 12BX may be surrounded, or the facing region 12BX may be surrounded from three directions of upward, downward and left directions.
  • the non-opposing width H of the non-opposing region 12BY becomes too large locally, so that the non-opposing width H is locally large.
  • the decomposition reaction of the electrolytic solution is less likely to be suppressed in the facing region 12BY. Therefore, in order to effectively suppress the decomposition reaction of the electrolytic solution, in order to prevent the decomposition reaction of the electrolytic solution from being promoted due to the local increase in the non-opposing width H, FIG.
  • the non-opposing region 12BY surrounds the facing region 12BX from all sides, that is, the entire positive electrode active material layer 11B faces the region inside the outer edge 12G of the negative electrode active material layer 12B. It is preferable to have.
  • each of the joint portion 11Z and the positive electrode lead 14 is not particularly limited, the number is not limited to one, and may be two or more.
  • the number of each of the joint portion 12Z and the negative electrode lead 15 is not particularly limited, so the number is not limited to one, and may be two or more. In these cases, the same effect can be obtained.
  • the number of each of the positive electrode lead 14 and the negative electrode lead 15 is two or more, the electric resistance of the secondary battery is lowered, so that a higher effect can be obtained.
  • a separator 13 made of a porous membrane was used. However, although not specifically shown here, a laminated separator containing a polymer compound layer may be used instead of the separator 13 made of a porous membrane.
  • the laminated type separator includes a porous layer made of the above-mentioned porous film and a polymer compound layer provided on one side or both sides of the porous layer. This is because the adhesion of the separator to each of the positive electrode 11 and the negative electrode 12 is improved, so that the misalignment of the battery element 10 is less likely to occur. As a result, even if a decomposition reaction of the electrolytic solution occurs, the secondary battery is less likely to swell.
  • the polymer compound layer contains a polymer compound such as polyvinylidene fluoride. This is because it has excellent physical strength and is electrochemically stable.
  • one or both of the porous layer and the polymer compound layer may contain any one or more of a plurality of particles such as a plurality of inorganic particles and a plurality of resin particles. This is because a plurality of particles dissipate heat when the secondary battery generates heat, so that the heat resistance and safety of the secondary battery are improved.
  • the inorganic particles may be any one of inorganic materials such as aluminum oxide (alumina), aluminum nitride, boehmite, silicon oxide (silica), titanium oxide (titania), magnesium oxide (magnesia) and zirconia oxide (zirconia). Includes two or more types.
  • the positive electrode 11 and the negative electrode 12 are alternately laminated via the separator 13 and the electrolyte layer.
  • This electrolyte layer is interposed between the positive electrode 11 and the separator 13 and is interposed between the negative electrode 12 and the separator 13.
  • the electrolyte layer contains a polymer compound together with the electrolytic solution, and the electrolytic solution is held by the polymer compound in the electrolyte layer.
  • the structure of the electrolytic solution is as described above.
  • the polymer compound contains polyvinylidene fluoride and the like.
  • the use of the secondary battery is mainly for machines, devices, appliances, devices and systems (aggregates of a plurality of devices, etc.) in which the secondary battery can be used as a power source for driving or a power storage source for storing power. If so, it is not particularly limited.
  • the secondary battery used as a power source may be a main power source or an auxiliary power source.
  • the main power source is a power source that is preferentially used regardless of the presence or absence of another power source.
  • the auxiliary power supply may be a power supply used in place of the main power supply, or may be a power supply that can be switched from the main power supply as needed.
  • the type of main power source is not limited to the secondary battery.
  • Secondary batteries Specific examples of applications for secondary batteries are as follows.
  • Electronic devices such as video cameras, digital still cameras, mobile phones, laptop computers, cordless phones, headphone stereos, portable radios, portable TVs and portable information terminals.
  • It is a portable living appliance such as an electric shaver.
  • a storage device such as a backup power supply and a memory card.
  • Power tools such as electric drills and saws.
  • It is a battery pack that is installed in notebook computers as a removable power source. Medical electronic devices such as pacemakers and hearing aids.
  • It is an electric vehicle such as an electric vehicle (including a hybrid vehicle).
  • It is a power storage system such as a household battery system that stores power in case of an emergency.
  • the battery structure of the secondary battery may be the above-mentioned laminated film type or cylindrical type, or may be another battery structure other than these. Further, a plurality of secondary batteries may be used as the battery pack, the battery module, and the like.
  • the battery pack and the battery module are applied to relatively large equipment such as electric vehicles, power storage systems and electric tools.
  • a single battery or an assembled battery may be used.
  • the electric vehicle is a vehicle that operates (runs) using a secondary battery as a driving power source, and may be a vehicle (hybrid vehicle or the like) that also has a drive source other than the secondary battery as described above.
  • the power storage system is a system that uses a secondary battery as a power storage source. In a household electric power storage system, since electric power is stored in a secondary battery which is an electric power storage source, it is possible to use the electric power for household electric products and the like.
  • the configuration of the application example described below is just an example, and can be changed as appropriate.
  • the type of the secondary battery used in the following application examples is not particularly limited, and may be a laminated film type or a cylindrical type.
  • FIG. 5 shows a block configuration of a battery pack using a cell.
  • the battery pack described here is a simple battery pack (so-called soft pack) using one secondary battery, and is mounted on an electronic device represented by a smartphone.
  • this battery pack includes a power supply 31 and a circuit board 32.
  • the circuit board 32 is connected to the power supply 31 and includes a positive electrode terminal 33, a negative electrode terminal 34, and a temperature detection terminal (so-called T terminal) 35.
  • the power supply 31 includes one secondary battery.
  • the positive electrode lead is connected to the positive electrode terminal 33
  • the negative electrode lead is connected to the negative electrode terminal 34. Since the power supply 31 can be connected to the outside via the positive electrode terminal 33 and the negative electrode terminal 34, it can be charged and discharged via the positive electrode terminal 33 and the negative electrode terminal 34.
  • the circuit board 32 includes a control unit 36, a switch 37, a heat-sensitive resistance element (PTC (Positive Temperature Coefficient) element) 38, and a temperature detection unit 39. However, the PTC element 38 may be omitted.
  • the control unit 36 includes a central processing unit (CPU: Central Processing Unit), a memory, and the like, and controls the operation of the entire battery pack.
  • the control unit 36 detects and controls the usage state of the power supply 31 as needed.
  • the control unit 36 disconnects the switch 37 so that the charging current does not flow in the current path of the power supply 31. To do so. Further, when a large current flows during charging or discharging, the control unit 36 cuts off the charging current by disconnecting the switch 37.
  • the overcharge detection voltage and the overdischarge detection voltage are not particularly limited. As an example, the overcharge detection voltage is 4.2V ⁇ 0.05V, and the overdischarge detection voltage is 2.4V ⁇ 0.1V.
  • the switch 37 includes a charge control switch, a discharge control switch, a charging diode, a discharging diode, and the like, and switches whether or not the power supply 31 is connected to an external device according to an instruction from the control unit 36.
  • This switch 37 includes a field effect transistor (MOSFET: Metal-Oxide-Semiconductor Field-Effect Transistor) using a metal oxide semiconductor, and the charge / discharge current is detected based on the ON resistance of the switch 37. ..
  • the temperature detection unit 39 includes a temperature detection element such as a thermistor, measures the temperature of the power supply 31 using the temperature detection terminal 35, and outputs the measurement result of the temperature to the control unit 36.
  • the temperature measurement result measured by the temperature detection unit 39 is used when the control unit 36 performs charge / discharge control when abnormal heat generation occurs, or when the control unit 36 performs correction processing when calculating the remaining capacity.
  • FIG. 6 shows a block configuration of a battery pack using an assembled battery.
  • components of a battery pack using a cell see FIG. 5 will be cited from time to time.
  • this battery pack includes a positive electrode terminal 51 and a negative electrode terminal 52.
  • the battery pack contains a control unit 41, a power supply 42, a switch 43, a current measurement unit 44, a temperature detection unit 45, a voltage detection unit 46, and a switch control unit inside the housing 40. It includes 47, a memory 48, a temperature detection element 49, and a current detection resistor 50.
  • the power supply 42 includes an assembled battery in which two or more secondary batteries are connected to each other, and the connection form of the two or more secondary batteries is not particularly limited. Therefore, the connection method may be in series, in parallel, or a mixed type of both. As an example, the power supply 42 includes six secondary batteries connected to each other so as to be in two parallels and three series.
  • the configurations of the control unit 41, the switch 43, the temperature detection unit 45, and the temperature detection element 49 are the same as the configurations of the control unit 36, the switch 37, and the temperature detection unit 39 (temperature detection element).
  • the current measuring unit 44 measures the current using the current detection resistor 50, and outputs the measurement result of the current to the control unit 41.
  • the voltage detection unit 46 measures the battery voltage of the power supply 42 (secondary battery) and supplies the measurement result of the analog-to-digital converted voltage to the control unit 41.
  • the switch control unit 47 controls the operation of the switch 43 according to the signals input from the current measurement unit 44 and the voltage detection unit 46.
  • the switch control unit 47 disconnects the switch 43 (charge control switch) so that the charge current does not flow in the current path of the power supply 42. ..
  • the switch control unit 47 cuts off the charging current or the discharging current when a large current flows during charging or discharging.
  • control unit 41 may also function as the switch control unit 47.
  • the overcharge detection voltage and the overdischarge detection voltage are not particularly limited, but are the same as those described for the battery pack using a single battery.
  • the memory 48 includes an EEPROM (Electrically Erasable Programmable Read-Only Memory) which is a non-volatile memory, and the memory 48 includes a numerical value calculated by the control unit 41 and a secondary battery measured in the manufacturing process. Information (initial resistance, full charge capacity, remaining capacity, etc.) is stored.
  • EEPROM Electrically Erasable Programmable Read-Only Memory
  • the positive electrode terminal 51 and the negative electrode terminal 52 are terminals connected to an external device (such as a notebook personal computer) that operates using the battery pack and an external device (such as a charger) that is used to charge the battery pack. is there.
  • the power supply 42 (secondary battery) can be charged and discharged via the positive electrode terminal 51 and the negative electrode terminal 52.
  • FIG. 7 shows a block configuration of a hybrid vehicle which is an example of an electric vehicle.
  • this electric vehicle includes a control unit 61, an engine 62, a power supply 63, a motor 64, a differential device 65, a generator 66, and a transmission 67 inside the housing 60. It also includes a clutch 68, inverters 69 and 70, and various sensors 71. Further, the electric vehicle includes a front wheel drive shaft 72 and a pair of front wheels 73 connected to the differential device 65 and the transmission 67, and a rear wheel drive shaft 74 and a pair of rear wheels 75.
  • the engine 62 is a main power source such as a gasoline engine.
  • the driving force (rotational force) of the engine 62 is transmitted to the front wheels 73 and the rear wheels 75 via the differential device 65, the transmission 67, and the clutch 68, which are the driving units. Since the rotational force of the engine 62 is transmitted to the generator 66, the generator 66 uses the rotational force to generate AC power, and the AC power is converted into DC power via the inverter 70. Therefore, the DC power is stored in the power source 63.
  • the motor 64 which is a conversion unit
  • the electric power (DC power) supplied from the power supply 63 is converted into AC power via the inverter 69, and the AC power is used to convert the motor. 64 is driven.
  • the driving force (rotational force) converted from the electric power by the motor 64 is transmitted to the front wheels 73 and the rear wheels 75 via the differential device 65, the transmission 67, and the clutch 68, which are the driving units.
  • the resistance force at the time of deceleration is transmitted to the motor 64 as a rotational force, so that the motor 64 may generate AC power by using the rotational force. Since this AC power is converted into DC power via the inverter 69, the DC regenerative power is stored in the power supply 63.
  • the control unit 61 includes a CPU and the like, and controls the operation of the entire electric vehicle.
  • the power supply 63 includes one or more secondary batteries and is connected to an external power source. In this case, the power supply 63 may store electric power by being supplied with electric power from an external power source.
  • the various sensors 71 are used to control the rotation speed of the engine 62 and to control the opening degree (throttle opening degree) of the throttle valve.
  • the various sensors 71 include any one or more of the speed sensor, the acceleration sensor, the engine speed sensor, and the like.
  • the electric vehicle may be a vehicle (electric vehicle) that operates using only the power supply 63 and the motor 64 without using the engine 62.
  • the secondary battery is applicable to the power storage system.
  • This power storage system includes a control unit, a power source including one or more secondary batteries, a smart meter, and a power hub inside a house such as a general house and a commercial building.
  • the power supply is connected to electrical equipment such as a refrigerator installed inside the house, and can also be connected to an electric vehicle such as a hybrid vehicle parked outside the house.
  • the power supply is connected to a private power generator such as a solar power generator installed in a house via a power hub, and is also connected to a centralized power system such as an external thermal power plant via a smart meter and a power hub. Has been done.
  • the secondary battery can be applied to electric tools such as electric drills and electric saws.
  • This power tool includes a control unit and a power supply including one or more secondary batteries inside a housing to which a movable portion such as a drill portion and a saw blade portion is attached.
  • a secondary battery was manufactured by the following procedure.
  • the positive electrode active material layer 11B was formed by drying the agent slurry.
  • the positive electrode active material layer 11B was compression molded using a roll press machine. As a result, the positive electrode active material layers 11B were formed on both sides of the positive electrode current collector 11A, so that the positive electrode 11 was produced.
  • the area S1 is set by setting the formation dimensions (length L1 (mm) and width W1 (mm)) of the positive electrode active material layer 11B as shown in Tables 1 and 2. Was adjusted.
  • the negative electrode mixture layer 12B was formed by drying the negative electrode mixture slurry.
  • the negative electrode active material layer 12B was compression molded using a roll press machine. As a result, the negative electrode active material layers 12B were formed on both sides of the negative electrode current collector 12A, so that the negative electrode 12 was produced.
  • the entire positive electrode active material layer 11B can face the region inside the outer edge 12G of the negative electrode active material layer 12B (opposing region 12BX).
  • the non-opposing widths H on all four sides of the facing region 12BX were made equal to each other.
  • the area S2 was adjusted by setting the formation dimensions (length L2 (mm) and width W2 (mm)) of the negative electrode active material layer 12B.
  • Each value of the length L2 and the width W2 is a value obtained by rounding off the value at the fourth decimal place.
  • the area ratio R was adjusted based on the areas S1 and S2.
  • the amount of the positive electrode active material and the negative electrode active material are adjusted so that the open circuit voltage (so-called battery voltage) when the secondary battery is fully charged is 4.45 V. Each of the amounts of was adjusted.
  • the solvent was prepared.
  • this solvent include ethylene carbonate and propylene carbonate which are carbonic acid ester compounds (cyclic carbonate ester), diethyl carbonate which is a carbonic acid ester compound (chain carbonate ester), and propyl propionate which is a carboxylic acid ester compound.
  • an electrolyte salt lithium hexafluorophosphate (LiPF 6 )
  • LiPF 6 lithium hexafluorophosphate
  • a cyclic acid anhydride (cyclic dicarboxylic acid anhydride) was added to the solvent to which the electrolyte salt was added, and then the solvent was stirred.
  • the types of cyclic dicarboxylic acid anhydrides and the content (% by weight) of the cyclic acid anhydrides in the electrolytic solution are as shown in Tables 1 and 2.
  • the electrolyte salt and the cyclic acid anhydride were dispersed or dissolved in the solvent, respectively, so that an electrolytic solution was prepared.
  • an electrolytic solution was prepared by the same procedure except that cyclic acid anhydride was not used.
  • a laminated separator 13 was used.
  • a polymer compound polyvinylidene fluoride
  • organic solvent N-methyl-2-pyrrolidone
  • the dispersion was prepared by stirring the organic solvent.
  • the mixing ratio weight ratio
  • a laminated body was produced by laminating the positive electrode 11 and the negative electrode 12 with each other via a laminated separator 13. Subsequently, a plurality of protruding portions 11AT were welded to each other to form a joint portion 11Z, and then an aluminum positive electrode lead 14 was welded to the joint portion 11Z. Further, after forming the joint portion 12Z by welding the plurality of protruding portions 12AT to each other, the copper negative electrode lead 15 was welded to the joint portion 12Z.
  • the exterior film 20 is folded so as to sandwich the laminate housed inside the recessed portion 20U, and then the outer peripheral edges of the two sides of the exterior film 20 are heat-sealed to each other to form a bag.
  • the laminate was housed inside the outer film 20 in the shape of a shape.
  • the outer peripheral edges of the remaining one side of the exterior film 20 were heat-sealed to each other in a reduced pressure environment.
  • the adhesive film 22 polypropylene film
  • Thickness 5 ⁇ m
  • the battery was charged with a constant current of 0.2 C until the battery voltage reached 4.45 V, and then charged with a current of 4.45 V until the current reached 0.05 C.
  • a constant current was discharged with a current of 0.2 C until the battery voltage reached 2.0 V.
  • 0.2C is a current value that can completely discharge the battery capacity (theoretical capacity) in 5 hours
  • 0.05C is a current value that can completely discharge the above-mentioned battery capacity in 20 hours.
  • the swelling characteristics of the secondary battery depend on the composition of the positive electrode 11 and the negative electrode 12 (area ratio R) and the composition of the electrolytic solution (content of cyclic acid anhydride in the electrolytic solution). It fluctuated greatly accordingly.
  • the electrolytic solution contains cyclic acid anhydride and the area ratio R is 1.001.
  • the three conditions of ⁇ 1.1 and the content of the cyclic acid anhydride are 0.001% by weight to 1% by weight are simultaneously satisfied (Experimental Examples 1-1 to 1-5, 1-). 7 to 1-26, 1-28 to 1-42), as compared with the case where the three conditions are not satisfied at the same time (Experimental Examples 1-6, 1-27, 1-43 to 1-50). , The swelling rate has decreased significantly.
  • the swelling rate is further reduced and the content of the cyclic acid anhydride is 0.01 weight by weight.
  • the swelling rate was further reduced.
  • the entire positive electrode active material layer 11B faces a part of the negative electrode active material layer 12B, and the electrolytic solution contains a cyclic acid anhydride such as a cyclic dicarboxylic acid anhydride.
  • the content of the cyclic acid anhydride in the electrolytic solution was 0.001% by weight to 1% by weight and the area ratio R was 1.001 to 1.1, the swelling rate was improved. Therefore, excellent swelling characteristics were obtained in the secondary battery.
  • the battery structure of the secondary battery is a laminated film type
  • the battery structure is not particularly limited, other battery structures such as a cylindrical type, a square type, a coin type, and a button type are described. But it may be.
  • the element structure of the battery element is a laminated type
  • the wound type and the electrodes (positive electrode and negative electrode) in which the electrodes (positive electrode and negative electrode) are wound are described.
  • Other element structures such as a ninety-nine-fold type in which the negative electrode) is folded in a zigzag manner may be used.
  • the electrode reactant is lithium has been described, but the electrode reactant is not particularly limited. Specifically, as described above, the electrode reactant may be another alkali metal such as sodium and potassium, or an alkaline earth metal such as beryllium, magnesium and calcium. In addition, the electrode reactant may be another light metal such as aluminum.

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Abstract

La présente invention concerne une batterie secondaire pourvue : d'une électrode négative qui comprend une couche de matériau actif d'électrode négative ; d'une électrode positive qui comprend une couche de matériau actif d'électrode positive de telle manière que la totalité de la couche de matériau actif d'électrode positive fait face à une partie de la couche de matériau actif d'électrode négative ; et d'une solution électrolytique qui contient un anhydride d'acide cyclique qui contient au moins un anhydride d'acide choisi parmi un anhydride d'acide dicarboxylique cyclique, un anhydride d'acide disulfonique cyclique, un anhydride d'acide sulfonique d'acide carboxylique cyclique et un anhydride d'acide phosphonique cyclique. La teneur de l'anhydride d'acide cyclique dans la solution électrolytique est de 0 001 % en poids à 1 % en poids ; et le rapport de la superficie totale de la couche de matériau actif d'électrode négative sur la superficie totale de la couche de matériau actif d'électrode positive est de 1,001 à 1,1.
PCT/JP2020/046018 2019-12-26 2020-12-10 Batterie secondaire WO2021131742A1 (fr)

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