WO2015037367A1 - Batterie rechargeable à électrolyte non aqueux - Google Patents

Batterie rechargeable à électrolyte non aqueux Download PDF

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WO2015037367A1
WO2015037367A1 PCT/JP2014/070698 JP2014070698W WO2015037367A1 WO 2015037367 A1 WO2015037367 A1 WO 2015037367A1 JP 2014070698 W JP2014070698 W JP 2014070698W WO 2015037367 A1 WO2015037367 A1 WO 2015037367A1
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negative electrode
secondary battery
aqueous electrolyte
electrolyte secondary
group
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PCT/JP2014/070698
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English (en)
Japanese (ja)
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川崎　大輔
入山　次郎
伊紀子 島貫
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日本電気株式会社
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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
    • H01M10/056—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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery characterized by the relationship between the amount of water in the negative electrode and the additive in the electrolyte.
  • a secondary battery using such a non-aqueous electrolyte (hereinafter referred to as a non-aqueous electrolyte secondary battery) is mainly composed of an electrode active material capable of reversibly occluding and releasing chemical species (lithium ions) as charge carriers.
  • a non-aqueous electrolyte is inserted and sealed between electrodes (positive electrode and negative electrode) provided with an electrode active material layer on the electrode current collector.
  • non-aqueous electrolyte secondary batteries particularly lithium ion non-aqueous electrolyte secondary batteries
  • the liquid may contain about 20 ppm or more of water.
  • the active material layer in the positive electrode and the negative electrode can contain moisture.
  • Patent Document 1 discloses that the existence is allowed.
  • the positive electrode or negative electrode active material layer is formed by adding an appropriate solvent and dispersing an active material together with a binder, applying the obtained paste or slurry to a current collector, and drying.
  • As the positive electrode active material lithium manganate composite oxide and lithium iron phosphate, which are more resource-efficient than conventional lithium cobaltate composite oxides, are becoming mainstream.
  • As the negative electrode active material a carbon-based negative electrode material is mainstream.
  • an active material such as graphite (natural or artificial), graphitizable carbon (soft carbon), non-graphitizable carbon (hard carbon), and fibrous carbon is used as a binder ( It can be obtained by dispersing in water together with styrene-butadiene rubber (SBR) and a thickener (carboxymethyl cellulose: CMC), preparing an aqueous slurry, applying it, and drying.
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • water-based thickeners such as CMC are extremely hygroscopic and require treatment at high temperatures to remove moisture to a high degree, but cracks occur in the active material layer due to the low decomposition temperature. There is.
  • Patent Document 2 describes the surface of the active material layer before the formation of the porous inorganic layer in order to prevent the binder for the porous inorganic layer from covering the surface of the active material when forming the porous inorganic layer on the surface of the active material layer. It is disclosed that the water concentration of this is about 100 to 500 ppm.
  • the water content of the final negative electrode sheet is 200 ppm or less, preferably 100 ppm or less.
  • the negative electrode active material layer is applied, dried, and then exposed to an environment having a dew point temperature of 17 ° C. to 52 ° C. for at least 30 minutes. Drying is adjusted so that the water concentration is 500 ppm or less.
  • Patent Documents 4 to 6 As a method of suppressing the decomposition reaction of the electrolytic solution by forming a protective film on the electrode surface, a technique using a secondary battery electrolytic solution containing a cyclic sulfonic acid ester having at least two sulfonyl groups, or unsaturated Techniques using a cyclic or chain disulfonic acid ester having a bond are disclosed (Patent Documents 4 to 6).
  • Patent Document 7 describes a lithium ion secondary battery having an electrolytic solution containing a chain disulfonic acid ester and a cyclic disulfonic acid ester, and a negative electrode containing one type of carbon as a negative electrode active material.
  • the amount of moisture in the non-aqueous electrolyte secondary battery particularly the amount of moisture in the negative electrode
  • the additive in the non-aqueous electrolyte particularly the addition of a protective film to suppress SEI formation on the surface of the negative electrode active material layer
  • the negative electrode active material not only the water-based negative electrode mixture described above, but also an organic solvent-based negative electrode mixture using polyvinylidene fluoride (PVdF) or the like as a binder, the negative electrode active material, the conductive material, and the organic solvent easily absorb moisture. It is often composed of materials and may contain a lot of moisture depending on the manufacturing environment.
  • PVdF polyvinylidene fluoride
  • the present invention focuses on the relationship between the protective film-forming additive in the non-aqueous electrolyte and the amount of moisture in the negative electrode, and an object is to provide a non-aqueous electrolyte secondary battery excellent in battery characteristics, particularly coulomb efficiency.
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an amino group, provided that at least one of R 1 and R 2 is hydrogen.
  • R 3 is an alkylene group having 1 to 5 carbon atoms, a carbonyl group, a sulfinyl group, a fluoroalkylene group having 1 to 6 carbon atoms, an alkylene unit or a carbon number 2 in which a fluoroalkylene unit is bonded via an ether bond.
  • a linking group selected from the group consisting of divalent groups of 6 to 6 is shown.
  • the embodiment of the present invention can provide a non-aqueous electrolyte secondary battery excellent in coulomb efficiency.
  • nonaqueous electrolyte solution is a cyclic represented by the general formula (1) as an additive.
  • Contains a sulfonic acid ester hereinafter sometimes simply referred to as “compound of general formula (1)”.
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an amino group, provided that at least one of R 1 and R 2 is hydrogen.
  • R 3 is an alkylene group having 1 to 5 carbon atoms, a carbonyl group, a sulfinyl group, a fluoroalkylene group having 1 to 6 carbon atoms, an alkylene unit or a carbon number 2 in which a fluoroalkylene unit is bonded via an ether bond.
  • a linking group selected from the group consisting of divalent groups of 6 to 6 is shown.
  • the cyclic sulfonate ester represented by the general formula (1) contained in the nonaqueous electrolytic solution is decomposed by an electrochemical redox reaction during the charge / discharge reaction to form a film on the surface of the negative electrode active material.
  • the decomposition of the supporting salt can be suppressed. This is considered to be effective in extending the life of the lithium ion secondary battery.
  • the electrolytic solution containing such a compound of the general formula (1) storage stability is improved and deterioration is suppressed, and when this electrolytic solution is used, capacity maintenance and storage characteristics of the lithium ion secondary battery, In particular, the remaining capacity maintenance characteristic accompanying self-discharge is remarkably improved.
  • Cyclic sulfonic acid ester represented by the above general formula (1) is compared by either R 1, R 2 is replaced with a sulfonic acid ester both of R 1, R 2 is a hydrogen atom
  • the film forming ability formed on the negative electrode surface is improved.
  • the cyclic sulfonate ester represented by the general formula (1) is substituted with a compound in which either R 1 or R 2 is a hydrogen atom because either R 1 or R 2 is substituted.
  • the ⁇ -position carbon substituted by R 1 and R 2 in the general formula (1) is water in the negative electrode in the case of an unsubstituted additive (in this case, R 3 is a compound of methylene and is referred to as additive X1).
  • R 3 is a compound of methylene and is referred to as additive X1.
  • the additive X1 adsorbed on the negative electrode surface is combined with free Li ions (formula (a)) in the electrolytic solution after hydrogen is extracted to form a Li salt and elute into the electrolytic solution.
  • the ability to form a film on the surface of the negative electrode active material is reduced.
  • the ⁇ -position carbon is substituted with a substituent such as a methyl group, hydrogen abstraction from the ⁇ -position carbon is suppressed, and a decrease in film forming ability is suppressed.
  • a compound in which at least one of R 1 and R 2 is an alkyl group is preferable.
  • Particularly preferred are compounds in which one is an alkyl group and the other is a hydrogen atom, or both are alkyl groups.
  • Alkyl groups for R 1 and R 2 include methyl, ethyl, propyl, butyl and pentyl, which may be linear or branched. In particular, methyl, ethyl and propyl are preferred.
  • the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is preferable.
  • R 3 represents an alkylene group having 1 to 5 carbon atoms, a carbonyl group, a sulfinyl group, a fluoroalkylene group having 1 to 6 carbon atoms, or an alkylene unit or 2 having 2 to 6 carbon atoms bonded to each other via an ether bond.
  • a linking group selected from the group consisting of valent groups is shown.
  • the alkylene group having 1 to 5 carbon atoms is preferably methylene, ethylene (1,1-ethylene, 1,2-ethylene) or 2,2-propylene.
  • the fluoroalkylene group having 1 to 6 carbon atoms is monofluoro Methylene, difluoromethylene, monofluoroethylene, difluoroethylene, trifluoroethylene and tetrafluoroethylene are preferred.
  • R 3 is preferably an alkylene group having 1 to 5 carbon atoms, a fluoroalkylene group having 1 to 6 carbon atoms, or a carbonyl group, and among them, methylene or ethylene is most preferable.
  • the compounds represented by the general formula (1) may be used singly or in combination of two or more. Although the typical example of a compound of General formula (1) is specifically illustrated in Table 1, this invention is not limited to these.
  • the compound of the general formula (1) is produced by, for example, a production method described in US Pat. No. 4,950,768 (Japanese Patent Laid-Open No. 61-501089, Japanese Patent Publication No. 5-44946), Japanese Patent Laid-Open No. 2005-336155, etc. Can be used.
  • the proportion of the compound of the general formula (1) in the electrolytic solution is not particularly limited, but it is preferably contained in 0.005 to 10% by mass of the entire electrolytic solution.
  • concentration of the compound of the general formula (1) By setting the concentration of the compound of the general formula (1) to 0.005% by mass or more, a low resistance film can be obtained. More preferably, when 0.01% by mass or more is added, battery characteristics can be further improved.
  • the raise of the viscosity of electrolyte solution and the increase in resistance accompanying it can be suppressed. More preferably, 5% by mass or less is added. By doing so, the battery characteristics can be further improved.
  • the compound of the said General formula (1) can be added and used for the solution which melt
  • lithium salt examples include LiPF 6 , lithium imide salt, LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6, and the like.
  • the lithium imide salt LiN (C k F 2k + 1 SO 2) (C m F 2m + 1 SO 2) (k and m is a natural number independently, preferably 1 or 2). These may use only 1 type and may use 2 or more types together. In particular, it is preferable to contain one or more fluorine-containing lithium salts, and LiPF 6 is most preferable among them.
  • the concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.7 mol / L or more and 2.0 mol / L or less.
  • concentration of the lithium salt By setting the concentration of the lithium salt to 0.7 mol / L or more, sufficient ionic conductivity can be obtained.
  • concentration of lithium salt 2.0 mol / L or less a viscosity can be made low and the movement of lithium ion is not prevented.
  • At least one solvent selected from the group consisting of cyclic carbonates, chain carbonates, aliphatic carboxylic acid esters, ⁇ -lactones, cyclic ethers and chain ethers can be used.
  • the cyclic carbonate include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and derivatives thereof (including fluorinated products).
  • the chain carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dipropyl carbonate (DPC), and derivatives thereof (including fluorinated products).
  • Examples of the aliphatic carboxylic acid ester include methyl formate, methyl acetate, ethyl propionate, and derivatives thereof (including fluorinated products).
  • Examples of ⁇ -lactone include ⁇ -butyrolactone and its derivatives (including fluorinated products).
  • Examples of the cyclic ether include tetrahydrofuran, 2-methyltetrahydrofuran and derivatives thereof (including fluorinated products).
  • Examples of the chain ether include 1,2-diethoxyethane (DEE), ethoxymethoxyethane (EME), ethyl ether, diethyl ether, and derivatives thereof (including fluorinated compounds).
  • non-aqueous solvents include dimethyl sulfoxide, dioxolane derivatives such as 1,3-dioxolane and substituted dioxolane, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, and phosphate triesters. , Trimethoxymethane, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, 1,3-propane sultone, anisole, N-methylpyrrolidone, and derivatives thereof (fluorine Can also be used. These may use only 1 type and may use 2 or more types together. In particular, a combination of a cyclic carbonate and a chain carbonate can be preferably used.
  • the electrolyte solution of the present embodiment can further include a compound having at least one sulfonyl group.
  • the compound having at least one sulfonyl group (hereinafter also referred to as a sulfonyl group-containing compound) is a compound different from the cyclic sulfonate ester represented by the general formula (1).
  • sulfonyl group-containing compound there are compounds overlapping with the above non-aqueous solvent, but “sulfonyl group-containing compounds” are usually cyclic carbonates, chain carbonates, aliphatic carboxylic acid esters, ⁇ - It is used with at least one non-aqueous solvent selected from the group consisting of lactones, cyclic ethers, chain ethers and fluorine derivatives of these compounds.
  • the sulfonyl group-containing compound is preferably a sultone compound represented by the following general formula (2) or (3).
  • n represents an integer of 0 to 2
  • R 4 to R 9 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or Represents an aryl group having 6 to 12 carbon atoms.
  • m represents an integer of 0 to 3
  • R 10 to R 13 represent a hydrogen atom, a fluorine atom or an alkyl group which may contain a fluorine atom having 1 to 12 carbon atoms, a carbon number of 3 Represents a cycloalkyl group having 6 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • Examples of the compound represented by the general formula (2) include saturated cyclic sulfonic acid esters such as 1,3-propane sultone (PS) and 1,4-butane sultone, which are represented by the general formula (3).
  • Examples of the compound include unsaturated cyclic sulfonic acid esters such as 1,3-prop-2-ene sultone. These can be used alone or in combination of two or more.
  • the sulfonyl group-containing compound is used in the range of 0.005 to 10% by mass of the entire electrolyte.
  • the electrolytic solution of the present embodiment can further include vinylene carbonate or a derivative thereof.
  • vinylene carbonate or derivatives thereof include vinylene carbonate (VC), 4-methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, 4-ethyl vinylene carbonate, 4,5-diethyl vinylene carbonate, 4-propyl vinylene carbonate, 4, Mention may be made of vinylene carbonates such as 5-dipropyl vinylene carbonate, 4-phenyl vinylene carbonate and 4,5-diphenyl vinylene carbonate; and vinyl alkylene carbonates such as vinyl ethylene carbonate (VEC) and divinyl ethylene carbonate.
  • VEC vinyl ethylene carbonate
  • VEC divinyl ethylene carbonate
  • Vinylene carbonate or a derivative thereof is used at 0.005 to 10% by mass of the entire electrolytic solution.
  • the electrolyte solution can also contain other additives other than the above compounds, if necessary.
  • additives include an overcharge inhibitor and a surfactant.
  • the negative electrode can be produced by forming a negative electrode active material layer containing a negative electrode active material and a binder (binder) on the negative electrode current collector.
  • the negative electrode active material the following materials that can occlude and release lithium ions can be used alone or in admixture of two or more.
  • Carbonaceous materials such as cokes, glassy carbons, graphite materials (graphites), non-graphitizable carbons, graphitizable carbons, pyrolytic carbons, carbon fibers,
  • An active material mainly composed of Al, Si, Pb, Sn, Zn, Cd, Sb or the like, or a metal or semi-metal material such as an alloy of these and lithium, LiFe 2 O 3, WO 2, MoO 2, SiO, SiO 2, CuO, SnO, SnO 2, Nb 3 O 5, Li x Ti 2-x O 4 (0 ⁇ x ⁇ 1), PbO 2, PbO 5 etc.
  • Metal oxides Metal sulfides such as SnS and FeS 2 ; Metallic lithium, lithium alloy, polyacene, polythiophene, Li 5 (Li 3 N), Li 7 MnN 4, Li 3 FeN 2, Li 2.5 Co 0.5 N, Li 3 lithium nitride such as CoN, complexes thereof with carbon.
  • the resistance of the interface between the film formed on the surface of the negative electrode active material and the film formed at the binder / electrolyte interface is reduced, and the movement of lithium ions is further improved. It can be smooth.
  • the graphite material may be coated on the surface with carbon having lower crystallinity than the core material.
  • Examples of natural graphite include flaky natural graphite, spherical natural graphite, massive natural graphite, and earth-like natural graphite. Of these, spherical natural graphite is preferable.
  • Examples of the artificial graphite include spherical artificial graphite such as massive artificial graphite, scaly artificial graphite, and MCMB (mesophase micro beads). Among these, massive artificial graphite is preferable.
  • Examples of the shape of the non-graphitizable carbon include a lump shape, a flake shape, and a scale shape, and a lump shape is preferable among these. Examples of the shape of graphitizable carbon include a lump shape, a flake shape, and a scale shape, and among these, a scale shape is preferable.
  • the ratio is the ratio of the length in the short axis direction (length in the shortest direction) to the length in the long axis direction (length in the longest direction) (short axis).
  • (/ major axis) is larger than 0.2, it can be determined as a spherical or massive shape.
  • the (minor axis) / (major axis) of the spherical graphite is preferably 0.3 or more, more preferably 0.5 or more.
  • Spherical graphite is manufactured using scaly graphite as a raw material, and has a structure in which scaly graphite is folded into a spherical shape. For this reason, a cut is observed in the spherical graphite, and it has a cabbage-like appearance in which the cut is directed in various directions. In addition, voids are observed on the fracture surface of the spherical graphite.
  • the crystal orientation is directed in various directions even after the rolling process at the time of electrode preparation, so that lithium ions can be easily moved between the electrodes.
  • voids suitable for holding the electrolyte solution can be obtained between the negative electrode active materials, so that a lithium ion non-aqueous electrolyte secondary battery excellent in high output characteristics can be obtained.
  • the lump graphite has a uniform shape without the fact that it is observed with the above spherical graphite.
  • the average particle diameter D 50m of natural graphite is not particularly limited, but is preferably, for example, 5 to 80 ⁇ m.
  • the average particle diameter D 50v of massive artificial graphite and massive non-graphitizable carbon is, for example, 5 to 40 ⁇ m. It is preferable that
  • the penetration of the electrolyte into the negative electrode active material layer and the liquid replenishment property are improved.
  • a material capable of inserting and extracting lithium a silicon-based oxide or the like can be used in combination with a carbonaceous material.
  • the graphite material has high electron conductivity, excellent adhesion with a current collector made of a metal such as copper and voltage flatness, and is formed at a high processing temperature. Therefore, the content of impurities is small, which is advantageous and favorable for improving the negative electrode performance.
  • As a negative electrode active material it is more preferable to contain 20 mass% or more of graphite, and it is further more preferable to contain 60 mass% or more of graphite.
  • the negative electrode current collector aluminum, nickel, copper, silver, and alloys thereof are preferable in view of electrochemical stability.
  • Examples of the shape include foil, flat plate, and mesh.
  • the negative electrode active material is dispersed in a suitable solvent together with a binder to obtain a paste or slurry-like composition for forming a negative electrode active material layer (negative electrode mixture), and then the negative electrode It can be formed by applying a mixture to the surface of the negative electrode current collector.
  • a thin film of aluminum, nickel, or an alloy thereof may be formed by a method such as vapor deposition or sputtering to form a negative electrode current collector.
  • the binder is not particularly limited as long as it is a material that is stable with respect to a non-aqueous electrolyte solution or a solvent used during electrode production.
  • resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, cellulose, and nitrocellulose
  • SBR styrene-butadiene rubber
  • isoprene rubber butadiene rubber, fluorine rubber
  • NBR Acrylonitrile / butadiene rubber
  • rubbery polymers such as ethylene / propylene rubber; styrene / butadiene / styrene block copolymers or hydrogenated products thereof;
  • EPDM ethylene / propylene / diene terpolymer
  • styrene / ethylene / Thermoplastic elastomeric polymer such as butadiene / styrene copolymer, styren
  • the electrolytic solution is less likely to permeate into the styrene-based polymer, it is possible to prevent the negative electrode active material and the electrolytic solution from contacting with each other through the binder, thereby preventing a side reaction between the negative electrode active material and the electrolytic solution.
  • coat is formed in the negative electrode active material surface, and decomposition
  • styrene monomer according to the present invention examples include styrene, ⁇ -methylstyrene, dimethylstyrene, vinyltoluene and the like. Among these, styrene is preferable.
  • Vinyl monomers such as acrylonitrile, methacrylonitrile, fumaronitrile, A methacrylic acid monomer comprising methacrylic acid, Methacrylate monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, Butadiene monomers such as butadiene, isoprene and chloroprene, Acrylic acid monomer consisting of acrylic acid, Acrylic ester monomers such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, Unsaturated dicarboxylic acid anhydride type monomers
  • the styrene polymer at least a copolymer containing a styrene monomer and a butadiene monomer, or a copolymer containing a styrene monomer and an acrylic acid monomer is preferable. Moreover, it is good also as a copolymer which further contains monomers other than these monomers.
  • Copolymers containing styrene monomer and butadiene monomer include styrene / butadiene copolymer (SBR), styrene / ethylene / butadiene copolymer, methyl methacrylate / styrene / butadiene copolymer, methyl methacrylate / A styrene / butadiene copolymer and other monomers added to the styrene / butadiene copolymer, such as styrene / butadiene copolymer and acrylonitrile / styrene / butadiene copolymer, may be used.
  • SBR styrene / butadiene copolymer
  • styrene / ethylene / butadiene copolymer methyl methacrylate / styrene / butadiene copolymer
  • copolymer containing a styrene monomer and an acrylic acid monomer a styrene / acrylic copolymer or an acrylic / styrene / acrylonitrile copolymer may be used.
  • the styrenic polymer as a binder, it is possible to more reliably suppress binder elution into the electrolytic solution in a high temperature environment, and thus it is possible to more reliably maintain electrode adhesion.
  • the range of the content of the styrene monomer in the styrenic polymer is preferably 5 to 80% by mass, more preferably 15 to 70% by mass, and further preferably 25 to 60% by mass. good. By setting it as these ranges, the resistance of the film
  • the amount of the binder to be used is 0.3 to 16% by mass in the negative electrode active material layer, preferably 0.3 to 8.% from the viewpoint of sufficient binding force and high energy which are in a trade-off relationship. It is good to contain in the range of 0 mass%. When a styrenic polymer is used, it is more preferably contained in the range of 0.5 to 6.0% by mass, further preferably 0.8 to 5.0% by mass, particularly 1.0 to 3.5% by mass. Is good.
  • any type can be used as long as it is a solvent capable of dissolving or dispersing a negative electrode active material, a binder, a thickener used as necessary, and a conductive material.
  • a solvent capable of dissolving or dispersing a negative electrode active material, a binder, a thickener used as necessary, and a conductive material there is no particular limitation, and either an aqueous solvent or an organic solvent may be used.
  • aqueous solvents include water and mixed solvents such as alcohols compatible with water.
  • organic solvents include amide solvents such as N-methylpyrrolidone (NMP), dimethylformamide and dimethylacetamide, acetone. , Ketone solvents such as methyl ethyl ketone and cyclohexanone, esters such as methyl acetate and methyl acrylate, organic amines such as diethyltriamine and N, N-dimethylaminopropylamine, tetrahydrofuran (THF), toluene, diethyl ether, hexamethyl Examples include phosphalamide, dimethyl sulfoxide (DMSO), benzene, xylene, quinoline, pyridine, methylnaphthalene, hexane, and the like.
  • amide solvents such as N-methylpyrrolidone (NMP), dimethylformamide and dimethylacetamide, acetone.
  • a fluorine-based polymer such as PVdF when used as the binder, a combination with an organic solvent such as NMP is preferable, and in the case of a styrene polymer such as SBR, a combination with an aqueous solvent is preferable.
  • the preparation of the mixture is preferably performed in a low humidity environment with a dew point temperature of 10 ° C. (25 ° C., relative humidity 40%) or less.
  • aqueous thickener In order to disperse the negative electrode active material and the binder in the aqueous solvent with good dispersibility, and to adjust the viscosity of the slurry, it is preferable to add an aqueous thickener or a dispersing agent.
  • aqueous thickeners include cellulose polymers such as carboxymethylcellulose (CMC), methylcellulose (MC), cellulose acetate phthalate (CAP), hydroxypropylmethylcellulose (HPMC), and hydroxypropylmethylcellulose phthalate (HPMCP); polyvinyl Alcohol (PVA) etc. are illustrated.
  • CMC carboxymethylcellulose
  • MC methylcellulose
  • CAP cellulose acetate phthalate
  • HPMC hydroxypropylmethylcellulose
  • HPMC hydroxypropylmethylcellulose phthalate
  • PVA polyvinyl Alcohol
  • Such a negative electrode mixture is applied and dried to form a negative electrode active material layer.
  • the surface of the obtained negative electrode is cracked, and the battery characteristics such as Coulomb efficiency are remarkably lowered. There are harmful effects. Therefore, drying to less than 50 ppm should be avoided.
  • the water content in the negative electrode active material layer is controlled in the range of 50 to 1000 ppm.
  • the moisture content in a negative electrode active material layer can be confirmed by measuring with a general Karl Fischer method. “Ppm” is based on mass.
  • the amount of moisture depends on the drying conditions such as drying temperature, drying time, and drying atmosphere conditions (humidity (dew point temperature) and pressure) depending on the amount of moisture in the paste or slurry negative electrode mixture and the components in the negative electrode mixture. By adjusting, it is adjusted to be within the above range. Further, before drying or after drying, the negative electrode having a desired film thickness can be formed by pressing in the thickness direction as desired.
  • the negative electrode after drying is preferably stored in an environment where the dew point temperature is controlled.
  • the dew point temperature is controlled to 0 ° C. or lower, preferably ⁇ 5 ° C. or lower.
  • the dew point temperature since the upper limit value of the moisture content is relatively high, it is not necessary to set the dew point temperature to an excessively low value, for example, ⁇ 30 ° C. Typically, it is kept in an environment with a dew point temperature of ⁇ 10 ° C.
  • the negative electrode mixture may contain other components such as a conductive agent, a reinforcing material, a leveling agent, and an electrolytic solution additive having functions such as suppression of electrolytic solution decomposition.
  • the positive electrode active material examples include lithium-containing composite oxides such as LiCoO 2 , LiNiO 2 , Li (Ni, Mn, Co) O 2 , and LiMn 2 O 4 .
  • the transition metal portion of these lithium-containing composite oxides may be replaced with another element.
  • a lithium-containing composite oxide having a plateau at 4.2 V or higher at the metal lithium counter electrode potential can be used.
  • the lithium-containing composite oxide examples include spinel-type lithium manganese composite oxide, olivine-type lithium-containing composite oxide, and reverse spinel-type lithium-containing composite oxide.
  • the lithium-containing composite oxide examples include a compound represented by the following formula (4).
  • Li a (M x Mn 2-x ) O 4 (4) (In Formula (4), 0 ⁇ x ⁇ 2 and 0 ⁇ a ⁇ 1.2.
  • M is at least selected from the group consisting of Ni, Co, Fe, Cr, and Cu) It is a kind.
  • the same negative electrode binder can be used.
  • polyvinylidene fluoride is preferable from the viewpoint of versatility and low cost.
  • the amount of the positive electrode binder used is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material from the viewpoints of binding force and energy density which are in a trade-off relationship.
  • binders other than polyvinylidene fluoride (PVdF) vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, polytetrafluoroethylene, polypropylene,
  • PVdF polyvinylidene fluoride
  • Examples include polyethylene, polyimide, and polyamideimide.
  • the positive electrode current collector aluminum, nickel, silver, and alloys thereof are preferable.
  • the shape include foil, flat plate, and mesh.
  • an active material is dispersed and kneaded in a solvent such as N-methyl-2-pyrrolidone (NMP) together with a conductive material such as carbon black and a binder such as polyvinylidene fluoride (PVdF). It can obtain by apply
  • NMP N-methyl-2-pyrrolidone
  • PVdF polyvinylidene fluoride
  • FIG. 1 is an example of a schematic configuration diagram of a secondary battery using the nonaqueous electrolytic solution of the present invention.
  • the battery according to the present invention has a structure as shown in FIG.
  • the positive electrode is formed by forming a layer 1 containing a positive electrode active material on a positive electrode current collector 3.
  • the negative electrode is formed by forming a layer 2 containing a negative electrode active material on a negative electrode current collector 4.
  • the positive electrode and the negative electrode each show a case where the active material layers are formed on both surfaces of the current collector, but the present invention is not limited thereto, and the positive electrode and the negative electrode may be formed only on one side.
  • These positive electrode and negative electrode are arranged to face each other with a porous separator 5 interposed therebetween.
  • the porous separator 5 is disposed substantially parallel to the layer 2 containing the negative electrode active material.
  • the electrode element in which the positive electrode and the negative electrode are arranged to face each other, and the electrolytic solution 6 are included in the outer package 9.
  • a positive electrode tab 7 is connected to the positive electrode current collector 3
  • a negative electrode tab 8 is connected to the negative electrode current collector 4, and these tabs are drawn out of the exterior body 9.
  • a method for manufacturing the secondary battery in FIG. 1 a method for manufacturing the secondary battery in FIG. 1 will be described.
  • an exterior body 9 such as a flexible film made of a laminate of a synthetic resin and a metal foil. Impregnated with water electrolyte 6. And a favorable membrane
  • coat can be formed on a negative electrode by charging a non-aqueous-electrolyte secondary battery before sealing the exterior body 9 after sealing.
  • porous separator 5 porous films, such as polyolefin, such as a polypropylene and polyethylene, a fluororesin, are used.
  • the exterior body 9 can be appropriately selected as long as it is stable to the electrolytic solution 6 and has a sufficient water vapor barrier property.
  • a laminated laminate type secondary battery a laminate film made of aluminum, silica-coated polypropylene, polyethylene, or the like can be used as the outer package.
  • an aluminum laminate film from the viewpoint of suppressing volume expansion.
  • the shape of the non-aqueous electrolyte secondary battery according to the present embodiment is not limited to the illustrated laminate exterior type, but is a cylindrical type in which a positive electrode and a negative electrode are wound oppositely and wound in a metal can, Examples include a square battery and a coin battery.
  • Example 1 (Production of battery) The production of the battery of this example will be described.
  • An aluminum foil having a thickness of 20 ⁇ m is used as the positive electrode current collector, and Li (Mn 0.95 Li 0.01 Mg 0.01 Al 0.01 Co 0.01 B 0.01 ) 2 O 4 and LiNi 0 are used as the positive electrode active material. .5 with a mixture of a weight ratio of 30:70 between the Mn 0.3 Co 0.2 O 2.
  • PVdF Karl Co., Ltd. KF polymer
  • acetylene black manufactured by Timcal Graphite and Carbon
  • a copper foil having a thickness of 10 ⁇ m was used as the negative electrode current collector
  • graphite was used as the negative electrode active material on this copper foil
  • PVdF KF polymer manufactured by Kureha Corporation
  • acetylene was used as the conductivity-imparting material.
  • Black manufactured by Timcal Graphite and Carbon was used.
  • the negative electrode was formed by dispersing 45 parts by mass of graphite (average particle size: 10 ⁇ m), 2.5 parts by mass of PVdF, and 2.5 parts by mass of acetylene black in 50 parts by mass of NMP (water content: 800 ppm). A paste was prepared and applied to a thickness of 70 ⁇ m on the negative electrode current collector using an applicator. Thereafter, the negative electrode was dried under reduced pressure at 200 ° C. in an environment with a dew point minus 10 ° C. The negative electrode water content at this time was confirmed to be 68 ppm by measurement by the Karl Fischer method (300 ° C.). And the negative electrode and the positive electrode were laminated
  • a lead terminal is attached and sealed to each of the positive electrode and negative electrode current collectors of the electrode element, and the nonaqueous electrolyte solution is injected and vacuum-sealed, and the nonaqueous electrolyte secondary battery is sealed. Produced. Using this non-aqueous secondary battery, a charge / discharge test of the battery was performed, and the coulomb efficiency was measured. The results are shown in Table 3.
  • the charging / discharging conditions at this time were CCCV charge rate 1.0C, CC discharge rate 1.0C, charge end voltage 4.2V, and discharge end voltage 3.0V. Note that 1.0 C is a current value that can be discharged in one hour from a fully charged state.
  • Example 2 A copper foil having a thickness of 10 ⁇ m was used as the negative electrode current collector.
  • CMC carboxymethylcellulose
  • styrene-based heavy polymer styrene-based heavy polymer
  • the negative electrode which contains 2 mass% of CMC and 2 mass% of styrene-type polymers with respect to the whole negative electrode active material layer was produced by compression molding with a roll press.
  • a secondary battery was produced in the same manner as in Example 1 except for the negative electrode used, and the Coulomb efficiency was examined in the same manner as in Example 1.
  • Example 3 A secondary battery was produced in the same manner as in Example 2 except that the vacuum drying treatment temperature of the negative electrode was changed to 180 ° C., and the Coulomb efficiency was examined in the same manner as in Example 1. The results are shown in Table 3.
  • Example 4 A secondary battery was produced in the same manner as in Example 2 except that the vacuum drying treatment temperature of the negative electrode was changed to 130 ° C., and the Coulomb efficiency was examined in the same manner as in Example 1. The results are shown in Table 3.
  • Example 5 The vacuum drying treatment temperature of the negative electrode was set to 80 ° C., and after the vacuum drying treatment, the negative electrode was left in an environment having a dew point of ⁇ 10 ° C. for 1 week (168 h). Thereafter, a secondary battery was produced in the same manner as in Example 2, and the Coulomb efficiency was examined in the same manner as in Example 1. The results are shown in Table 3.
  • Example 5 A secondary battery was produced in the same manner as in Example 2 except that the vacuum drying treatment temperature of the negative electrode was 250 ° C., and the Coulomb efficiency was examined in the same manner as in Example 1. The results are shown in Table 3.
  • Example 7 A secondary battery was produced in the same manner as in Example 2 except that the vacuum drying treatment temperature of the negative electrode was set to 180 ° C. and then left for 24 hours in a general atmosphere where dew point control was not performed. The efficiency was examined. The results are shown in Table 3.
  • Examples 6 to 13 As an additive, Compound No. A secondary battery was produced in the same manner as in Example 3 except that the compounds listed in Table 3 were used instead of 4, and the Coulomb efficiency was examined in the same manner as in Example 1. The results are shown in Table 3.
  • the batteries shown in Examples 1 to 13 have a negative electrode moisture content in the range of 50 to 1000 ppm, and the comparison with the specific electrolyte solution additive is outside the scope of the present invention. Compared to Examples 1 to 8, it was confirmed that the coulomb efficiency was improved.
  • Examples of use of the present invention include driving devices such as electric vehicles, hybrid vehicles, electric motorcycles, and electric assist bicycles, tools such as electric tools, electronic devices such as portable terminals and laptop computers, household power storage systems, and solar power generation. Examples include storage batteries such as systems.

Abstract

L'invention concerne une batterie rechargeable à électrolyte non aqueux, qui présente d'excellentes caractéristiques de capacité, en particulier de capacité initiale. La teneur en humidité de l'électrode négative de cette batterie est réglée entre 50 et 1000 ppm inclus, et un dérivé de sulfonate cyclique, représenté par la formule générale (1), est utilisé en tant qu'additif formant un film de protection, lequel est ajouté à l'électrolyte non aqueux. Dans la formule générale (1), R1 et R2 représentent chacun indépendamment un hydrogène, un halogène, un groupe alkyle en C1-5 ou un groupe amino, R1 et/ou R2 représentant autre chose qu'un hydrogène, et R3 représentant un groupe de liaison sélectionné dans le groupe constitué par des groupes alkylène en C1-5, un carbonyle, un sulfinyle, des groupes fluoroalkylène en C1-6 et des groupes en C2-6 divalents comportant un motif alkylène ou un motif fluoroalkylène lié à ceux-ci par l'intermédiaire d'une liaison éther.
PCT/JP2014/070698 2013-09-13 2014-08-06 Batterie rechargeable à électrolyte non aqueux WO2015037367A1 (fr)

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JP2017147188A (ja) * 2016-02-19 2017-08-24 エリーパワー株式会社 電池電極スラリーの作製方法
WO2018146866A1 (fr) * 2017-02-08 2018-08-16 株式会社村田製作所 Solution électrolytique pour batteries secondaires, batterie secondaire, bloc-batterie, véhicule électrique, système d'accumulation d'énergie électrique, outil électrique et dispositif électronique
CN109728340A (zh) * 2017-10-30 2019-05-07 宁德时代新能源科技股份有限公司 锂离子电池
JP2020087569A (ja) * 2018-11-19 2020-06-04 トヨタ自動車株式会社 非水電解質二次電池の製造方法
CN112701353A (zh) * 2021-01-04 2021-04-23 昆山宝创新能源科技有限公司 电解液及其应用
EP3940819A1 (fr) * 2020-07-15 2022-01-19 SK Innovation Co., Ltd. Électrode pour batterie secondaire

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