WO2014080870A1 - Batterie rechargeable lithium-ion - Google Patents

Batterie rechargeable lithium-ion Download PDF

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Publication number
WO2014080870A1
WO2014080870A1 PCT/JP2013/081085 JP2013081085W WO2014080870A1 WO 2014080870 A1 WO2014080870 A1 WO 2014080870A1 JP 2013081085 W JP2013081085 W JP 2013081085W WO 2014080870 A1 WO2014080870 A1 WO 2014080870A1
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formula
positive electrode
secondary battery
fluorinated
active material
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PCT/JP2013/081085
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Japanese (ja)
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佐々木　英明
野口　健宏
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日本電気株式会社
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Priority to JP2014548556A priority Critical patent/JP6332033B2/ja
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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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium ion secondary battery.
  • lithium ion secondary batteries Since lithium ion secondary batteries have a small volume, a large mass capacity density, and a high voltage can be taken out, they are widely used as power sources for small devices. For example, it is used as a power source for mobile devices such as mobile phones and notebook computers. Also, in recent years, in addition to small mobile device applications, large secondary devices that require a long life with a large capacity, such as electric vehicles (EV) and power storage fields, are being considered due to consideration for environmental issues and increased awareness of energy conservation. Application to batteries is expected.
  • EV electric vehicles
  • a positive electrode active material based on LiMO 2 having a layered structure (M is at least one of Co, Ni, and Mn) or LiMn 2 O 4 having a spinel structure is used.
  • a lithium ion secondary battery having a positive electrode containing such a positive electrode active material mainly uses a charge / discharge region of 4.2 V or less (hereinafter referred to as a positive electrode having an operating potential of 4.2 V or less with respect to lithium metal). May be described as “4V class positive electrode”).
  • a carbon material such as graphite is used as the negative electrode active material.
  • a material obtained by substituting a part of Mn of LiMn 2 O 4 with Ni or the like shows a high charge / discharge region of 4.5 to 4.8 V with respect to lithium metal.
  • spinel compounds such as LiNi 0.5 Mn 1.5 O 4 are not redox of conventional Mn 3+ and Mn 4+ , but Mn exists in the state of Mn 4+ and redox of Ni 2+ and Ni 4+ Therefore, a high operating voltage of 4.5 V or higher is shown.
  • Such a material is called a 5V class active material and is expected to be a promising positive electrode material because it can improve the energy density by increasing the voltage.
  • a technique of adding an additive to an electrolytic solution is widely performed in order to improve battery performance or suppress deterioration.
  • the oxidative decomposition of the electrolyte on the positive electrode is not the main cause of the deterioration, so the additive used in the 4V class battery is not always effective for the 5V class battery. The effect may be different.
  • Patent Documents 1 to 4 disclose bis (fluorosulfonyl) imide lithium salt represented by Li + [(FSO 2 ) 2 N] ⁇ .
  • Patent Document 1 describes that LiFSI can be applied as an electrolyte of a non-aqueous solvent, and Patent Document 2 can improve output characteristics after high-temperature storage by using in combination with a specific compound. Is described.
  • Patent Document 3 describes a nonaqueous electrolytic solution containing a sulfonylimide lithium containing a fluorine atom, a fluorinated diether, and a fluorinated monoether.
  • Patent Document 4 describes a nonaqueous electrolytic solution for a secondary battery containing a fluorinated cyclic carbonate and lithium bisfluorosulfonylimide.
  • Patent Documents 1 to 4 can sufficiently solve problems such as high temperature cycle characteristics and gas generation in a battery using a 5 V class active material that exhibits a voltage as high as 4.5 V or more with respect to lithium metal. It wasn't.
  • the electrolytic solution described in Patent Document 4 has a large practical problem because a large amount of gas is generated during a high-temperature cycle although not specifically mentioned.
  • JP 2012-94454 A Japanese Patent No. 3878206 JP 2011-187163 A JP 2010-129449 A
  • the present invention solves the above-mentioned problems in a lithium ion secondary battery using a 5V class active material, and provides a lithium ion secondary battery with a high capacity retention rate of charge / discharge cycles at high temperatures and reduced gas generation. With the goal.
  • the present invention is a lithium ion secondary battery comprising a positive electrode and a non-aqueous electrolyte
  • the positive electrode includes a positive electrode active material having an operating potential of 4.5 V or more with respect to lithium metal
  • the non-aqueous electrolyte is (A) N (SO 2 F) 2 anion (FSI anion); (B) a cyclic carbonate; (C) A fluorinated ether represented by the following formula (1), a fluorinated phosphate ester represented by the following formula (2), and a sulfone compound represented by the following formula (3) or the following formula (4) At least one selected from the group consisting of:
  • the present invention relates to a lithium ion secondary battery.
  • R 101 and R 102 each independently represents an alkyl group or a fluorinated alkyl group, and at least one of R 101 and R 102 is a fluorinated alkyl group
  • R 1 , R 2 and R 3 each independently represents an alkyl group or a fluorinated alkyl group, and at least one of them is a fluorinated alkyl group
  • R 1 and R 2 each independently represent a substituted or unsubstituted alkyl group
  • R 3 represents a substituted or unsubstituted alkylene group.
  • the cycle characteristics of a lithium ion secondary battery containing a 5 V class active material can be improved and gas generation can be suppressed.
  • a positive electrode active material having an operating potential of 4.5 V or higher with respect to lithium metal may be referred to as a “5 V class active material”.
  • the lithium ion secondary battery of this embodiment is A positive electrode and a non-aqueous electrolyte
  • the positive electrode includes a positive electrode active material (hereinafter sometimes referred to as “5 V class active material”) having an operating potential of 4.5 V or more with respect to lithium metal
  • the non-aqueous electrolyte is (A) N (SO 2 F) 2 anion (FSI anion); (B) a cyclic carbonate; (C) A fluorinated ether represented by the following formula (1), a fluorinated phosphate ester represented by the following formula (2), and a sulfone compound represented by the following formula (3) or the following formula (4) At least one selected from the group consisting of: including.
  • R 101 and R 102 each independently represents an alkyl group or a fluorinated alkyl group, and at least one of R 101 and R 102 is a fluorinated alkyl group
  • R 1 , R 2 and R 3 each independently represents an alkyl group or a fluorinated alkyl group, and at least one of them is a fluorinated alkyl group
  • R 1 and R 2 each independently represent a substituted or unsubstituted alkyl group
  • R 3 represents a substituted or unsubstituted alkylene group.
  • a positive electrode including a positive electrode active material having an operating potential of 4.5 V or higher with respect to lithium metal may be referred to as a “5 V class positive electrode”.
  • the non-aqueous electrolyte provided in the lithium ion secondary battery of this embodiment is (A) an N (SO 2 F) 2 anion (hereinafter sometimes referred to as “FSI anion”) and a nonaqueous electrolytic solvent;
  • the non-aqueous electrolytic solvent is (B) a cyclic carbonate, and (C) at least selected from a fluorinated ether represented by formula (1), a fluorinated phosphate ester represented by formula (2), and a sulfone compound represented by formula (3) or formula (4) 1 type.
  • the nonaqueous electrolytic solution contains an FSI anion.
  • the FSI anion is considered to form a film on the negative electrode and the positive electrode.
  • Such a film is also referred to as a SEI film (Solid Electrolyte Interface), and has an ionic conductivity but no electronic conductivity, and thus plays a role of preventing a reaction between the active material and the electrolytic solution.
  • SEI film Solid Electrolyte Interface
  • the film formed on the positive electrode suppresses the decomposition reaction between the 5V class active material and the electrolytic solution.
  • the film formed on the negative electrode suppresses the decomposition reaction between the negative electrode and the electrolytic solution, and by-products of the electrolytic solution generated at the positive electrode or transition metal ions such as Mn and Ni eluted from the positive electrode react with the negative electrode. To prevent precipitation. As a result, the capacity maintenance rate of the charge / discharge cycle is improved, and gas generation can be sufficiently suppressed.
  • the positive electrode has a positive electrode active material having an operating potential of 4.5 V or more with respect to lithium metal, but the effect of the FSI anion is 5 V class than the conventional secondary battery using a 4 V class positive electrode.
  • a secondary battery having an active material is more highly effective. This is considered to be because an oxidative decomposition film by FSI anion is easily formed on the positive electrode because the positive electrode has a high potential.
  • the FSI anion is generated when a compound containing the FSI anion is dissolved in the non-aqueous electrolyte.
  • a salt of an FSI anion and an alkali metal is preferable, and examples thereof include LiFSI, NaFSI, and KFSI.
  • LiFSI is particularly preferable because it can serve as an electrolyte of a lithium ion battery and can improve ion conductivity of the electrolytic solution.
  • LiFSI is described as an example, but the coating of FSI anion is also formed other than the lithium salt, and is not limited to LiFSI.
  • the amount of LiFSI added to the total mass of the electrolytic solution is preferably 0.1 to 5% by mass, and more preferably 0.2 to 3% by mass.
  • the electrolytic solution contains a cyclic carbonate as a nonaqueous electrolytic solvent.
  • the cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC).
  • EC ethylene carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • VC vinylene carbonate
  • some or all of hydrogen in these compounds may be substituted with fluorine.
  • the fluorinated cyclic carbonate include 4-fluoro-1,3-dioxolan-2-one ⁇ monofluoroethylene carbonate (FEC) ⁇ , (cis or trans) 4,5-difluoro-1,3-dioxolane-2.
  • a cyclic carbonate can be used individually by 1 type or in mixture of 2 or more types.
  • EC and PC are preferable because they have a high dielectric constant and excellent electrolyte solubility, and EC is more preferable.
  • LiFSI has poor solubility in organic solvents as compared with other lithium salts such as LiPF 6 , but the solubility of LiFSI can be further increased by including a cyclic carbonate in the electrolytic solution.
  • the content of cyclic carbonate in the total nonaqueous electrolytic solvent is preferably 1 to 50% by volume, more preferably 5 to 40% by volume, and further preferably 10 to 40% by volume. If the content of the cyclic carbonate is too small, the conductivity of the electrolytic solution is lowered, and the cycle characteristics may be deteriorated. If the content of the cyclic carbonate is too large, the cyclic carbonate is likely to be decomposed at a high potential. Therefore, in a lithium ion secondary battery containing a 5V-grade positive electrode active material, gas generation may increase.
  • the nonaqueous electrolytic solvent is a fluorinated ether represented by the formula (1) (hereinafter sometimes simply referred to as “fluorinated ether”), the formula (2), in addition to the cyclic carbonate.
  • a sulfone compound represented by formula (3) or formula (4) (hereinafter simply referred to as “fluorinated phosphate ester”). It may be described as “sulfone compound”.), And at least one selected from the group consisting of 2 or more is more preferable.
  • the nonaqueous electrolytic solvent can contain a fluorinated ether represented by the following formula (1).
  • R 101 and R 102 each independently represents an alkyl group or a fluorinated alkyl group, and at least one of R 101 and R 102 is a fluorinated alkyl group).
  • the total number of carbon atoms of R 101 and R 102 is preferably 10 or less.
  • the fluorinated alkyl group is an alkyl group having at least one fluorine atom.
  • the fluorine atom content in the fluorinated alkyl group is preferably 50% or more, more preferably 60% or more, based on the total of fluorine atoms and hydrogen atoms.
  • the withstand voltage is further improved, and even when a positive electrode active material that operates at a potential of 4.5 V or higher with respect to lithium is used, deterioration of battery capacity after cycling is more effectively reduced. Is possible.
  • fluorinated ethers represented by the following formula (1-1) are more preferable.
  • n and m are each independently 1 to 8.
  • X 1 to X 6 are each independently a fluorine atom or a hydrogen atom, provided that X 1 to X 6 At least one is a fluorine atom, and when n is 2 or more, a plurality of X 2 and X 3 are independent from each other, and when m is 2 or more, a plurality of X 4 and X 5 are Are independent of each other.
  • the fluorinated ether is more preferably a compound represented by the following formula (1-2) from the viewpoint of voltage resistance and compatibility with other electrolytes.
  • X 1- (CX 2 X 3 ) n -CH 2 O-CX 4 X 5 -CX 6 X 7 -X 8 (1-2) (In the formula (1-2), n is 1 to 7, and X 1 to X 8 are each independently a fluorine atom or a hydrogen atom, provided that at least one of X 1 to X 3 is a fluorine atom. And at least one of X 4 to X 8 is a fluorine atom).
  • n 2 or more
  • a plurality of X 2 may be the same or different from each other
  • a plurality of X 3 are the same or different from each other. Also good.
  • the fluorinated ether compound is more preferably represented by the following formula (1-3).
  • n is 1, 2, 3 or 4.
  • Y 1 to Y 8 are each independently a fluorine atom or a hydrogen atom. However, at least one of Y 1 to Y 4 is a fluorine atom, and at least one of Y 5 to Y 8 is a fluorine atom.
  • n 2 or more, a plurality of Y 1 to Y 4 may be the same or different from each other.
  • fluorinated ether examples include CF 3 OCH 3 , CF 3 OC 2 H 5 , F (CF 2 ) 2 OCH 3 , F (CF 2 ) 2 OC 2 H 5 , and CF 3 (CF 2 ).
  • the content of the fluorinated ether compound represented by the formula (1) is preferably 0% by volume to 90% by volume and more preferably 15% by volume to 80% by volume in the nonaqueous electrolytic solvent. 30 volume% or more and 70 volume% or less is more preferable, 30 volume% or more and 60 volume% or less is more preferable, and 30 volume% or more and 50 volume% or less is further more preferable.
  • the content of the fluorinated ether is too large, the dielectric constant of the electrolytic solution is lowered, the supporting salt cannot be dissociated, and the capacity is similarly reduced.
  • the fluorinated ether has high oxidation resistance
  • the oxidative decomposition of the solvent can be suppressed in a lithium ion secondary battery containing a 5V class active material.
  • LiFSI forms a film on the negative electrode and the positive electrode.
  • a high-quality film is hardly formed or the effect of the film is hindered.
  • the effect of the film by LiFSI can be enhanced.
  • the nonaqueous electrolytic solvent can contain a fluorinated phosphate ester represented by the following formula (2).
  • R 1 , R 2 and R 3 each independently represents an alkyl group or a fluorinated alkyl group, and at least one of them is a fluorinated alkyl group).
  • the fluorinated alkyl group is an alkyl group having at least one fluorine atom.
  • R 1 , R 2 and R 3 each independently have 1 to 3 carbon atoms.
  • At least one of R 1 , R 2 and R 3 is preferably a fluorinated alkyl group in which 50% or more of the hydrogen atoms of the corresponding unsubstituted alkyl group are substituted with fluorine atoms.
  • all of R 1 , R 2 and R 3 are fluorinated alkyl groups, and 50% or more of the hydrogen atoms of the unsubstituted alkyl group to which R 1 , R 2 and R 3 correspond are substituted with fluorine atoms.
  • a fluorinated alkyl group More preferred is a fluorinated alkyl group.
  • the content of fluorine atoms is large, the voltage resistance is further improved, and even when a positive electrode active material that operates at a potential of 4.5 V or higher with respect to lithium is used, the deterioration of battery capacity after cycling is further reduced. Because it can.
  • the ratio of fluorine atoms in the substituent containing a hydrogen atom in the fluorinated alkyl group is more preferably 55% or more.
  • fluorinated phosphate ester examples include, but are not limited to, for example, tris (trifluoromethyl) phosphate, tris (pentafluoroethyl) phosphate, tris phosphate.
  • (2,2,2-trifluoroethyl) Tris (2,2,2-trifluoroethyl) phosphate (TTFP)] tris (2,2,3,3-tetrafluoropropyl) phosphate (Tris (2,2 , 3,3-tetrafluoropropyl) phosphate), tris (3,3,3-trifluoropropyl) phosphate (Tris (3,3,3-trifluorofluoro) phosphate), Phosphate tris (2,2,3,3,3-pentafluoro-propyl) (Tris (2,2,3,3,3-pentafluoropropyl) phosphate) fluorinated alkyl phosphoric acid ester compounds and the like.
  • the content of the fluorinated phosphate ester contained in the nonaqueous electrolytic solvent is not particularly limited, but is preferably 0% by volume to 95% by volume in the nonaqueous electrolytic solvent, and is preferably 10% by volume to 95% by volume. Is more preferable, 20 vol% or more and 70 vol% or less is more preferable, 20 vol% or more and 50 vol% or less is more preferable, and 20 vol% or more and 40 vol% or less is more preferable.
  • the content of the fluorinated phosphate ester in the nonaqueous electrolytic solvent is 10% by volume or more, the effect of increasing the voltage resistance is further improved.
  • the ion conductivity of electrolyte solution improves that the content rate in the nonaqueous electrolytic solvent of fluorinated phosphate ester is 95 volume% or less, and the charge / discharge rate of a battery becomes more favorable.
  • the fluorinated phosphate ester also has high oxidation resistance, oxidative decomposition of the solvent when a 5V class active material is used can be suppressed. As a result, it is possible to improve the capacity maintenance rate of the charge / discharge cycle and reduce gas generation.
  • LiFSI forms a film on the negative electrode and the positive electrode. However, if a large amount of decomposable product of the solvent is present on the electrode, it is difficult to form a good film or the effect of the film is hindered. That is, the effect of the film by LiFSI can be strengthened by coexisting fluorinated phosphate ester having high oxidation resistance and LiFSI.
  • the nonaqueous electrolytic solvent can contain a sulfone compound represented by the following formula (3).
  • R 1 and R 2 each independently represents a substituted or unsubstituted alkyl group.
  • R 2 of R 1 is 1 ⁇ n 1 ⁇ 12,1 ⁇ n 2 ⁇ 12 , respectively, 1 ⁇ n 1 ⁇ 6, 1 ⁇ n 2 ⁇ 6 are more preferable, and 1 ⁇ n 1 ⁇ 3 and 1 ⁇ n 2 ⁇ 3 are still more preferable.
  • the alkyl group includes linear, branched, or cyclic groups.
  • R 1 and R 2 may have a substituent.
  • substituents include an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group). Group), aryl groups having 6 to 10 carbon atoms (for example, phenyl group, naphthyl group), halogen atoms (for example, chlorine atom, bromine atom, fluorine atom) and the like.
  • Examples of the sulfone compound represented by the formula (3) include ethyl methyl sulfone, ethyl isopropyl sulfone, ethyl isobutyl sulfone, dimethyl sulfone, and diethyl sulfone. Of these, dimethyl sulfone, ethyl methyl sulfone, ethyl isopropyl sulfone, and ethyl isobutyl sulfone are preferable.
  • the nonaqueous electrolytic solvent can contain a sulfone compound represented by the following formula (4).
  • R 3 represents a substituted or unsubstituted alkylene group.
  • the alkylene group preferably has 4 to 9 carbon atoms, and more preferably 4 to 6 carbon atoms.
  • examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group), halogen atom (for example, chlorine atom, bromine atom, fluorine atom). Atom) and the like.
  • a cyclic sulfone compound represented by the following formula (4-1) is preferable.
  • m is an integer of 1 to 6).
  • m is an integer of 1 to 6, and preferably an integer of 1 to 3.
  • Preferred examples of the cyclic sulfone compound represented by the formula (4) include tetramethylene sulfone (sulfolane), pentamethylene sulfone, hexamethylene sulfone and the like.
  • Preferred examples of the cyclic sulfone compound having a substituent include 3-methylsulfolane and 2,4-dimethylsulfolane. Since these materials are compatible with the fluorinated ether compound and have a relatively high dielectric constant, they have the advantage of being excellent in the dissolution / dissociation action of the lithium salt.
  • a sulfone compound can be used individually by 1 type or in mixture of 2 or more types.
  • the content of the sulfone compound is preferably 0% by volume or more and 75% by volume or less in the nonaqueous electrolytic solvent, more preferably 5% by volume or more and 50% by volume or less, and more preferably 5% by volume or more and 30% by volume or less. More preferably, it is more preferably 5% by volume or more and 20% by volume or less. If the content of the sulfone compound is too large, the viscosity of the electrolytic solution increases, and the capacity of the cycle characteristics at room temperature may be reduced.
  • the sulfone compound also has high oxidation resistance, it is possible to suppress oxidative decomposition of the solvent particularly when a 5V class active material is used. As a result, it is possible to improve the capacity maintenance rate of the charge / discharge cycle and reduce gas generation.
  • LiFSI forms a film on the negative electrode and the positive electrode. However, if a large amount of decomposition products of the solvent are present on the electrode, a high-quality film is hardly formed or the effect of the film is hindered.
  • membrane by LiFSI can be strengthened by coexisting a sulfo compound with high oxidation resistance and LiFSI. Further, since the sulfone compound is a material having a relatively high dielectric constant, it is preferable from the viewpoint of easily dissolving the lithium salt.
  • the nonaqueous electrolytic solvent includes at least one selected from fluorinated ethers, fluorinated phosphates, and sulfone compounds, and more preferably includes two or more.
  • the higher the concentration of these solvents the better the decomposition of the electrolytic solution is suppressed, but it is preferable to include two or more in order to further improve the compatibility with the cyclic carbonate and the solubility of the lithium salt. There is.
  • the nonaqueous electrolytic solvent may further contain a chain carbonate.
  • the cyclic carbonate has a high viscosity, the viscosity can be reduced by mixing the chain carbonate.
  • the chain carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dipropyl carbonate (DPC), and derivatives thereof (including fluorinated products).
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • DPC dipropyl carbonate
  • the concentration in the electrolytic solution is preferably 10% by volume or less, more preferably 5% by volume or less, and even more preferably 2% or less.
  • the nonaqueous electrolytic solvent may contain an aliphatic carboxylic acid ester, ⁇ -lactone, a cyclic ether, a chain ether other than the above formula (1), and the like.
  • the aliphatic carboxylic acid ester include methyl formate, methyl acetate, ethyl propionate, and derivatives thereof (including fluorinated products).
  • ⁇ -lactone include ⁇ -butyrolactone and its derivatives (including fluorinated products).
  • the cyclic ether include tetrahydrofuran, 2-methyltetrahydrofuran and derivatives thereof (including fluorinated products).
  • chain ether examples include 1,2-ethoxyethane (DEE), ethoxymethoxyethane (EME), diethyl ether, and derivatives thereof (including fluorinated compounds). These can be used individually by 1 type or in mixture of 2 or more types.
  • nonaqueous electrolytic solvents include, for example, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, dioxolane, acetonitrile, propyl nitrile, nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane Derivatives, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, anisole, N-methylpyrrolidone, and derivatives thereof (including fluorinated products) may also be used. it can.
  • the electrolytic solution preferably further contains a cyclic sulfonic acid ester represented by the following formula (5) as an additive.
  • the cyclic sulfonate ester can form a film on the negative electrode.
  • a and B each independently represent an alkylene group or a fluorinated alkylene group.
  • X represents a single bond or —OSO 2 — group).
  • the number of carbon atoms of the alkylene group is, for example, 1 to 8, preferably 1 to 6, and more preferably 1 to 4.
  • the fluorinated alkylene group represents a substituted alkylene group having a structure in which at least one hydrogen atom of the unsubstituted alkylene group is substituted with a fluorine atom.
  • the carbon number of the fluorinated alkylene group is, for example, 1 to 8, preferably 1 to 6, and more preferably 1 to 4.
  • the -OSO 2 -group may be in any direction.
  • the cyclic sulfonate ester is preferably a cyclic monosulfonate ester, and the cyclic monosulfonate ester is preferably a compound represented by the following formula (5-1).
  • R 101 and R 102 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and n is 0, 1, 2, 3, or 4) .
  • the cyclic sulfonate ester is preferably a cyclic disulfonate ester, and the cyclic disulfonate ester is preferably a compound represented by the following formula (5-2).
  • R 201 to R 204 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and n is 1, 2, 3, or 4.
  • n is 2 or more
  • a plurality of R 203 may be the same or different from each other, and a plurality of R 204 may be the same or different from each other. .
  • cyclic sulfonate ester examples include 1,3-propane sultone, 1,2-propane sultone, 1,4-butane sultone, 1,2-butane sultone, 1,3-butane sultone, 2,4-butane sultone, 1,3 -Monosulfonic acid esters such as pentane sultone (when X in formula (5) is a single bond), disulfonic acid esters such as methylenemethane disulfonic acid ester and ethylenemethane disulfonic acid ester (X in formula (5) is- OSO 2 - for group).
  • PS 1,3-propane sultone
  • BS 1,4-butane sultone
  • MMDS methylene methanedisulfonic acid ester
  • the content of the cyclic sulfonic acid ester in the electrolytic solution is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and 0.3 to 3% by mass. Is more preferable. If the content is too low, the effect as a film cannot be obtained sufficiently, and if it is too high, the internal resistance may increase.
  • LiFSI and cyclic sulfonic acid ester are allowed to coexist, a greater effect can be obtained than when they are used alone.
  • the cyclic sulfonic acid ester forms an excellent film on the negative electrode, but hardly forms a film on the positive electrode.
  • LiFSI can form a film on both the negative electrode and the positive electrode, but the effect of the film on the negative electrode is lower than that of the cyclic sulfonate ester. Therefore, it is considered that a good quality film can be formed in a balanced manner on both the negative electrode and the positive electrode by mixing LiFSI and cyclic sulfonic acid ester.
  • the nonaqueous electrolytic solution is obtained by dissolving an electrolyte made of a lithium salt in a nonaqueous electrolytic solvent.
  • the lithium salt is not particularly limited, for example, (except for compounds containing FSI anion) lithium imide salt, LiPF 6, LiAsF 6, LiAlCl 4, LiClO 4, LiBF 4, LiSbF 6 , and the like. Among these, LiPF 6 and LiBF 4 are preferable.
  • the lithium imide salt for example, LiN (C k F 2k + 1 SO 2) (C m F 2m + 1 SO 2) (k and m are each independently 1 or 2).
  • a lithium salt can be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the concentration of the lithium salt in the electrolytic solution is preferably 0.5 to 1.5 mol / L. By setting the concentration of the lithium salt within this range, it is easy to adjust the density, viscosity, electrical conductivity, and the like to an appropriate range.
  • the positive electrode in the present embodiment includes a positive electrode active material (5 V class active material) having an operating potential of 4.5 V or higher with respect to lithium metal. That is, the positive electrode active material used in the present embodiment has a charge / discharge region at 4.5 V or higher with respect to lithium metal.
  • the 5V class active material is preferably a lithium-containing composite oxide.
  • Examples of the 5V class active material of the lithium-containing composite oxide include spinel-type lithium manganese composite oxide, olivine-type lithium manganese-containing composite oxide, reverse spinel-type lithium manganese-containing composite oxide, Li 2 MnO 3 -based solid solution, and the like. Can be mentioned.
  • the positive electrode active material it is preferable to use a lithium manganese composite oxide represented by the following formula (6).
  • M includes only Ni or one or more of Co and Fe containing Ni as a main component.
  • A is more preferably one or more of B, Mg, Al, and Ti.
  • Z is more preferably F. Such a substitution element serves to stabilize the crystal structure and suppress the deterioration of the active material.
  • the average particle diameter (D 50 ) of the positive electrode active material is preferably 1 to 50 ⁇ m, and more preferably 5 to 25 ⁇ m.
  • the average particle diameter (D 50 ) of the positive electrode active material can be measured by a laser diffraction scattering method (microtrack method).
  • the 5V class active material is a positive electrode active material other than the above formula (6) as long as it is a positive electrode active material having a charge / discharge region of 4.5 V (vs. Li / Li + ) or more with respect to lithium metal. It doesn't matter. It is considered that the quality and stability of the film formed on the surface of the positive electrode active material are dominated by the potential and are not directly influenced by the composition of the active material.
  • Li x MPO 4 F y (0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, M is at least one of Co and Ni).
  • Si-containing composite oxide represented by Li x MSiO 4 (0 ⁇ x ⁇ 2, M: at least one of Mn, Fe and Co); Li x [Li a M b Mn 1-ab ] O 2 (0 ⁇ x ⁇ 1, 0.02 ⁇ a ⁇ 0.3, 0.1 ⁇ b ⁇ 0.7, M is at least Ni, Co, Fe and Cr
  • One type of positive electrode active material may be used alone, or two or more types may be used in combination.
  • a 4V class active material may be included.
  • Negative electrode active material Although it does not restrict
  • a negative electrode active material can be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the positive electrode has, for example, a positive electrode active material layer formed on at least one surface of a positive electrode current collector.
  • a positive electrode active material layer is comprised by the positive electrode active material which is a main material, a binder, and a conductive support agent, for example.
  • the negative electrode is configured, for example, by forming a negative electrode active material layer on at least one surface of a negative electrode current collector.
  • a negative electrode active material layer is comprised by the negative electrode active material which is a main material, a binder, and a conductive support agent, for example.
  • binder used in the positive electrode examples include polyvinylidene fluoride (PVDF) and acrylic polymers.
  • binder used in the negative electrode examples include styrene butadiene rubber (SBR) and the like other than the binder that can be used in the positive electrode.
  • SBR styrene butadiene rubber
  • a thickener such as carboxymethyl cellulose (CMC) can be used in combination.
  • carbon materials such as carbon black, granular graphite, flake graphite, and carbon fiber can be used for both the positive electrode and the negative electrode.
  • carbon black having low crystallinity for the positive electrode.
  • positive electrode current collector for example, aluminum, stainless steel, nickel, titanium, or an alloy thereof can be used.
  • negative electrode current collector for example, copper, stainless steel, nickel, titanium, or an alloy thereof can be used.
  • the electrode is prepared by dispersing and kneading an active material, a binder, and a conductive aid in a solvent such as N-methyl-2-pyrrolidone (NMP) in a predetermined blending amount. It can be obtained by applying to an electric body to form an active material layer. The obtained electrode can be compressed to a suitable density by a method such as a roll press.
  • NMP N-methyl-2-pyrrolidone
  • the separator is not particularly limited, and for example, a porous film made of a polyolefin such as polypropylene or polyethylene, a fluororesin, an inorganic separator made of cellulose, glass, or the like can be used.
  • the exterior body for example, coin-shaped, rectangular, cylindrical, etc. cans and laminate exterior bodies can be used. From the viewpoint of reducing the weight and improving the battery energy density, synthetic resin and metal A laminate outer package using a flexible film made of a laminate with a foil is preferred. Since the laminate type battery is excellent in heat dissipation, it is suitable as an in-vehicle battery such as an electric vehicle.
  • an aluminum laminate film, a SUS laminate film, a laminate film made of 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 and cost.
  • the configuration of the secondary battery according to the present embodiment is not particularly limited, and for example, an electrode element in which a positive electrode and a negative electrode are opposed to each other and an electrolytic solution may be included in an exterior body. it can.
  • the shape of the secondary battery is not particularly limited, and examples thereof include a cylindrical shape, a flat wound rectangular shape, a laminated rectangular shape, a coin shape, a flat wound laminated shape, and a laminated laminated shape.
  • FIG. 1 shows a laminated secondary battery as an example of the secondary battery according to this embodiment.
  • the secondary battery shown in FIG. 1 includes a positive electrode composed of a positive electrode active material layer 1 including a positive electrode active material and a positive electrode binder, and a positive electrode current collector 3, and a negative electrode active material layer 2 including a negative electrode active material capable of occluding and releasing lithium. And the negative electrode current collector 4 is sandwiched between the separator 5.
  • the positive electrode current collector 3 is connected to the positive electrode tab 8, and the negative electrode current collector 4 is connected to the negative electrode tab 7.
  • a laminated outer package 6 is used as the outer package, and the inside of the secondary battery is filled with the nonaqueous electrolytic solution according to the present embodiment.
  • a positive electrode tab and a negative electrode tab are connected to the positive electrode for a secondary battery and the negative electrode according to this embodiment via a positive electrode current collector and a negative electrode current collector, respectively.
  • the positive electrode and the negative electrode are arranged opposite to each other with the separator interposed therebetween, and an electrode laminate is produced in which the positive electrode and the negative electrode are laminated.
  • the electrode laminate is accommodated in an exterior body and immersed in an electrolytic solution.
  • a secondary battery is manufactured by sealing the exterior body so that a part of the positive electrode tab and the negative electrode tab protrudes to the outside.
  • Example 1 (Preparation of negative electrode) Natural graphite powder (average particle size (D 50 ): 20 ⁇ m, specific surface area: 1 m 2 / g) as a negative electrode active material and PVDF as a binder are uniformly dispersed in NMP at a mass ratio of 95: 5 Thus, a negative electrode slurry was produced. By applying this negative electrode slurry on both sides of a 15 ⁇ m thick copper foil serving as a negative electrode current collector and drying at 125 ° C. for 10 minutes to evaporate NMP, a negative electrode active material layer is formed and further pressed. A negative electrode was produced. In addition, the weight of the negative electrode active material layer per unit area after drying was set to 0.015 g / cm 2 .
  • LiNi 0.5 Mn 1.5 O 4 powder (average particle diameter (D 50 ): 10 ⁇ m, specific surface area: 0.5 m 2 / g) as a positive electrode active material was prepared.
  • a positive electrode active material, PVDF as a binder, and carbon black as a conductive additive were uniformly dispersed in NMP at a mass ratio of 93: 4: 3 to prepare a positive electrode slurry.
  • the positive electrode slurry was applied to both surfaces of a 20 ⁇ m thick aluminum foil serving as a positive electrode current collector, and then dried at 125 ° C. for 10 minutes to evaporate NMP, thereby producing a positive electrode.
  • the weight of the positive electrode active material layer per unit area after drying was set to 0.040 g / cm 2 .
  • a non-aqueous solvent was prepared by mixing. LiPF 6 was dissolved in a non-aqueous solvent at a concentration of 0.8 mol / L as an electrolyte. In this electrolytic solution, 1 mass% of LiFSI as an additive was dissolved with respect to the total mass of the nonaqueous electrolytic solution to prepare a nonaqueous electrolytic solution.
  • the positive electrode and the negative electrode were cut into 1.5 cm ⁇ 3 cm. Five layers of the obtained positive electrode and six layers of the negative electrode were alternately stacked while sandwiching a polypropylene porous film as a separator. The ends of the positive electrode current collector not covered with the positive electrode active material and the negative electrode current collector not covered with the negative electrode active material are welded respectively, and further, the positive electrode terminal made of aluminum and the negative electrode terminal made of nickel are connected to the welded portion. Each was welded to obtain an electrode element having a planar laminated structure. The electrode element was wrapped with an aluminum laminate film as an outer package, and an electrolyte solution was injected therein, and then sealed while reducing the pressure to produce a secondary battery.
  • a secondary battery was prepared and evaluated in the same manner as in Example 1 except that a nonaqueous solvent mixed at a ratio of 20: 10: 40: 30 was used.
  • Example 1 Comparative Example 1
  • a secondary battery was fabricated and evaluated.
  • Comparative Example 2 A secondary battery was prepared and evaluated in the same manner as in Comparative Example 1 except that LiFSI was not added.
  • Example 6 A secondary battery was fabricated in the same manner as in Example 3 except that 1% by mass of methylenemethane disulfonate (MMDS) was added as an additive in the total mass of the non-aqueous electrolyte instead of LiFSI in Example 3. ,evaluated.
  • MMDS methylenemethane disulfonate
  • Example 4 In place of the additive of Example 3, as additive, LiFSI was added in an amount of 0.5% by mass in the total mass of the nonaqueous electrolytic solution and MMDS was added in an amount of 0.5% by mass in the total mass of the nonaqueous electrolytic solution. Produced and evaluated a secondary battery in the same manner as in Example 3.
  • Table 1 shows the measurement results of capacity retention rate and volume increase of Comparative Examples 1 to 6 and Examples 1 to 5. Furthermore, the graph which compared the capacity
  • the electrolyte contains LiFSI as an additive, and further contains, as the non-aqueous solvent, one or more selected from the group consisting of fluorinated ethers, fluorinated phosphates, and sulfone compounds. It was shown that it is more preferable to include the above. More preferably, the non-aqueous solvent contains a fluorinated ether.
  • Example 4 had a higher capacity retention rate and a smaller volume increase than Comparative Examples 6 and 3. From this, it was shown that the combined use of cyclic sulfonate ester (MMDS) and LIFSI has a synergistic effect and is more preferable.
  • Example 4 used both PC and EC
  • Example 5 used only EC
  • Example 5 was better with a smaller volume increase rate. This is probably because EC has a higher dielectric constant than PC and a high ability to dissolve LiFSI.
  • Example 6 A secondary battery was prepared and evaluated in the same manner as in Example 4 except that CH 3 CH 2 O (CF 2 ) 4 F (FE2) was used as the fluorinated ether instead of FE1.
  • Example 7 A secondary battery was prepared and evaluated in the same manner as in Example 4 except that H (CF 2 ) 4 CH 2 O (CF 2 ) 2 H was used as the fluorinated ether instead of FE1.
  • Example 8 A secondary battery was produced and evaluated in the same manner as in Example 4 except that CF 3 CHFCF 2 OCH 2 (CF 2 ) 2 F was used as the fluorinated ether instead of FE1.
  • Example 9 A secondary battery was prepared and evaluated in the same manner as in Example 4 except that dimethyl sulfone (DMS) was used instead of SL as the sulfone compound.
  • DMS dimethyl sulfone
  • Example 10 A secondary battery was prepared and evaluated in the same manner as in Example 4 except that ethyl methyl sulfone (EMS) was used as the sulfone compound instead of SL.
  • EMS ethyl methyl sulfone
  • Example 11 A secondary battery was prepared and evaluated in the same manner as in Example 4 except that ethyl isopropyl sulfone (EiPS) was used instead of SL as the sulfone compound.
  • EiPS ethyl isopropyl sulfone
  • Table 2 shows the results of Examples 6 to 11. As described above, Examples 6 to 8 were obtained by using other fluorinated ethers instead of FE1 of Example 4, and Examples 9 to 11 were different sulfone compounds instead of SL of Example 4. Is used. In either case, it was confirmed that good results were obtained in both capacity retention ratio and volume increase.
  • Example 12 A secondary battery was prepared and evaluated in the same manner as in Example 4 except that 1,3-propane sultone (PS) was used instead of MMDS as the cyclic sulfonate ester.
  • PS 1,3-propane sultone
  • Example 13 A secondary battery was prepared and evaluated in the same manner as in Example 4 except that 1,4-butane sultone (BS) was used instead of MMDS as the cyclic sulfonate ester.
  • BS 1,4-butane sultone
  • Example 12 and Example 13 show the measurement results of Example 12 and Example 13. As described above, Examples 12 and 13 are obtained by changing the type of the cyclic sulfonate ester of the additive in Example 4. In Examples 12 and 13, the capacity retention rate and the volume increase amount are slightly inferior to those in the case where MMDS, which is a cyclic disulfonic acid ester, is used as an additive (Example 4), but both have good characteristics. It was confirmed.
  • LiMn 2 O 4 powder (average particle diameter (D 50 ): 13 ⁇ m, specific surface area: 0.5 m 2 / g) was used, and the unit area A secondary battery was fabricated and evaluated in the same manner as in Comparative Example 6 except that the weight of the positive electrode active material layer per hit was 0.050 g / cm 2 and the upper limit voltage was 4.2 V.
  • LiMn 2 O 4 powder (average particle diameter (D 50 ): 13 ⁇ m, specific surface area: 0.5 m 2 / g) was used, and the unit area A secondary battery was produced and evaluated in the same manner as in Example 3 except that the weight of the positive electrode active material layer was 0.050 g / cm 2 and the upper limit voltage was 4.2 V.
  • Comparative Example 8 and Comparative Example 9 are secondary batteries using a 4V class active material
  • Comparative Example 8 uses only MMDS as an additive
  • Comparative Example 9 uses only LiFSI as an additive.
  • the capacity retention rate of Comparative Example 8 was 73%
  • the volume increase amount was 5%
  • the capacity maintenance rate of Comparative Example 9 was 70%
  • the volume increase amount was 6%.
  • the improvement effect of the capacity maintenance rate and the volume increase amount was not recognized as compared with the case where the cyclic sulfonic acid ester was used. .
  • LiFSI has a particularly remarkable effect on the 5V class active material.
  • Comparative Example 10 Secondary in the same manner as in Comparative Example 3 except that LiCoPO 4 was used instead of LiNi 0.5 Mn 1.5 O 4 as the positive electrode active material, the upper limit voltage was 5.1 V, and the cycle number was 100 cycles. A battery was made and evaluated.
  • Example 14 Secondary using LiCoPO 4 instead of LiNi 0.5 Mn 1.5 O 4 as the positive electrode active material, the upper limit voltage is 5.1 V, and the number of cycles is 100 cycles. A battery was made and evaluated.
  • Li (Li 0.15 Ni 0.2 Mn 0.65 ) O 2 was used instead of LiNi 0.5 Mn 1.5 O 4 as the positive electrode active material, and the weight of the positive electrode active material layer per unit area was 0
  • a secondary battery was fabricated and evaluated in the same manner as in Comparative Example 3 except that 0.025 g / cm 2 , the upper limit voltage was 4.7 V, the lower limit voltage was 2.5 V, and the cycle number was 100 cycles.
  • Example 15 Li (Li 0.15 Ni 0.2 Mn 0.65 ) O 2 was used instead of LiNi 0.5 Mn 1.5 O 4 as the positive electrode active material, and the weight of the positive electrode active material layer per unit area was 0 and .025g / cm 2, the upper limit voltage 4.7V, the lower limit voltage was 2.5V, except that the number of cycles is 100 cycles to produce a secondary battery in the same manner as in example 1 and evaluated.
  • Table 4 shows the capacity retention rates after 100 cycles at 45 ° C. of Comparative Examples 10 and 11 and Examples 14 and 15.
  • This embodiment in which LiFSI was added to olivine type LiCoPO 4 and layered structure Li (Li 0.15 Ni 0.2 Mn 0.65 ) O 2 was effective in improving cycle characteristics. From this, it was shown that the effect of adding LiFSI can be obtained with a 5V class positive electrode active material regardless of the structure of the positive electrode active material.

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Abstract

La présente invention concerne une batterie rechargeable lithium-ion comprenant : une électrode positive comprenant une substance active d'électrode positive avec un potentiel de fonctionnement d'au moins 4,5 V par rapport au lithium métal ; et un électrolyte non aqueux comprenant (a) un anion N(SO2F)2, (b) un carbonate annulaire, et (c) au moins un type sélectionné dans un groupe constitué d'un éther fluoré, d'un organophosphate fluoré et d'un composé sulfonique qui sont décrits par une formule prédéterminée.
PCT/JP2013/081085 2012-11-20 2013-11-18 Batterie rechargeable lithium-ion WO2014080870A1 (fr)

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WO2018212276A1 (fr) * 2017-05-19 2018-11-22 日本電気株式会社 Batterie rechargeable au lithium-ion
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JPWO2019054411A1 (ja) * 2017-09-13 2020-10-15 日本電気株式会社 リチウムイオン二次電池
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