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WO2013069790A1 - Cellule secondaire à électrolyte non aqueux - Google Patents

Cellule secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2013069790A1
WO2013069790A1 PCT/JP2012/079179 JP2012079179W WO2013069790A1 WO 2013069790 A1 WO2013069790 A1 WO 2013069790A1 JP 2012079179 W JP2012079179 W JP 2012079179W WO 2013069790 A1 WO2013069790 A1 WO 2013069790A1
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Prior art keywords
compound
aqueous electrolyte
formula
secondary battery
electrolyte secondary
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PCT/JP2012/079179
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English (en)
Japanese (ja)
Inventor
真男 岩谷
康人 神座
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旭硝子株式会社
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Publication of WO2013069790A1 publication Critical patent/WO2013069790A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/52—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

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery, particularly a lithium ion secondary battery.
  • Lithium ion secondary batteries are widely used in portable electronic devices such as mobile phones and notebook computers. In recent years, it is also expected to be used as an in-vehicle power source for driving a motor, which is the key to the spread of electric vehicles, in order to solve environmental and energy problems. However, in order to obtain a practical on-vehicle power source for driving a motor, a discharge capacity capable of obtaining a sufficient travel distance is required, and a battery having a higher energy density is desired.
  • lithium cobalt oxide LiCoO 2
  • LiNiO 2 lithium nickel compound
  • LiCo cobalt nickel manganese composite oxide for example, LiCo 1/3 Ni 1/3 Mn 1
  • Layered rock salt type compounds such as / 3 O 2
  • spinel type manganese compounds LiMn 2 O 4
  • olivine iron lithium compounds LiFePO 4
  • any of these positive electrode materials has a capacity density of less than 200 mAh / g, and a sufficient discharge capacity cannot be obtained as an in-vehicle power source for driving a motor.
  • Patent Document 1 proposes a positive electrode material for a lithium ion battery, characterized in that an oxidation treatment is performed on a positive electrode material for a lithium ion battery using the same solid solution.
  • Patent Document 3 a nonaqueous electrolyte mainly composed of ⁇ -butyrolactone has been proposed as a nonaqueous electrolyte that can withstand a high charging voltage.
  • Patent Document 4 a non-aqueous electrolyte containing a specific bissulfonylimide salt has been proposed.
  • the solid solution positive electrode using Li 2 MnO 3 which is a high-capacity positive electrode candidate material described in Patent Document 1
  • the charge / discharge voltage is increased, the cycle characteristics are poor.
  • it deteriorated easily by repeated discharge. Therefore, even a lithium ion battery using such a solid solution positive electrode as a high-capacity positive electrode has a problem that cycle durability under a high-capacity use condition is poor, and deterioration occurs immediately when charging / discharging at a high voltage. It was.
  • Patent Document 2 an attempt is made to improve the above-described degradation problem by oxidation treatment, but the high-voltage charge / discharge cycle characteristics still do not have practically sufficient performance.
  • the non-aqueous electrolyte of Patent Document 3 has only been confirmed to have cycle characteristics of about 10 cycles while being able to withstand a high charge voltage, and can withstand the use of repeated charge / discharge required in practice. I can not say.
  • the non-aqueous electrolyte of patent document 4 it is not examined whether practically sufficient cycle characteristics can be obtained by charging and discharging at a high voltage.
  • the present invention has been made in view of the above problems, can be charged at a high voltage, can have a high capacity, and can withstand the use of repetitive charging / discharging that is practically required as an in-vehicle power source for driving a motor. It is an object to provide a nonaqueous electrolyte secondary battery to be obtained.
  • a positive electrode having a compound represented by the general formula (I) as a positive electrode active material, a negative electrode, and a nonaqueous electrolytic solution The non-aqueous electrolyte is One or more compounds ( ⁇ ) selected from the group consisting of a cyclic carbonate compound, a chain carbonate compound, a cyclic ester compound, and a chain ester compound, and LiPF 6 , LiClO 4 , LiBF 4 , and the general formula (A) Compounds represented by general formula (B), compounds represented by general formula (C), LiCF 3 SO 3 , LiC 4 F 9 CO 2 , LiC (CF 3 SO 2 ) 3 , and LiN A base electrolyte containing at least one lithium salt ( ⁇ ) selected from the group consisting of (CF 3 SO 2 ) 2 , a compound represented by the general formula (II), and a general formula (III)
  • a non-aqueous electrolyte secondary battery comprising: one or more compounds ( ⁇ ) selected from the group consisting of
  • R 1 to R 4 are each independently an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group that may contain an etheric oxygen atom
  • Y is an ether An alkylene group having 1 to 4 carbon atoms or a fluorine-containing alkylene group which may contain a functional oxygen atom.
  • R 1 to R 4 of the compound represented by the formula (II) and the compound represented by the formula (III) are all CH 3 —, CH 3 CH 2 —, CF 3 CH 2 — or CHF 2 CF 2
  • non-aqueous electrolyte secondary battery that can be charged at a high voltage to obtain a high capacity and that can withstand the use of repeated charge and discharge that is practically required.
  • the non-aqueous electrolyte secondary battery of the present invention has a positive electrode and a negative electrode facing each other with a separator interposed therebetween, and a non-aqueous electrolyte.
  • a compound represented by the following formula (I) or formula (I ′) is used as the positive electrode active material.
  • the notation of the compound represented by the formula (I) or the formula (I ′) is a composition formula before performing treatment such as charge / discharge and activation.
  • the activation means removing lithium oxide (Li 2 O) or lithium and lithium oxide from the positive electrode active material.
  • an ordinary activation method there is an electrochemical activation method in which charging is performed at a voltage higher than 4.4 V or 4.6 V (a value expressed as a potential difference from the oxidation-reduction potential of Li + / Li).
  • the activation method performed chemically is mentioned by performing the chemical reaction using acids, such as a sulfuric acid, hydrochloric acid, or nitric acid.
  • Me ′ is at least one selected from Co, Ni, Cr, Fe, Al, Ti, Zr and Mg. Further, x, y, z, p, and q in the formula (I) satisfy the relationships of the following formulas (I-1) to (I-8). 0.09 ⁇ x ⁇ 0.3 ............
  • the proportion of Li exceeds 1.2 times mol with respect to the total of transition metal elements Mn and Me ′.
  • the composition ratio of Li element to the total molar amount of the transition metal element is preferably 1.25 ⁇ (1 + x) / (y + z) ⁇ 1.75, and 1.35 ⁇ (1 + x) / (y + z) ⁇ 1.65. More preferably, 1.40 ⁇ (1 + x) / (y + z) ⁇ 1.55 is particularly preferable.
  • the composition ratio is in the above range, a positive electrode material having a high discharge capacity per unit mass can be obtained when a high charging voltage of 4.6 V or higher is applied.
  • the compound (I) contains Mn. Further, the ratio of Mn to the total amount of Mn and Me ′ is 0.4 to 0.8 as shown in the formula (I-6), and preferably 0.55 to 0.75. When the proportion of Mn is in the range of formula (I-6), the discharge capacity becomes high.
  • q represents the proportion of F, but includes 0 as shown in Formula (I-5). That is, the compound (I) includes a compound in which F is not present.
  • p is a value determined according to x, y, z, and q, and is in a range exceeding 1.9 and less than 2.1 as shown in Formula (I-4).
  • the compound (I ′) represented by the following formula (I ′) is more preferable.
  • the proportion of Li exceeds 1.2 times mol with respect to the total of transition metal elements Mn, Ni, and Co. Less than 8.
  • the composition ratio of the Li element to the total molar amount of the transition metal element is preferably 1.35 ⁇ (1 + x) / (y + v + w) ⁇ 1.65, and 1.45 ⁇ (1 + x) / (y + v + w) ⁇ 1.55. More preferred.
  • the composition ratio is in the above range, a positive electrode material having a high discharge capacity per unit mass can be obtained when a high charging voltage of 4.6 V or higher is applied.
  • Compound (I) or Compound (I ′) preferably has a layered rock salt type crystal structure (space group R-3m).
  • XRD X-ray diffraction
  • the surface of the compound (I) or the compound (I ′) is at least one metal element selected from the group consisting of Al, Y, Ga, In, La, Pr, Nd, Gd, Dy, Er, and Yb.
  • a compound containing Li and a nonmetallic element P, S, B).
  • the positive electrode is formed by forming a positive electrode layer containing a positive electrode active material, a conductivity-imparting agent, and a binder on a current collector.
  • a conductivity-imparting agent in addition to a carbon material, a conductive oxide powder or the like can be used.
  • the binder a resin binder such as polyvinylidene fluoride and / or a rubber binder such as hydrocarbon rubber or fluorine rubber can be used.
  • As the current collector a metal thin film mainly composed of Al or the like can be used.
  • the content of the conductivity-imparting agent in the positive electrode is preferably 1 to 10% by mass of the entire positive electrode layer, and the content of the binder is also preferably about 1 to 10% by mass of the entire positive electrode layer.
  • the ratio between the conductivity-imparting agent and the binder is equal to or less than the preferable upper limit value, the ratio of the active material in the positive electrode layer can be sufficiently secured, and a sufficient capacity per unit mass can be obtained. If the ratio between the conductivity-imparting agent and the binder is too small, the conductivity may not be maintained, or a problem of electrode peeling may occur.
  • the proportion of the active material in the positive electrode layer is preferably 80 to 98% by mass.
  • the negative electrode is formed by forming a negative electrode layer containing a powdered negative electrode active material, a conductivity-imparting agent, and a binder on a current collector.
  • the negative electrode active material used for the negative electrode is not particularly limited as long as lithium ions can be occluded during charging and released during discharging, and known materials can be used. Specific examples include carbon materials such as graphite, coke, and hard carbon, lithium alloys such as lithium-aluminum alloy, lithium-lead alloy, and lithium-tin alloy, lithium metal, Si, SnO 2 , SnO, TiO 2 , and Nb 2.
  • a metal oxide having a base potential lower than that of the positive electrode active material such as O 2 SiO, can be used.
  • the negative electrode binder and the conductivity-imparting agent those equivalent to the positive electrode can be used.
  • the current collector a metal thin film mainly composed of Cu or the like can be used.
  • the negative electrode active material can keep its shape by itself (for example, a lithium metal thin film), the negative electrode can be formed only with the negative electrode active material.
  • a non-aqueous electrolyte is an electrolyte that does not substantially contain water, and even if it contains water, the amount of water is in a range where performance degradation of a secondary battery using the non-aqueous electrolyte is not observed.
  • the amount of water that can be contained in the non-aqueous electrolyte is preferably 500 ppm by mass or less, more preferably 100 ppm by mass or less, and 50 ppm by mass or less with respect to the total mass of the non-aqueous electrolyte. It is particularly preferred.
  • the lower limit of the moisture content is 0 mass ppm.
  • the nonaqueous electrolytic solution in the present invention comprises a base electrolytic solution and one or more compounds ( ⁇ ) described later.
  • the base electrolyte contains one or more compounds ( ⁇ ) and one or more lithium salts ( ⁇ ) described below.
  • the compound ( ⁇ ) is a compound selected from the group consisting of a cyclic carbonate compound, a chain carbonate compound, a cyclic ester compound, and a chain ester compound.
  • the proportion of the compound ( ⁇ ) in the base electrolyte is preferably 50 to 99.8% by mass, more preferably 60 to 99.5% by mass, and 70 to 99% by mass. Particularly preferred.
  • the lithium salt ( ⁇ ) can be dissolved well. Moreover, if it is below a preferable upper limit, sufficient quantity of lithium salt ((beta)) can be contained.
  • the cyclic carbonate compound is a compound in which the ring skeleton has a ring structure composed of carbon atoms and oxygen atoms, and the ring structure has a carbonate bond represented by —O—C ( ⁇ O) —O—. .
  • the ring structure in the cyclic carbonate compound is preferably a 4- to 10-membered ring, more preferably a 4- to 7-membered ring, more preferably a 5- to 6-membered ring, and particularly preferably a 5-membered ring from the viewpoint of availability.
  • the ring structure of the cyclic carbonate compound is preferably a ring structure having one carbonate bond.
  • a ring structure in which a carbonate bond is formed by linking with a linear alkylene group or vinylene group is more preferable.
  • the linear alkylene group preferably has 1 to 7 carbon atoms, more preferably 1 to 4, more preferably 2 or 3. 2 is particularly preferable.
  • Specific examples include propylene carbonate (PC) and ethylene carbonate (EC).
  • Examples of the carbonate compound having a ring structure in which a carbonate bond is linked to a vinylene group include vinylene carbonate and dimethyl vinylene carbonate, and vinylene carbonate is particularly preferable.
  • the cyclic carbonate compound is also preferably a compound in which one or more hydrogen atoms of the linear alkylene group are substituted with a substituent.
  • a substituent for example, a halogen atom, an alkyl group, a halogenated alkyl group, a vinyl group, or an allyl group is preferable. Specific examples include fluoroethylene carbonate.
  • the base electrolyte contains a cyclic carbonate compound
  • the cyclic carbonate compound may be only one type or two or more types. The inclusion of a cyclic carbonate compound is preferable because the dielectric constant of the non-aqueous electrolyte can be increased.
  • the chain carbonate compound is a chain compound having no carbonate structure and having a carbonate bond represented by —O—C ( ⁇ O) —O—.
  • the chain carbonate compound is preferably a chain monocarbonate having one carbonate bond. Examples of the chain monocarbonate include dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC).
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • the chain carbonate compound may be only one type or two or more types. It is preferable to contain a chain carbonate compound because the viscosity of the nonaqueous electrolytic solution can be reduced.
  • the cyclic ester compound is a compound in which the ring skeleton has a ring structure composed of a carbon atom and an oxygen atom, and the ring structure has an ester bond represented by —O—C ( ⁇ O) —C—. .
  • the cyclic ester compound is preferably a compound that does not contain a carbon-carbon unsaturated bond in the molecule.
  • the cyclic structure in the cyclic ester compound is preferably a 4- to 10-membered ring, more preferably a 4- to 7-membered ring, more preferably a 5- to 6-membered ring, and particularly preferably a 5-membered ring from the viewpoint of availability.
  • the ring structure of the cyclic ester compound is preferably a ring structure having one ester bond, and more preferably a ring structure formed by linking an ester bond with a linear alkylene group.
  • the linear alkylene group preferably has 1 to 7 carbon atoms, more preferably 1 to 4, more preferably 2 or 3, and particularly preferably 2.
  • the cyclic ester compound may be a compound in which one or more hydrogen atoms of the linear alkylene group are substituted with a substituent. Examples of the substituent include a halogen atom, an alkyl group, and a halogenated alkyl group.
  • cyclic ester compounds such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, and ⁇ -valerolactone, and one hydrogen atom bonded to the carbon atom forming the ring structure of the cyclic ester compound.
  • examples thereof include compounds in which at least one group is substituted with a halogen atom, an alkyl group, or a halogenated alkyl group.
  • ⁇ -butyrolactone or ⁇ -valerolactone is preferable, and ⁇ -butyrolactone is particularly preferable from the viewpoint of easy availability and properties of the electrolytic solution.
  • the cyclic ester compound may be only one type or two or more types.
  • the inclusion of a cyclic ester compound is preferable because the stability of the electrolytic solution is improved.
  • the chain ester compound is a chain compound that has no ring structure and has an ester bond represented by —O—C ( ⁇ O) —C—.
  • the chain ester compound is preferably a chain monoester having one ester bond. Examples of the chain monoester include ethyl acetate, ethyl butyrate, butyl acetate and the like.
  • the chain ester compound may be only one type or two or more types. It is preferable to include a chain ester compound because the viscosity of the electrolytic solution can be easily reduced.
  • the base electrolyte may contain any two or more of a cyclic carbonate compound, a chain carbonate compound, a cyclic ester compound, and a chain ester compound. You may contain all four types.
  • the base electrolyte solution preferably contains one or more compounds ( ⁇ ′) selected from the group consisting of the following compound (1), compound (2), and compound (3).
  • R 5 to R 16 are each independently a hydrogen atom, a halogen atom, an alkyl group, or a halogenated alkyl group, and X is an oxygen atom or CH 2 .
  • R 5 to R 16 are halogen atoms, each is preferably independently a fluorine atom or a chlorine atom.
  • R 5 to R 16 are alkyl groups, the alkyl group preferably has 1 to 6 carbon atoms.
  • R 5 to R 16 are halogenated alkyl groups the alkyl group preferably has 1 to 6 carbon atoms, and the halogen atom is preferably a fluorine atom or a chlorine atom.
  • the proportion of the compound ( ⁇ ′) in the base electrolyte solution that is, the proportion of the total amount of the compound (1), the compound (2) and the compound (3) in the base electrolyte solution is 50 to 99.8% by mass. It is preferably 60 to 99.5% by mass, more preferably 70 to 99% by mass.
  • the ratio of each of the compound (1), the compound (2), and the compound (3) to the entire compound ( ⁇ ′) is 5 to 100 mass% for the compound (1) and 0 to 95 mass for the compound (2).
  • the compound (3) is preferably 0 to 10% by mass, the compound (1) is 10 to 100% by mass, the compound (2) is 0 to 90% by mass, and the compound (3) is 0 to 5% by mass. More preferably, the compound (1) is 20 to 100% by mass, the compound (2) is 0 to 80% by mass, and the compound (3) is particularly preferably 0 to 3% by mass.
  • the lithium salt ( ⁇ ) is LiPF 6 , LiClO 4 , LiBF 4 , the following compound (A) (where k is an integer of 1 to 5), the following compound (B), the following compound (C), LiCF 3.
  • Examples of the compound (A) include the following compound (A-1) to compound (A-4).
  • the compound (A) preferably includes a compound (A-2) in which k is 2, and is composed of a compound (A-2) in which k is 2, from the viewpoint of easily obtaining a non-aqueous electrolyte with high conductivity. It is more preferable.
  • the concentration of the lithium salt ( ⁇ ) in the base electrolyte is preferably 0.5 mol / l to 1.5 mol / l. In terms of mass, it is preferably 5 to 50% by mass, more preferably 8 to 30% by mass, and further preferably 10 to 20% by mass. If this concentration is too high, the viscosity increases, and if the concentration is too low, the electrical conductivity decreases.
  • the lithium salt ( ⁇ ) is preferably dissolved in the base electrolyte.
  • the base electrolyte may contain a conventional nonaqueous electrolyte solvent other than those described above.
  • chain ethers such as 1,2-dimethoxymethane (DME), 1,2-diethoxyethane (DEE) and ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, dimethyl sulfoxide , Formamide, acetamide, dimethylformamide, dioxolane, acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, trimethoxymethane, dioxolane derivative, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2 -Oxazolidinone, ethylene carbonate derivative, propylene carbonate derivative, tetrahydrofuran derivative, ethyl ether, anisole, N-methylpyr
  • the nonaqueous electrolytic solution of the present invention contains one or more compounds ( ⁇ ) selected from the group consisting of a compound represented by the formula (II) and a compound represented by the general formula (III).
  • R 1 to R 4 are each independently an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group that may contain an etheric oxygen atom
  • Y is an ether An alkylene group having 1 to 4 carbon atoms or a fluorine-containing alkylene group which may contain a functional oxygen atom.
  • R 1 to R 3 are preferably the same as each other.
  • the fluorine-containing alkyl group of R 1 to R 4 is preferably a partially fluorinated alkyl group in which a part of the hydrogen atoms of the alkyl group is substituted with a fluorine atom.
  • R 1 to R 4 are all CH 3 —, CH 3 CH 2 —, CF 3 CH 2 —, or CHF 2 CF 2 CH 2 —, and Y may be —CH 2 CH 2 —. preferable.
  • the following compounds (II-1) to (II-4) or compound (III-1) are preferred.
  • the content of the compound ( ⁇ ) in the non-aqueous electrolyte is preferably 0.2 to 30.0 parts by mass, and 0.5 to 20.0 parts by mass with respect to 100 parts by mass of the base electrolyte. It is more preferable.
  • the content of the compound ( ⁇ ) is at least the preferred lower limit, it becomes easy to obtain good high potential charge / discharge cycle characteristics.
  • the content of the compound ( ⁇ ) is not more than the preferable upper limit value, various characteristics of the electrolytic solution such as conductivity and low temperature characteristics can be achieved at a high level.
  • the material and shape of the porous membrane as the separator are not particularly limited as long as it is stable with respect to the non-aqueous electrolyte and has excellent liquid retention properties.
  • Polyvinylidene fluoride, polytetrafluoroethylene, ethylene and tetrafluoroethylene A porous sheet or non-woven fabric made of a fluororesin such as a copolymer, polyimide, or a polyolefin such as polyethylene or polypropylene is preferred, and the material is preferably a polyolefin such as polyethylene or polypropylene.
  • the lithium secondary battery according to the present invention is, for example, laminated in a dry air or an inert gas atmosphere by laminating a negative electrode and a positive electrode via a separator, or winding the laminated one, and then in an outer container such as a can case.
  • a battery can be manufactured by housing, injecting an electrolytic solution, and sealing with a flexible film made of a laminate of a synthetic resin and a metal foil.
  • the configuration and shape of the battery is not particularly limited, and can take the form of a positive electrode facing the separator, a wound type wound with the negative electrode, a laminated type, etc., and a coin type, laminate pack, square type, etc. It can take the form of a cell, a cylindrical cell or the like.
  • the charging voltage of the lithium secondary battery according to the present invention is preferably 4.2 V or higher, more preferably 4.4 V or higher, and particularly preferably 4.5 V or higher. Moreover, 5.0V or less is preferable, 4.9V or less is more preferable, and 4.8V or less is especially preferable.
  • a negative electrode was prepared by punching a lithium metal foil having a thickness of 300 ⁇ m into a circle having a diameter of 19 mm.
  • a separator a polyolefin microporous film having a thickness of 20 ⁇ m was present between the positive electrode and the negative electrode, and 0.5 mL of each test electrolyte was added thereto to produce an evaluation cell.
  • Table 1 shows the number of cycles when the charge / discharge cycle test was stopped. Further, Table 1 shows the ratio of the discharge capacity at the time of completion of the 80th cycle or when the charge / discharge cycle test is stopped to the discharge capacity at the 5th cycle as the discharge capacity maintenance ratio.
  • Table 2 shows the ratio of the average discharge voltage at the completion of 80 cycles to the average discharge voltage at the fifth cycle as the average discharge voltage maintenance ratio.
  • Table 3 shows the ratio with respect to the discharge energy of the 5th cycle of the discharge energy at the time of 80th cycle completion as a discharge energy maintenance factor.
  • the discharge energy is a numerical value represented by the product of the discharge capacity and the average discharge voltage. The larger the numerical value, the larger the work that can be performed by the nonaqueous electrolyte secondary battery.
  • Example 1 As shown in Tables 1 and 2, in Example 1, high values were obtained for both the discharge capacity retention ratio and the average discharge voltage at the 80th cycle. As a result, as shown in Table 3, a high discharge energy maintenance rate was obtained.
  • the non-aqueous electrolyte secondary battery of the present invention can be charged at a high voltage to obtain a high capacity, and can be used as a vehicle-mounted power source for driving a motor. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2011-247639 filed on November 11, 2011 are incorporated herein as the disclosure of the specification of the present invention. Is.

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention porte sur une cellule secondaire à électrolyte non aqueux qui se charge à des tensions élevées, qui peut obtenir des capacités élevées et qui peut résister à l'utilisation répétée demandée dans des applications réelles en tant que source d'énergie montée sur véhicule pour entraîner un moteur. Cette cellule secondaire à électrolyte non aqueux comprend une électrode positive ayant Li(LixMnyMe'z)OpFq (Me' est au moins un élément choisi à partir du groupe consistant en Co, Ni, Cr, Fe, Al, Ti, Zr et Mg. En outre, 0,09 < x < 0,3, y > 0, z > 0, 1,9 < p < 2,1, 0 ≤ q ≤ 0,1, 0,4 ≤ y / (y+z) ≤ 0,8, x+y+z = 1 et 1,2 < (1+x) / (y+z)) en tant que substance active d'électrode positive, une électrode négative et un électrolyte non aqueux contenant un sel du lithium, l'électrolyte non aqueux contenant un ou plusieurs composés d'ester d'acide phosphorique spécifiques en tant que composant essentiel.
PCT/JP2012/079179 2011-11-11 2012-11-09 Cellule secondaire à électrolyte non aqueux WO2013069790A1 (fr)

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JP2011-247639 2011-11-11
JP2011247639A JP2015018601A (ja) 2011-11-11 2011-11-11 非水電解液二次電池

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JP2015130343A (ja) * 2013-12-30 2015-07-16 三星精密化学株式会社Ｓａｍｓｕｎｇ Ｆｉｎｅ Ｃｈｅｍｉｃａｌｓ Ｃｏ．， Ｌｔｄ． リチウム二次電池用正極活物質、その製造方法、及びこれを含むリチウム二次電池

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JP2017182917A (ja) * 2016-03-28 2017-10-05 株式会社カネカ リチウムイオン二次電池及びその製造方法、ならびに組電池

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JP2004006382A (ja) * 2003-06-30 2004-01-08 Ube Ind Ltd リチウム二次電池用非水電解液及びリチウム二次電池
JP2007242581A (ja) * 2006-02-08 2007-09-20 Sanyo Electric Co Ltd 非水電解質二次電池
WO2008038798A1 (fr) * 2006-09-29 2008-04-03 Mitsui Mining & Smelting Co., Ltd. Batterie secondaire à électrolyte non aqueux
WO2008081839A1 (fr) * 2006-12-27 2008-07-10 Sanyo Electric Co., Ltd. Batterie secondaire électrolytique non aqueuse et son procédé de fabrication
JP2011014476A (ja) * 2009-07-06 2011-01-20 Hitachi Vehicle Energy Ltd リチウムイオン二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004006382A (ja) * 2003-06-30 2004-01-08 Ube Ind Ltd リチウム二次電池用非水電解液及びリチウム二次電池
JP2007242581A (ja) * 2006-02-08 2007-09-20 Sanyo Electric Co Ltd 非水電解質二次電池
WO2008038798A1 (fr) * 2006-09-29 2008-04-03 Mitsui Mining & Smelting Co., Ltd. Batterie secondaire à électrolyte non aqueux
WO2008081839A1 (fr) * 2006-12-27 2008-07-10 Sanyo Electric Co., Ltd. Batterie secondaire électrolytique non aqueuse et son procédé de fabrication
JP2011014476A (ja) * 2009-07-06 2011-01-20 Hitachi Vehicle Energy Ltd リチウムイオン二次電池

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015130343A (ja) * 2013-12-30 2015-07-16 三星精密化学株式会社Ｓａｍｓｕｎｇ Ｆｉｎｅ Ｃｈｅｍｉｃａｌｓ Ｃｏ．， Ｌｔｄ． リチウム二次電池用正極活物質、その製造方法、及びこれを含むリチウム二次電池

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