WO2015046174A1 - Batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux Download PDF

Info

Publication number
WO2015046174A1
WO2015046174A1 PCT/JP2014/075138 JP2014075138W WO2015046174A1 WO 2015046174 A1 WO2015046174 A1 WO 2015046174A1 JP 2014075138 W JP2014075138 W JP 2014075138W WO 2015046174 A1 WO2015046174 A1 WO 2015046174A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
mass
fluorine
aqueous electrolyte
secondary battery
Prior art date
Application number
PCT/JP2014/075138
Other languages
English (en)
Japanese (ja)
Inventor
室谷　英介
祐 小野崎
鈴木　俊夫
豊和 遠田
Original Assignee
旭硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to JP2015539221A priority Critical patent/JPWO2015046174A1/ja
Publication of WO2015046174A1 publication Critical patent/WO2015046174A1/fr

Links

Classifications

    • 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
    • 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
    • H01M10/0569—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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • 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 excellent in safety.
  • Non-aqueous electrolyte secondary batteries having a positive electrode, a negative electrode, and a non-aqueous electrolyte are widely used in portable electronic devices such as mobile phones and notebook computers.
  • a positive electrode of a non-aqueous electrolyte secondary battery using a lithium salt as an electrolyte for example, a positive electrode using LiCoO 2 is known.
  • Patent Documents 2 and 3 Proposals for adding Al or Mg
  • proposals for coating the surface of active material particles Patent Document 4
  • a non-aqueous electrolyte secondary battery using a Co-based positive electrode has a problem that metal is eluted from the positive electrode during use.
  • the amount of metal elution from the positive electrode increases, there is a problem that the crystal structure is partially collapsed and battery characteristics are deteriorated, and a negative electrode dendrite is formed, thereby causing a short circuit and thermal runaway.
  • a method for suppressing metal elution a method of adding an additive to the positive electrode, a method of coating the surface of the positive electrode, etc. are known (Patent Document 5, Non-Patent Document 1), but the effect is insufficient. .
  • carbonate solvents such as ethylene carbonate and dimethyl carbonate have been widely used.
  • carbonate-based solvent is flammable, there is a risk of ignition due to heat generation of the battery.
  • fluorine-containing solvent it has been proposed to use a fluorine-containing solvent.
  • Nonaqueous electrolyte solution for obtaining a non-aqueous electrolyte secondary battery that is flame-retardant and has good battery characteristics (cycle characteristics, discharge capacity)
  • a fluorinated solvent for obtaining a non-aqueous electrolyte secondary battery that is flame-retardant and has good battery characteristics (cycle characteristics, discharge capacity)
  • a fluorinated solvent for obtaining a non-aqueous electrolyte secondary battery that is flame-retardant and has good battery characteristics (cycle characteristics, discharge capacity)
  • a fluorinated solvent for obtaining a non-fluorinated cyclic carbonate
  • a non-fluorine Nonaqueous electrolytes containing a cyclic ester and a lithium salt are known (Patent Documents 7 and 8).
  • Patent Documents 7 and 8 describe only evaluation using general LiCoO 2 , and it is difficult to estimate the effect when the above-described other metal is added or the surface is coated. It is.
  • non-aqueous electrolyte secondary batteries have been actively applied to in-vehicle power sources for electric vehicles that require greater energy, non-aqueous electrolytes that can be used stably even at high voltages. There is a need for an electrolyte secondary battery.
  • the object of the present invention is to maintain good cycle characteristics even at a high voltage, further reduce the amount of metal elution from the positive electrode, hardly cause thermal runaway, have excellent thermal stability, and have high flame resistance.
  • the next battery is to provide.
  • a non-aqueous electrolyte secondary battery having a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the positive electrode includes a lithium transition metal composite oxide represented by the following formula (1), and the non-aqueous electrolyte
  • the electrolytic solution contains a lithium salt and a liquid composition, and the liquid composition contains at least one kind selected from the group consisting of a fluorine-containing ether compound, a fluorine-containing chain carboxylic acid ester compound, and a fluorine-containing chain carbonate compound.
  • a non-aqueous electrolyte secondary battery comprising a fluorine solvent ( ⁇ ) and a cyclic carboxylic acid ester compound.
  • Li x Co y Me z O p F q ⁇ (1) (In the formula (1), Me is at least one metal element selected from the group consisting of transition metal elements other than Co, Ni and Mn, Al and alkaline earth metal elements, and 0.9 ⁇ (x ⁇ 1.2, 0.95 ⁇ y ⁇ 2, 0 ⁇ z ⁇ 0.05, 1.9 ⁇ p ⁇ 2.1, 0 ⁇ q ⁇ 0.05)
  • Me in Formula (1) is one metal element selected from the group consisting of Al, Ti, Zr, Mg, Hf, Nb, Ta, Sn and Zn, [1] or [2] Non-aqueous electrolyte secondary battery.
  • the liquid composition is at least selected from the group consisting of a saturated cyclic carbonate compound, a saturated chain carbonate compound having no fluorine atom, a saturated cyclic sulfone compound (excluding a lithium salt), and a phosphate ester compound.
  • the nonaqueous electrolyte secondary battery according to any one of [1] to [3], further comprising one kind of compound ( ⁇ ).
  • N A / N Li which is a ratio of the total number of moles (N A ) of the cyclic carboxylic acid ester compound to the total number of moles (N Li ) of lithium atoms derived from the lithium salt is 1.5 to 7.0.
  • N Li said N A, wherein the ratio of the sum of the total number of moles (N B) of the compound ( ⁇ ) (N A + N B) / N Li is 3.0 to 7.0, The nonaqueous electrolyte secondary battery according to any one of [4] to [6].
  • R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, or 3 to 10 carbon atoms. Or a fluorinated alkyl group having 2 to 10 carbon atoms having one or more etheric oxygen atoms, or a fluorinated alkyl group having 2 to 10 carbon atoms having one or more etheric oxygen atoms.
  • R 1 and R 2 is a fluorinated alkyl group having 1 to 10 carbon atoms, a fluorinated cycloalkyl group having 3 to 10 carbon atoms, or 2 to 2 carbon atoms having one or more etheric oxygen atoms. 10 fluorinated alkyl groups.
  • the compound represented by the formula (2) is CF 3 CH 2 OCF 2 CHF 2 , CF 3 CH 2 OCF 2 CHFCF 3 , CHF 2 CF 2 CH 2 OCF 2 CHF 2 , or CH 3 CH 2 CH 2.
  • the lithium salt includes LiPF 6, wherein [1] to one of the non-aqueous electrolyte secondary battery of [13].
  • the non-aqueous electrolyte secondary battery of the present invention can maintain good cycle characteristics even at a high voltage, and further, the amount of metal elution from the positive electrode is reduced, it is difficult to cause thermal runaway, has excellent thermal stability, and flame retardant. High nature.
  • a compound represented by the formula (1) is referred to as a compound (1).
  • the following definitions of terms apply throughout this specification and the claims.
  • Transition metal element means a transition metal of Group 4, Group 5, Group 6, Group 7, Group 8, Group 9, Group 10, Group 11 and Group 12 of the Periodic Table.
  • non-aqueous electrolyte is an electrolyte that does not substantially contain water, and even if water is included, the water content of the secondary battery using the non-aqueous electrolyte does not deteriorate in performance. It means an electrolyte solution in a range of amounts.
  • 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 particularly preferably 50 ppm by mass or less with respect to the total mass of the non-aqueous electrolyte.
  • the lower limit of the moisture content is 0 mass ppm.
  • Other compounds (other solvents, additives, etc.) other than lithium salt, fluorine-containing solvent ( ⁇ ), cyclic carboxylic acid ester compound and compound ( ⁇ ) are defined as “other components”, and lithium salt and liquid composition Differentiated from things.
  • the “fluorinated ether compound” means a chain or cyclic compound having an ether bond and having a fluorine atom.
  • “Fluorine-containing chain carboxylic acid ester compound” means a chain compound having an ester bond in a chain structure, no ring structure containing an ester bond, and having a fluorine atom.
  • “Fluorine-containing chain carbonate compound” refers to a chain structure having a carbonate bond represented by —O—C ( ⁇ O) —O—, having no ring structure containing a carbonate bond, and having a fluorine atom Means a chain-like compound having
  • the “fluorinated alkane compound” means a compound in which one or more hydrogen atoms of an alkane are substituted with fluorine atoms, and hydrogen atoms remain.
  • the “cyclic carboxylic acid ester compound” means a cyclic compound having an ester bond as a part of the ring skeleton.
  • the “saturated cyclic carbonate compound” is a compound in which a ring skeleton is composed of carbon atoms and oxygen atoms, and has a carbonate bond represented by —O—C ( ⁇ O) —O— as a part of the ring skeleton. It means a cyclic compound having no carbon unsaturated bond.
  • the “saturated chain carbonate compound having no fluorine atom” is a chain structure having a carbonate bond represented by —O—C ( ⁇ O) —O— and having a ring structure including a carbonate bond. It means a chain compound having no fluorine atom and no carbon-carbon unsaturated bond.
  • Fluorinated and fluorinated mean that some or all of the hydrogen atoms bonded to the carbon atom are replaced by fluorine atoms.
  • the “fluorinated alkyl group” means a group in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
  • the partially fluorinated groups are hydrogen atoms and fluorine atoms.
  • Carbon-carbon unsaturated bond means a carbon-carbon double bond or a carbon-carbon triple bond.
  • Examples of the positive electrode of the non-aqueous electrolyte secondary battery of the present invention include an electrode in which a positive electrode layer containing a positive electrode active material, a conductivity-imparting agent, and a binder is formed on a current collector.
  • the positive electrode in the present invention contains the following compound (1). That is, the positive electrode of the nonaqueous electrolyte secondary battery of the present invention contains the following compound (1) as the positive electrode active material.
  • the positive electrode containing the compound (1) contains a non-aqueous electrolyte described later, excellent cycle characteristics can be obtained even at a high voltage, and the amount of metal elution from the positive electrode is reduced, and thermal runaway is unlikely to occur. Thus, a non-aqueous electrolyte secondary battery having high thermal stability is obtained.
  • Me is at least one metal element selected from the group consisting of transition metal elements other than Co, Ni and Mn, Al and alkaline earth metal elements, and 0.9 ⁇ (x ⁇ 1.2, 0.95 ⁇ y ⁇ 2, 0 ⁇ z ⁇ 0.05, 1.9 ⁇ p ⁇ 2.1, 0 ⁇ q ⁇ 0.05)
  • Me in the compound (1) is one metal element selected from the group consisting of Al, Ti, Zr, Mg, Hf, Nb, Ta, Sn and Zn from the viewpoint of improving safety and cycle characteristics. And at least one metal element selected from the group consisting of Al, Ti, Zr and Mg is more preferable.
  • x is preferably 0.95 ⁇ x ⁇ 1.1 from the viewpoint that the amount of free alkali does not become too high and the discharge capacity and discharge rate characteristics are improved.
  • y is preferably 0.95 ⁇ y ⁇ 1.0 in terms of a good balance of discharge capacity, cycle characteristics, safety, and the like.
  • z is more preferably 0.01 ⁇ z ⁇ 0.025 from the viewpoint of good balance of discharge capacity, cycle characteristics, safety, and the like.
  • p is a value determined according to x, y, and z, and 1.9 ⁇ p ⁇ 2.1.
  • q represents the proportion of F, and q is 0 when F is not present. If q is larger than 0, the safety of the compound (1) becomes higher. Moreover, when q is 0, the reduction of the discharge capacity tends to be suppressed.
  • the compound (1) include the following compounds. Li 1.0 Co 0.98 Mg 0.01 Al 0.01 O 2 , Li 1.005 Co 0.975 Mg 0.01 Al 0.01 O 2 , Li 0.995 Co 0.975 Mg 0.01 Al 0.01 Ti 0.005 O 2 , Li 1.004 Co 0.974 Mg 0.01 Al 0.01 Zr 0.001 O 2 , Li 0.998 Co 0.978 Mg 0.01 Al 0.01 Zr 0.001 Ti 0.001 O 2 , Li 0.997 Co 0.977 Mg 0.11 Al 0.01 Zr 0.001 Ti 0.001 O 2 , Li 1.0 Co 0.9975 Mg 0.001 Al 0.001 Ti 0.0005 O 2 , Li 1.0 Co 0.9975 Mg 0.001 Al 0.001 Ti 0.0005 O 2 , Li 1.0 Co 0.9975 Mg 0.001 Al 0.001 Ti 0.0005 O 1.993 F 0.007 and the like.
  • a well-known manufacturing method is employable.
  • the method etc. of international publication 2007/052712 are mentioned.
  • a compound (1) may be used individually by 1 type, and may use 2 or more types together.
  • the positive electrode of the non-aqueous electrolyte secondary battery of the present invention may contain other positive electrode active materials other than the compound (1) in addition to the compound (1) as long as the effects of the present invention are not impaired.
  • positive electrode active materials include lithium transition metal composite oxides (LiCoO 2 , LiNiO 2 , LiMnO 2, etc.) other than the compound (1), transition metal oxides, olivine-type metal lithium salts, and the like. .
  • the content of the compound (1) in the positive electrode of the non-aqueous electrolyte secondary battery of the present invention is preferably 50% by mass or more and 100% by mass or less, and 80% by mass or more and 99% by mass with respect to 100% by mass of the total amount of the positive electrode active material. More preferable is 5% by mass. If the content of the compound (1) is at least the lower limit value, excellent cycle characteristics can be easily obtained even at high voltages, and battery characteristics such as discharge capacity and discharge voltage can be improved. If the total ratio of the compound (1) is equal to or less than the upper limit value, battery characteristics having characteristics (high safety, high voltage, etc.) of the positive electrode active material containing a metal other than Co can be obtained.
  • Conductivity imparting agent examples include carbon materials, metal substances (such as Al), and conductive oxide powders.
  • binder examples include a resin binder (such as polyvinylidene fluoride) and a rubber-based binder (such as hydrocarbon rubber and fluororubber).
  • resin binder such as polyvinylidene fluoride
  • rubber-based binder such as hydrocarbon rubber and fluororubber
  • Examples of the current collector include a metal thin film mainly composed of Al or the like.
  • the negative electrode is not particularly limited.
  • Examples of the negative electrode include an electrode in which a negative electrode layer containing a powdered negative electrode active material, a conductivity-imparting agent, and a binder is formed on a current collector.
  • the conductivity imparting material may not be included.
  • a negative electrode active material can maintain a shape by itself (for example, when it is a lithium metal thin film), a negative electrode can be formed only with a negative electrode active material.
  • Examples of the negative electrode active material include one or more selected from the group consisting of a lithium metal, a lithium alloy, and a carbon material capable of inserting and extracting lithium ions.
  • Examples of the lithium alloy include a Li—Al alloy, a Li—Pb alloy, and a Li—Sn alloy.
  • Examples of the carbon material include graphite, coke, and hard carbon.
  • Examples of the current collector include a metal thin film mainly composed of Cu or the like.
  • the non-aqueous electrolyte includes a lithium salt and a liquid composition, and includes other components as necessary.
  • the lower limit of the ionic conductivity at 25 ° C. of the nonaqueous electrolytic solution is preferably 0.4 S / m.
  • a secondary battery using a non-aqueous electrolyte having an ionic conductivity at 25 ° C. of less than 0.4 S / m has poor output characteristics and poor practicality. If the non-aqueous electrolyte has an ionic conductivity at 25 ° C. of 0.4 S / m or more, the secondary battery has good output characteristics.
  • Lithium salt is an electrolyte that dissociates in a non-aqueous electrolyte and supplies lithium ions.
  • the lithium salt include Li 2 PO 3 F, LiPO 2 F 2 , LiPF 6 , the following compound (A) (where k is an integer of 1 to 5), FSO 2 N (Li) SO 2 F, CF 3 SO 2 N (Li) SO 2 CF 3 , CF 3 CF 2 SO 2 N (Li) SO 2 CF 2 CF 3 , CF 3 CFHSO 2 N (Li) SO 2 CFHCF 3 , LiClO 4 , the following compound (B) The following compound (E), LiBF 4 and the like can be mentioned.
  • the lithium salt contained in the non-aqueous electrolyte preferably contains LiPF 6 and more preferably LiPF 6 only.
  • LiPF 6 can exhibit high ionic conductivity when dissolved in a solvent having a high solubility, but compared to other lithium salts such as CF 3 CF 2 SO 2 N (Li) SO 2 CF 2 CF 3. It is difficult to dissolve in a fluorine-containing solvent.
  • the combined use with a cyclic carboxylic acid ester compound improves the solubility of LiPF 6 in a fluorine-containing solvent. When LiPF 6 is uniformly dissolved in the fluorine-containing solvent, it becomes easy to obtain a nonaqueous electrolytic solution having practically sufficient ionic conductivity.
  • LiPF 6 is likely to be thermally decomposed and easily reduce the thermal stability of the battery.
  • the inclusion of the cyclic carboxylic acid ester compound makes it difficult for the battery to run out of heat in a non-aqueous electrolyte using LiPF 6 .
  • 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, since only a compound (A-2) in which k is 2 is preferable. More preferably, it consists of.
  • the liquid composition contains a fluorine-containing solvent ( ⁇ ) and a cyclic carboxylic acid ester compound, and may contain a compound ( ⁇ ) as necessary. That is, the liquid composition in the present invention comprises only the fluorinated solvent ( ⁇ ) and the cyclic carboxylic acid ester compound, or comprises the fluorinated solvent ( ⁇ ), the cyclic carboxylic acid ester compound and the compound ( ⁇ ), One of them.
  • the fluorine-containing solvent ( ⁇ ) contains at least one selected from the group consisting of fluorine-containing ether compounds, fluorine-containing chain carboxylic acid ester compounds and fluorine-containing chain carbonate compounds, and other fluorine-containing solvents (if necessary) However, the fluorine-containing cyclic carbonate compound may be excluded). Fluorine-containing ether compounds, fluorine-containing chain carboxylic acid ester compounds, and fluorine-containing chain carbonate compounds have similar characteristics in terms of chemical stability due to introduction of fluorine atoms, compatibility with other compounds, and the like. Yes, it can be treated as an equivalent compound.
  • the fluorine-containing solvent ( ⁇ ) is a solvent having a fluorine atom in the molecule and is excellent in flame retardancy.
  • a fluorine-containing solvent ((alpha)) may be used individually by 1 type, and may use 2 or more types together. When the number of fluorine-containing solvents ( ⁇ ) is two or more, the ratio can be arbitrarily determined.
  • the fluorine-containing solvent ( ⁇ ) preferably contains a fluorine-containing ether compound from the viewpoint of the solubility of the lithium salt, the flame retardancy, and the ionic conductivity of the nonaqueous electrolytic solution.
  • the fluorine-containing ether compound the following compound (2) is preferable from the viewpoint of the solubility of the lithium salt, the flame retardancy, and the ionic conductivity of the non-aqueous electrolyte.
  • a fluorine-containing ether compound may be used individually by 1 type, and may use 2 or more types together. When the compound (2) is included, the compound (2) may be used alone or in combination of two or more. When the number of fluorine-containing ether compounds is two or more, the ratio can be arbitrarily determined.
  • R 1 and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, or a fluorinated group having 3 to 10 carbon atoms.
  • Examples of the alkyl group and the alkyl group having an etheric oxygen atom in the compound (2) include a linear structure, a branched structure, or a group having a partial cyclic structure (for example, a cycloalkylalkyl group).
  • R 1 and R 2 is a fluorinated alkyl group having 1 to 10 carbon atoms, a fluorinated cycloalkyl group having 3 to 10 carbon atoms, or 2 to 10 carbon atoms having one or more etheric oxygen atoms.
  • R 1 and R 2 may be the same or different.
  • the compound (2-A) in which both R 1 and R 2 are fluorinated alkyl groups having 1 to 10 carbon atoms, R 1 is a fluorinated alkyl group having 2 to 10 carbon atoms containing one or more etheric oxygen atoms, and R 2 is a fluorinated alkyl group of 1 to 10 carbon atoms and (2-B), R 1 Is preferably a compound (2-C) wherein R 1 is a fluorinated alkyl group having 1 to 10 carbon atoms and R 2 is an alkyl group having 1 to 10 carbon atoms, and the compound (2-A) and the compound (2-C) are preferably More preferred is compound (2-A).
  • the total number of carbon atoms in the compound (2) is preferably 4 to 10 and more preferably 4 to 8 from the viewpoint that the boiling point is too low when the amount is too small and the viscosity increases when the amount is too large.
  • the molecular weight of the compound (2) is preferably 150 to 800, more preferably 150 to 500, and particularly preferably 200 to 500 from the viewpoint that if the molecular weight is too small, the boiling point is too low, and if it is too large, the viscosity becomes high.
  • the number of etheric oxygen atoms in the compound (2) is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1. The number of etheric oxygen atoms in the compound (2) affects flammability.
  • the fluorine content is the ratio of the total mass of fluorine atoms to the molecular weight. Although the upper limit of fluorine content is not specifically limited, Usually, it is 80 mass% or less.
  • the compound (2) is preferably a compound in which both R 1 and R 2 are alkyl groups in which some of the hydrogen atoms of the alkyl group are fluorinated from the viewpoint of excellent solubility in a lithium salt liquid composition, A compound in which one or both ends of R 1 and R 2 are —CF 2 H is more preferable.
  • Specific examples of the compound (2-A) and the compound (2-B), and specific examples of the fluorine-containing ether compound other than the compound (2-A) and the compound (2-B) include, for example, WO2009 / And the compounds described in No. 133899 (paragraphs 0034 to 0041).
  • CF 3 CH 2 OCF 2 CHF 2 , CF 3 CH 2 has excellent solubility in a liquid composition of lithium salt, excellent flame retardancy, low viscosity, and low boiling point.
  • the group consisting of OCF 2 CHFCF 3 , CHF 2 CF 2 CH 2 OCF 2 CHF 2 , CH 3 CH 2 CH 2 OCF 2 CHF 2 , CH 3 CH 2 OCF 2 CHF 2 , and CHF 2 CF 2 CH 2 OCF 2 CHFCF 3 At least one selected from is preferred. In particular, at least one selected from the group consisting of CF 3 CH 2 OCF 2 CHF 2 , CHF 2 CF 2 CH 2 OCF 2 CHF 2 and CHF 2 CF 2 CH 2 OCF 2 CHFCF 3 is preferable.
  • Fluorine-containing chain carboxylic acid ester compound preferably includes the following compound (3) from the viewpoint of viscosity, boiling point, and the like, and more preferably includes only the compound (3).
  • a fluorine-containing chain carboxylic acid ester compound may be used individually by 1 type, and may use 2 or more types together.
  • the compound (3) may be used alone or in combination of two or more.
  • the ratio can be arbitrarily determined.
  • R 3 and R 4 are each independently an alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms, and one or both of R 3 and R 4 have 1 to 3 carbon atoms 3 is a fluorinated alkyl group.
  • Examples of the alkyl group and the fluorinated alkyl group in the compound (3) include a linear structure and a branched structure, respectively.
  • One or both of R 3 and R 4 is a fluorinated alkyl group having 1 to 3 carbon atoms. By making one or both of R 3 and R 4 a fluorinated alkyl group having 1 to 3 carbon atoms, the oxidation resistance and flame retardancy of the compound (3) are improved.
  • R 3 and R 4 may be the same or different.
  • R 3 is preferably a methyl group, an ethyl group, a difluoromethyl group, a trifluoromethyl group, a tetrafluoroethyl group, or a pentafluoroethyl group from the viewpoint of viscosity, boiling point, or availability of the compound, a difluoromethyl group, or A trifluoromethyl group is more preferred.
  • R 4 is a methyl group, an ethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trimethyl group, from the viewpoint of viscosity, boiling point, or availability of the compound.
  • a fluoroethyl group is preferred, a methyl group, an ethyl group, or a 2,2,2-trifluoroethyl group is more preferred, and a methyl group or an ethyl group is still more preferred.
  • the total number of carbon atoms in the compound (3) is preferably from 3 to 7, more preferably from 3 to 6, and even more preferably from 3 to 5 from the viewpoint that if the amount is too small, the boiling point is too low and if the amount is too large, the viscosity increases.
  • the molecular weight of the compound (3) is preferably from 100 to 300, more preferably from 100 to 250, and particularly preferably from 100 to 200 from the viewpoint that if the molecular weight is too small, the boiling point is too low, and if it is too large, the viscosity increases.
  • the fluorine content in the compound (3) is preferably 25% by mass or more, and more preferably 30% by mass or more from the viewpoint of improving flame retardancy. Although the upper limit of fluorine content is not specifically limited, Usually, it is 55 mass% or less.
  • the compound (3) include acetic acid (2,2,2-trifluoroethyl), methyl difluoroacetate, ethyl difluoroacetate, ethyl trifluoroacetate and the like. From the viewpoint of availability and battery performance such as cycle characteristics, methyl difluoroacetate or ethyl trifluoroacetate is preferable.
  • Fluorine-containing chain carbonate compound preferably contains the following compound (4), more preferably only the compound (4), from the viewpoints of viscosity and boiling point.
  • a fluorine-containing chain carbonate compound may be used individually by 1 type, and may use 2 or more types together.
  • the compound (4) may be used alone or in combination of two or more.
  • the ratio can be arbitrarily determined.
  • R 5 and R 6 are each independently an alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms, and one or both of R 5 and R 6 are 3 is a fluorinated alkyl group.
  • Examples of the alkyl group and the fluorinated alkyl group in the compound (4) include a linear structure and a branched structure, respectively.
  • One or both of R 5 and R 6 is a fluorinated alkyl group having 1 to 3 carbon atoms. By making one or both of R 5 and R 6 a fluorinated alkyl group having 1 to 3 carbon atoms, the solubility and flame retardancy of the lithium salt are improved.
  • R 5 and R 6 may be the same or different.
  • the compound (4) is preferably a compound in which both R 5 and R 6 are fluorinated alkyl groups having 1 to 3 carbon atoms from the viewpoint of viscosity, boiling point, or availability of the compound.
  • R 5 and R 6 are preferably CF 3 CH 2 — or CHF 2 CF 2 CH 2 —.
  • the molecular weight of the compound (4) is preferably from 180 to 400, more preferably from 200 to 350, and particularly preferably from 210 to 300 from the viewpoint that if the molecular weight is too small, the boiling point is too low and if it is too large, the viscosity increases.
  • the fluorine content in the compound (4) is preferably 25% by mass or more, and more preferably 30% by mass or more from the viewpoint of improving flame retardancy. Although the upper limit of fluorine content is not specifically limited, Usually, it is 50 mass% or less.
  • the compound (4) include bis (2,2,2-trifluoroethyl) carbonate, bis (2,2,3,3-tetrafluoropropyl) carbonate and the like.
  • Bis (2,2,2-trifluoroethyl) carbonate is preferred from the viewpoint of battery performance such as viscosity, availability, and output characteristics.
  • the fluorine-containing solvent ( ⁇ ) may contain a fluorine-containing alkane compound as another fluorine-containing solvent.
  • a fluorine-containing alkane compound as another fluorine-containing solvent.
  • the fluorine-containing alkane compound is preferably a fluorine-containing alkane compound having 4 to 12 carbon atoms. If the fluorine-containing alkane compound has 4 or more carbon atoms, the vapor pressure of the non-aqueous electrolyte is lowered. When the fluorine-containing alkane compound has 12 or less carbon atoms, the lithium salt has good solubility.
  • the fluorine content in the fluorine-containing alkane compound is preferably 50 to 80% by mass. If the fluorine content in the fluorine-containing alkane compound is 50% by mass or more, the flame retardancy is excellent. If the fluorine content in the fluorine-containing alkane compound is 80% by mass or less, the solubility of the lithium salt is easily maintained.
  • fluorine-containing alkane compound a compound having a linear structure is preferable.
  • a fluorine-containing alkane compound may be used individually by 1 type, and may use 2 or more types together.
  • the liquid composition contains a cyclic carboxylic acid ester compound.
  • the lithium salt is uniformly dissolved in the fluorine-containing solvent ( ⁇ ).
  • the inclusion of the cyclic carboxylic acid ester compound makes it difficult for the non-aqueous electrolyte, the positive electrode, and the negative electrode to react with each other, making it difficult for thermal runaway in the secondary battery to occur.
  • the cyclic carboxylic acid ester compound may be one kind or two or more kinds.
  • cyclic carboxylic acid ester compound a saturated cyclic carboxylic acid ester compound having no carbon-carbon unsaturated bond in the molecule is preferable from the viewpoint of stability to redox reaction.
  • the ring structure in the cyclic carboxylic acid ester compound is preferably a 4- to 10-membered ring and more preferably a 4- to 7-membered ring from the viewpoints of structural stability and viscosity. From the viewpoint of availability, a 5- to 6-membered ring is more preferable, and a 5-membered ring is particularly preferable. From the viewpoint of easy availability, the total number of carbon atoms in the cyclic carboxylic acid ester compound is preferably 4 to 8, and more preferably 4 to 6.
  • the cyclic carboxylic acid ester compound is preferably composed of only a carbon atom, a hydrogen atom and an oxygen atom, and the portion other than the ester bond represented by the —C ( ⁇ O) —O— bond contained in the ring structure More preferably, it consists only of carbon atoms and hydrogen atoms.
  • the ring structure of the cyclic carboxylic acid ester compound is preferably a ring structure having one ester bond from the viewpoint of viscosity.
  • the cyclic carboxylic acid ester compound may be a compound in which one or more hydrogen atoms of the alkylene group are substituted with a substituent.
  • the substituent include a fluorine atom, a chlorine atom, an alkyl group, and a fluorinated alkyl group.
  • the carbon number of the alkyl group is preferably 1 or 2, and the carbon number of the fluorinated alkyl group is preferably 1 or 2.
  • the cyclic carboxylic acid ester compound preferably contains the following compound (5), and more preferably consists only of the compound (5), from the viewpoints of stability to redox reaction, structural stability, and viscosity.
  • R 7 to R 12 are each independently a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 2 carbon atoms, a fluorinated alkyl group having 1 to 2 carbon atoms, or one or more etheric oxygen atoms And an alkyl group having 2 to 3 carbon atoms.
  • n is an integer of 1 to 3.
  • R 7 to R 12 may be the same or different.
  • R 7 to R 12 are preferably a hydrogen atom, a methyl group, an ethyl group, or a fluorine atom from the viewpoint of stability to redox reaction, viscosity, and availability of the compound, and a hydrogen atom, a methyl group, or an ethyl group Is more preferable.
  • n is preferably 1 to 3 and more preferably 1 from the viewpoint of viscosity and availability of the compound.
  • Examples of the compound (5) include cyclic ester compounds such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -valerolactone, and ⁇ -caprolactone, and carbon atoms forming the ring of the cyclic ester compound.
  • 1 or more of the hydrogen atoms bonded to the carbon atom have a fluorine atom, a chlorine atom, an alkyl group having 1 to 2 carbon atoms, a fluorinated alkyl group having 1 to 2 carbon atoms, or one or more etheric oxygen atoms Examples thereof include compounds substituted with 2 to 3 alkyl groups.
  • the compound (5) is preferably at least one selected from the group consisting of ⁇ -butyrolactone, ⁇ -valerolactone and ⁇ -caprolactone from the viewpoint of easy availability and the effect of suppressing thermal runaway. Is more preferable.
  • Compound ( ⁇ ) Since the liquid composition has excellent lithium salt solubility and ionic conductivity, a saturated cyclic carbonate compound, a saturated chain carbonate compound having no fluorine atom (hereinafter also referred to as a non-fluorine-based saturated chain carbonate compound), It is preferable to further contain at least one compound ( ⁇ ) selected from the group consisting of saturated cyclic sulfone compounds (excluding lithium salts) and phosphate ester compounds.
  • saturated cyclic carbonate compound examples include propylene carbonate (PC), ethylene carbonate (EC), 4-fluoro-1,3-dioxolan-2-one (FEC), and the like.
  • non-fluorinated saturated chain carbonate compound examples include dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and the like.
  • saturated cyclic sulfone compound examples include sulfolane and 3-methylsulfolane.
  • phosphate ester compound examples include trimethyl phosphate, triethyl phosphate, and tris phosphate (2,2,2-trifluoroethyl).
  • the liquid composition preferably contains a non-fluorinated saturated chain carbonate compound.
  • the non-fluorinated saturated chain carbonate compound is included, the viscosity of the non-aqueous electrolyte can be lowered, and the lithium ion diffusion coefficient in the non-aqueous electrolyte and the ionic conductivity of the non-aqueous electrolyte are easily increased.
  • the non-aqueous electrolyte is a compound other than the lithium salt, the fluorine-containing solvent ( ⁇ ), the cyclic carboxylic acid ester compound, and the compound ( ⁇ ) as necessary, as long as the effects of the present invention are not impaired. , Additives, etc.).
  • the nonaqueous electrolytic solution may contain a solvent other than the fluorine-containing solvent ( ⁇ ), the cyclic carboxylic acid ester compound and the compound ( ⁇ ).
  • the non-aqueous electrolyte may contain conventionally known additives as necessary.
  • the additive include an overcharge inhibitor, a dehydrating agent, a deoxidizing agent, a property improving aid, and a surfactant.
  • Overcharge prevention agent examples include aromatic compounds (biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran, etc.), aromatic Partially fluorinated compounds (2-fluorobiphenyl, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene, etc.), fluorine-containing anisole compounds (2,4-difluoroanisole, 2,5-difluoroanisole, 2,6-difluoroanisole) All).
  • An overcharge inhibitor may be used individually by 1 type, and may use 2 or more types together.
  • Dehydrating agent examples include molecular sieves, mirabilite, magnesium sulfate, calcium hydride, sodium hydride, potassium hydride, lithium aluminum hydride and the like.
  • the liquid composition or other solvent used for the non-aqueous electrolyte those obtained by rectification after dehydration with a dehydrating agent are preferable. Moreover, what performed only the dehydration by the said dehydrating agent without performing rectification may be used.
  • the characteristic improving aid is for improving capacity maintenance characteristics and cycle characteristics after high temperature storage.
  • Examples of the property improving aid include unsaturated carbonate compounds (vinylene carbonate (VC), vinyl ethylene carbonate (VEC), 4-ethynyl-1,3-dioxolan-2-one, etc.), sulfur-containing compounds (ethylene sulfite).
  • a characteristic improvement adjuvant may be used individually by 1 type, and may use 2 or more types together.
  • the surfactant assists the impregnation of the non-aqueous electrolyte into the electrode mixture or separator.
  • the surfactant any of cationic surfactants, anionic surfactants, nonionic surfactants and amphoteric surfactants may be used.
  • Anionic surfactants are easily available and have a high surfactant effect. Agents are preferred.
  • a fluorine-containing surfactant is preferable from the viewpoint of high oxidation resistance and good cycle characteristics and rate characteristics. Only one surfactant may be used, or two or more surfactants may be used.
  • the upper limit value of the lithium salt content in the non-aqueous electrolyte is not particularly limited, but is preferably 1.5 mol / L, more preferably 1.4 mol / L, and still more preferably 1.3 mol / L.
  • the lower limit of the content of the lithium salt in the nonaqueous electrolytic solution is not particularly limited, but is preferably 0.7 mol / L, more preferably 0.8 mol / L, and still more preferably 0.9 mol / L.
  • the ratio of the mass of the lithium salt to the total mass of the non-aqueous electrolyte is preferably 5 to 20% by mass, more preferably 7 to 17% by mass, and even more preferably 9 to 14% by mass. If the ratio of lithium salt is more than the said lower limit, the ionic conductivity of a non-aqueous electrolyte will become high. If the proportion of the lithium salt is not more than the above upper limit value, the lithium salt is easily dissolved uniformly in the liquid composition, and the lithium salt does not precipitate even under low temperature conditions. Further, lithium ions are easily diffused into the non-aqueous electrolyte, and the lithium ion diffusion coefficient is increased.
  • the nonaqueous electrolytic solution of the present invention preferably contains at least LiPF 6 as a lithium salt.
  • the molar ratio of LiPF 6 to the total number of moles of lithium salt contained in the nonaqueous electrolytic solution is preferably 40 to 100 mol%, more preferably 50 to 100 mol%, still more preferably 65 to 100 mol%, and more preferably 80 to 100 mol%. Particularly preferred.
  • the molar ratio of LiPF 6 with respect to the total number of moles of lithium salt is equal to or more than the lower limit value, a nonaqueous electrolytic solution having excellent ion conductivity and high practicality is obtained.
  • the ratio of the mass of the fluorinated solvent ( ⁇ ) to the total mass of the nonaqueous electrolytic solution is not particularly limited, but the lower limit of the mass ratio of the fluorinated solvent ( ⁇ ) to the total mass of the nonaqueous electrolytic solution is 30% by mass. Is preferable, 40 mass% is more preferable, and 45 mass% is still more preferable.
  • the upper limit of the proportion of the fluorinated solvent ( ⁇ ) is preferably 80% by mass, more preferably 75% by mass, still more preferably 73% by mass, and particularly preferably 70% by mass.
  • the ratio of the fluorine-containing solvent ( ⁇ ) is at least the lower limit, the non-aqueous electrolyte has excellent flame retardancy, small positive electrode reactivity and negative electrode reactivity, hardly causes thermal runaway, and has high voltage resistance. Have. Moreover, elution of the metal component from an electrode can be suppressed.
  • the proportion of the fluorinated solvent ( ⁇ ) is not more than the above upper limit value, the lithium salt is uniformly dissolved and the lithium salt is unlikely to precipitate at a low temperature.
  • the ratio of the mass of the fluorinated solvent ( ⁇ ) to the total mass of the liquid composition is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, further preferably 40 to 80% by mass, and 45 to 75% by mass. Is particularly preferred. If the ratio of the fluorine-containing solvent ( ⁇ ) is at least the lower limit, the non-aqueous electrolyte has excellent flame retardancy, small positive electrode reactivity and negative electrode reactivity, hardly causes thermal runaway, and has high voltage resistance. Have. When the proportion of the fluorinated solvent ( ⁇ ) is not more than the above upper limit value, the lithium salt is uniformly dissolved and the lithium salt is unlikely to precipitate at a low temperature.
  • the fluorine-containing solvent ( ⁇ ) preferably contains a fluorine-containing ether compound from the viewpoint of the solubility of the lithium salt, the flame retardancy of the non-aqueous electrolyte, and the ionic conductivity.
  • the ratio of the mass of the fluorinated ether compound to the total mass of the fluorinated solvent ( ⁇ ) is preferably 25 to 100% by mass, more preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and 60 to 100% by mass. % Is more preferable, and 70 to 100% by mass is particularly preferable.
  • the fluorine-containing solvent ( ⁇ ) is most preferably composed of only a fluorine-containing ether compound.
  • the ratio of the mass of the fluorinated ether compound to the total mass of the non-aqueous electrolyte is preferably 10 to 80% by mass.
  • the lower limit of the proportion of the fluorine-containing ether compound is more preferably 20% by mass, further preferably 30% by mass, and particularly preferably 45% by mass.
  • the upper limit of the ratio of the fluorine-containing ether compound is more preferably 75% by mass, still more preferably 73% by mass, and particularly preferably 70% by mass.
  • the ratio of the mass of the fluorinated chain carboxylic acid ester compound to the total mass of the fluorinated solvent ( ⁇ ) is 0.01 to 50% by mass. Is preferably 0.01 to 40% by mass, more preferably 0.01 to 30% by mass, and particularly preferably 0.01 to 20% by mass.
  • the ratio of the mass of the fluorine-containing chain carbonate compound to the total mass of the fluorine-containing solvent ( ⁇ ) is preferably 0.01 to 50% by mass, 0.01 to 40% by mass is more preferable, 0.01 to 30% by mass is still more preferable, and 0.01 to 20% by mass is particularly preferable.
  • the ratio of the mass of the fluorinated alkane compound to the total mass of the nonaqueous electrolytic solution is preferably from 0.01 to 5% by mass. If the ratio of a fluorine-containing alkane compound is 0.01 mass% or more, it will be excellent in the flame retardance of a non-aqueous electrolyte. When the proportion of the fluorinated alkane is 5% by mass or less, the solubility of the lithium salt is easily maintained.
  • the fluorine-containing solvent ( ⁇ ) When the fluorine-containing solvent ( ⁇ ) is used in combination with one or more fluorine-containing ether compounds and one or more fluorine-containing chain carboxylic acid esters, fluorine-containing chain carbonate compounds, and fluorine-containing alkane compounds, the ratio thereof is arbitrary. I can decide.
  • the ratio of the mass of the cyclic carboxylic acid ester compound to the total mass of the non-aqueous electrolyte is preferably 4 to 50% by mass, more preferably 7 to 45% by mass, further preferably 10 to 40% by mass, and 15 to 35% by mass. Is particularly preferred. If the ratio of the cyclic carboxylic acid ester compound is equal to or more than the lower limit, the non-aqueous electrolyte uniformly dissolves the lithium salt, and the reactivity between the non-aqueous electrolyte and the positive and negative electrodes is small, causing thermal runaway. Hateful.
  • the non-aqueous electrolyte is excellent in flame retardancy.
  • the ratio of the weight of the cyclic carboxylic acid ester to the total weight of the liquid composition is preferably 4 to 60% by weight, more preferably 7 to 50% by weight, still more preferably 10 to 45% by weight, and particularly preferably 15 to 40% by weight. preferable.
  • the ratio of the cyclic carboxylic acid ester is not less than the lower limit, the liquid composition has excellent solubility, small positive electrode reactivity and negative electrode reactivity, hardly causes thermal runaway, and has high voltage resistance. If the ratio of cyclic carboxylic acid ester is below the said upper limit, a liquid composition will be excellent in a flame retardance.
  • the ratio N A / N Li of the total number of moles N A cyclic carboxylic acid ester compound to the total number of moles N Li of lithium atoms from the lithium salt is not particularly limited, 1.5 to 7.0 is preferred.
  • the lower limit value of the N A / N Li is more preferably 2, more preferably 2.5, and particularly preferably 3.
  • 6.5 is preferable, as for the upper limit of said N A / N Li , 6 is more preferable, 5 is still more preferable, 4.5 is especially preferable, and 4.2 is the most preferable.
  • N A / N Li is within the above range, the reactivity between the non-aqueous electrolyte and the positive and negative electrodes can be reduced while dissolving the lithium salt uniformly to obtain sufficient ionic conductivity for the following reasons.
  • the thermal runaway of the secondary battery can be suppressed.
  • the cyclic carboxylic acid ester compound forms a stable film on the electrode active material, particularly in the positive electrode, and the reaction between the electrode and the non-aqueous electrolyte is suppressed by the film. In connection with this, it is estimated that thermal runaway is suppressed. If N A / N Li is equal to or greater than the lower limit, the non-aqueous electrolyte contains a sufficient amount of the cyclic carboxylic acid ester compound, so that the coating is sufficiently formed and the reaction between the electrode and the non-aqueous electrolyte is suppressed. It is considered that a sufficient effect of suppressing thermal runaway can be obtained by sufficiently exhibiting the effect.
  • the cyclic carboxylic acid ester compound has a high affinity with the lithium salt, and is considered to promote the dissolution of the lithium salt in a solvent.
  • N A / N Li is equal to or higher than the lower limit, the lithium salt is sufficiently dissolved in the solvent, and an electrolytic solution having practically sufficient ionic conductivity is easily obtained.
  • fluorine-containing compounds such as fluorine-containing ether compounds, fluorine-containing chain carboxylic acid ester compounds, and fluorine-containing chain carbonate compounds are considered to have low affinity with lithium salts, and promote dissolution of lithium salts in solvents. The effect of doing this tends to be very small.
  • the film formed on the electrode active material is considered to be easily dissolved in a highly polar solvent, and even if a film is formed in a solvent having a high polarity, the film formation is likely to be insufficient. Presumed. If N A / N Li is not more than the above upper limit, the content of the cyclic carboxylic acid ester compound in the non-aqueous electrolyte does not become excessive, and the polarity of the entire non-aqueous electrolyte is within an appropriate range, It is considered that dissolution of the film formed on the electrode active material hardly occurs. By maintaining a sufficient coating on the electrode active material, an exothermic reaction between the electrode and the non-aqueous electrolyte is unlikely to occur, and thermal runaway is unlikely to occur.
  • fluorine-containing compounds such as a fluorine-containing ether compound, a fluorine-containing chain carboxylic acid ester compound, and a fluorine-containing chain carbonate compound are low in polarity, and thus the effect of dissolving the coating is considered to be very low.
  • the flame retardance of a non-aqueous electrolyte improves also by reducing content of the highly flammable cyclic carboxylic acid ester compound.
  • the ratio of the mass of the compound ( ⁇ ) to the total mass of the nonaqueous electrolytic solution is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass. . If the ratio of a compound ((beta)) is below the said upper limit, it will be easy to suppress reaction with a compound ((beta)) and an electrode, and the nonaqueous electrolyte solution excellent in stability will be obtained. Moreover, since content of a fluorine-containing solvent ((alpha)) can be increased, the nonaqueous electrolyte solution excellent in the flame retardance is easy to be obtained.
  • the ratio of the mass of the saturated cyclic carbonate compound to the total mass of the nonaqueous electrolytic solution is preferably 0.01 to 20% by mass, more preferably 0.01 to 15% by mass. 0.01 to 10% by mass is more preferable, and 0.01 to 5% by mass is particularly preferable. If the ratio of a saturated cyclic carbonate compound is below the said upper limit, a saturated cyclic carbonate compound and an electrode will be hard to react, a nonaqueous electrolyte solution is excellent in stability, and is excellent in a flame retardance.
  • the ratio of the mass of the non-fluorinated saturated chain carbonate compound to the total mass of the non-aqueous electrolyte is preferably 0.01 to 30% by mass. More preferably, the content is 01 to 20% by mass, and further preferably 0.01 to 15% by mass. If the proportion of the non-fluorinated saturated chain carbonate compound is less than or equal to the above upper limit, the non-fluorinated saturated chain carbonate compound and the electrode are less likely to react, and the non-aqueous electrolyte is excellent in stability and flame retardancy. .
  • the ratio of the total mass of the saturated cyclic carbonate compound and the non-fluorinated saturated chain carbonate compound to the total mass of the non-aqueous electrolyte is: 0.01 to 30% by mass is preferable, 0.01 to 20% by mass is more preferable, and 0.01 to 15% by mass is still more preferable.
  • the ratio of the total mass is equal to or less than the upper limit, even when a saturated cyclic carbonate compound and a non-fluorinated saturated chain carbonate compound are used, The dissolution of the coating can be suppressed, the reactivity between them and the electrode can be kept low, and it is easy to obtain a non-aqueous electrolyte with excellent stability. Moreover, it is easy to set it as the non-aqueous electrolyte which has the outstanding flame retardance by restraining content of a combustible compound low.
  • the ratio of the mass of the saturated cyclic sulfone compound to the total mass of the nonaqueous electrolytic solution is preferably 0.01 to 20% by mass, more preferably 0.01 to 15% by mass. 0.01 to 10% by mass is more preferable, and 0.01 to 5% by mass is particularly preferable. If the ratio of the saturated cyclic sulfone compound is not more than the above upper limit value, the saturated cyclic sulfone compound and the electrode are unlikely to react with each other, and the non-aqueous electrolyte is excellent in stability and flame retardancy.
  • the ratio of the mass of the phosphate ester compound to the total mass of the non-aqueous electrolyte is preferably 0.01 to 5% by mass.
  • the proportion of the phosphate ester compound is equal to or less than the upper limit, the phosphate ester compound and the electrode are difficult to react, and the non-aqueous electrolyte is excellent in stability and flame retardancy.
  • the ratio of the mass of the cyclic carboxylic acid ester compound to the total mass of the cyclic carboxylic acid ester compound and the compound ( ⁇ ) is preferably 30 to 100% by mass, and 35 to 100% by mass. Is more preferably 40 to 100% by mass, still more preferably 45 to 100% by mass, and particularly preferably 50 to 100% by mass.
  • the ratio of the cyclic carboxylic acid ester compound is within the above range, the reactivity between the non-aqueous electrolyte, the positive electrode, and the negative electrode can be reduced, and thermal runaway of the secondary battery can be suppressed.
  • liquid composition comprising the compound (beta), to the total mole number N Li of lithium atoms from the lithium salt, the total number of moles N A and the compound of the cyclic carboxylic acid ester compound with total number of moles N B of (beta)
  • the sum ratio (N A + N B ) / N Li is preferably 3.0 to 7.0.
  • the lower limit of the (N A + N B) / N Li is more preferably 3.2, 3.5 is more preferable.
  • the upper limit of (N A + N B) / N Li is more preferably 6.8, more preferably 6.5.
  • the compound ( ⁇ ) has a high affinity with the lithium salt similarly to the cyclic carboxylic acid ester compound, and is considered to have an effect of promoting dissolution of the lithium salt in a solvent.
  • (N A + N B ) / N Li is not less than the above lower limit, that is, the total amount of the cyclic carboxylic acid ester compound and the compound ( ⁇ ), which is considered to have a high lithium salt dissolution promoting effect, is a certain amount or more with respect to the amount of the lithium salt If the lithium salt solubility in the fluorine-containing solvent ( ⁇ ) is improved, the ionic conductivity of the nonaqueous electrolytic solution is improved, and in particular, when a lithium salt such as LiPF 6 that is difficult to dissolve in the fluorine-based solvent is used. Can be dissolved in a fluorine-based solvent, and practically sufficient ionic conductivity is easily obtained.
  • the ratio of the total mass of the other solvent and the compound ( ⁇ ) to the total mass of the non-aqueous electrolyte is preferably 0.01 to 30 mass, and preferably 0.1 to 20 The mass% is more preferable. If the ratio of the total mass of the other solvent and the compound ( ⁇ ) is less than or equal to the above upper limit value, it is easy to suppress the reaction between the other solvent and the compound ( ⁇ ) and the electrode, and the nonaqueous electrolyte solution is excellent in stability. Is obtained. Moreover, since content of a fluorine-containing solvent ((alpha)) can be increased, the nonaqueous electrolyte solution excellent in the flame retardance is easy to be obtained.
  • the ratio of the mass of the nitrile compound to the total mass of the non-aqueous electrolyte is less reactive with the positive electrode and the negative electrode, and is less likely to cause thermal runaway 10 mass% or less is preferable from the point which becomes easy to obtain a liquid, 5 mass% or less is more preferable, and 3 mass% or less is still more preferable.
  • the ratio of the mass of the ether compound having no fluorine atom to the total mass of the nonaqueous electrolyte is more reactive with the positive electrode and the negative electrode. From the viewpoint that it is easy to obtain a nonaqueous electrolyte solution that is low and hardly causes thermal runaway, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less.
  • the ratio of the mass of the overcharge inhibitor to the total mass of the non-aqueous electrolyte is preferably 0.01 to 5% by mass.
  • the ratio of the overcharge inhibitor is within the above range, it becomes easier to suppress the secondary battery from bursting and firing due to overcharge, and the secondary battery can be used more stably.
  • the ratio of the mass of the characteristic improving auxiliary to the total mass of the non-aqueous electrolytic solution is preferably 0.01 to 5% by mass.
  • the ratio of the mass of the surfactant to the total mass of the non-aqueous electrolyte is preferably 0.05 to 5% by mass, more preferably 0.05 to 3% by mass, More preferably, it is 0.05 to 2% by mass.
  • a separator is interposed between the positive electrode and the negative electrode to prevent a short circuit.
  • An example of the separator is a porous film.
  • a non-aqueous electrolyte is used by impregnating the porous membrane.
  • you may use as a gel electrolyte what impregnated the porous film with the nonaqueous electrolyte solution, and was made to gelatinize.
  • porous film one that is stable with respect to the non-aqueous electrolyte and excellent in liquid retention can be used.
  • a porous film a porous sheet or a nonwoven fabric is preferable.
  • porous membrane materials include fluororesins (polyvinylidene fluoride, polytetrafluoroethylene, copolymers of ethylene and tetrafluoroethylene, etc.), polyimides, polyolefins (polyethylene, polypropylene, etc.), oxidation resistance, air permeability From the viewpoint of availability, polyolefin is preferred.
  • Examples of the material for the battery outer package include nickel-plated iron, stainless steel, aluminum or an alloy thereof, nickel, titanium, a resin material, and a film material.
  • the shape of the nonaqueous electrolyte secondary battery of the present invention may be selected according to the application, and may be any shape such as a coin shape, a cylindrical shape, a square shape, and a laminate shape. Moreover, the shape of a positive electrode and a negative electrode can be suitably selected according to the shape of a secondary battery.
  • the open circuit voltage in the fully charged state per pair of positive electrode and negative electrode of the nonaqueous electrolyte secondary battery of the present invention is preferably 4.2 V or higher, more preferably 4.3 V or higher from the viewpoint of obtaining a high battery capacity. 4.35V or more is more preferable.
  • a specific positive electrode containing the compound (1), a specific non-aqueous electrolyte containing a fluorine-containing solvent ( ⁇ ) and a cyclic carboxylic acid ester compound Therefore, excellent cycle characteristics can be obtained even at a high voltage, and further, the amount of metal elution from the positive electrode can be reduced.
  • the non-aqueous electrolyte containing a fluorine-containing solvent ( ⁇ ) and a cyclic carboxylic acid ester compound has high flame retardancy, low reactivity with the electrode, and excellent thermal stability. For these reasons, the nonaqueous electrolyte secondary battery of the present invention is unlikely to cause thermal runaway.
  • AE3000 CF 3 CH 2 OCF 2 CHF 2 (trade name: AE-3000, manufactured by Asahi Glass Co., Ltd.), HFE458: CHF 2 CF 2 CH 2 OCF 2 CHF 2, HFE5510: CHF 2 CF 2 CH 2 OCF 2 CHFCF 3.
  • Metal dissolution evaluation 1. Metal dissolution test (A) The evaluation cell is installed in a thermostatic chamber maintained at 25 ° C., connected to a charger / discharger, and constant current charging is performed up to 3.4 V (cell voltage, the same shall apply hereinafter) at a constant current corresponding to 0.02 C. After the charging, the battery was charged to 4.2 V with a constant current corresponding to 0.2 C, and the constant voltage charging was continued until the charging current reached a current value of 0.02 C. The battery was discharged to 3.0 V with a constant current corresponding to 0.2C.
  • 1C means the amount of current that discharges the reference capacity of the battery in one hour.
  • the negative electrode was collected from the evaluation cell, washed with dimethyl carbonate, and then vacuum dried to obtain an evaluation sample.
  • the prepared negative electrode sample surface is observed by X-ray photoelectron spectroscopic analysis without exposure to air (measurement device ULVAC-PHI 5500, using transfer vessel), and the amount of Co deposited is determined to evaluate the amount of Co elution from the positive electrode. did.
  • Metal dissolution test (B) The evaluation cell is placed in a thermostatic chamber maintained at 25 ° C., and charged and discharged five times at a constant current corresponding to 0.2 C by the same method as the fifth cycle of the metal elution evaluation test (A). It was. Thereafter, the evaluation cell was moved into a thermostat kept at 50 ° C., connected to a charger / discharger, and charged with constant current up to 4.2 V at a constant current corresponding to 0.2 C. Charging was continued for 120 hours. Then, it discharged to 3.0V with the constant current equivalent to 0.2C. Subsequently, the elution amount of Co was evaluated by the same analysis method as in the metal elution evaluation test (A).
  • Metal dissolution test (C) The amount of Co elution was evaluated in the same manner as the metal elution test (B) except that the charging potential was changed to 4.35V.
  • Thermal stability evaluation 1. Thermal stability test (D) The following charging / discharging cycle was implemented about the cell for evaluation. In cycles 1 to 4, constant current charging was performed up to 4.2 V at a current corresponding to 0.5 C, and constant voltage charging was performed until the charging current reached a current value of 0.02 C. Then, constant current discharge was performed to 3.0V with the electric current equivalent to 0.2C. In cycle 5, constant current charging was performed up to 4.2 V at a current corresponding to 0.5 C, and further constant voltage charging was performed until the charging current reached a current value of 0.02 C. Thereafter, the obtained evaluation cell for a charged state was decomposed under an argon atmosphere to obtain a charged positive electrode.
  • the obtained positive electrode was washed three times with dimethyl carbonate (2 mL), vacuum-dried, then punched out to a diameter of 5 mm, placed in a sealed container made of SUS, and further, the nonaqueous electrolyte solution in each example (in the evaluation cell) 2 ⁇ L of the same as the non-aqueous electrolyte solution) was added and sealed to obtain an evaluation sample.
  • Each of the obtained evaluation samples was measured with a differential scanning calorimeter (DSC-6000 manufactured by SII Nano Technology) at a temperature range of 50 to 350 ° C. and a heating rate of 5 ° C./min.
  • the evaluation was performed based on the following criteria, with the temperature at the top of the exothermic peak appearing at the lowest temperature among the exothermic peaks exceeding 1 mW based on the calorific value at 70 ° C. in the above measurement. It was. (Excellent): Exothermic peak temperature is 300 ° C. or higher. ⁇ (good): Exothermic peak temperature is 250 ° C. or higher and lower than 300 ° C. ⁇ (defect): Exothermic peak temperature is 200 ° C. or higher and lower than 250 ° C. X (very poor): Exothermic peak temperature is less than 200 ° C.
  • Thermal stability test (E) The thermal stability was evaluated in the same manner as the thermal stability test (D) except that the charging potential was changed to 4.5V.
  • the evaluation cell was installed in a thermostatic chamber maintained at 25 ° C., connected to a charger / discharger, and charged with a constant current up to 3.4 V (cell voltage, the same shall apply hereinafter) with a constant current corresponding to 0.02 C. After that, charging was performed to a potential shown in Table 1 with a constant current corresponding to 0.2 C, and constant voltage charging was continued until the charging current reached a current value of 0.02 C. The battery was discharged to 3.0 V with a constant current corresponding to 0.2C.
  • Example 1 Manufacture of positive electrode
  • Magnesium carbonate (1.94 g) an aluminum maleate aqueous solution (20.93 g) having an Al content of 2.65% by mass, and citric acid monohydrate (7.20 g) were mixed with water (29.93 g).
  • aqueous solution Co content is 60.0% by mass
  • average particle size D50 particle size distribution on a volume basis, particle size at the point where the cumulative curve is 50% in the cumulative curve with the total volume being 100%
  • the obtained mixture was dried in a thermostatic bath at 80 ° C., mixed with lithium carbonate (77.08 g) having a Li content of 18.7% by mass in a mortar, and then fired at 990 ° C. for 14 hours in an oxygen-containing atmosphere. did.
  • the composition of the obtained fired product was Li 1.005 Co 0.975 Mg 0.01 Al 0.01 O 2 .
  • the fired product was crushed to obtain a lithium-containing composite oxide powder.
  • an aqueous solution of pH 8.5 obtained by diluting an aqueous zirconium carbonate carbonate solution (1.28 g) with a Zr content of 14.5 mass% with water (48.27 g), The mixture was dried at 120 ° C.
  • the obtained powder was calcined at 500 ° C. for 12 hours in an oxygen-containing atmosphere to obtain compound (1-1).
  • the composition of the obtained compound (1-1) was Li 1.004 Co 0.974 Mg 0.01 Al 0.01 Zr 0.001 O 2 .
  • the obtained compound (1-1) (10.0 g) and carbon black (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “Denka Black”, 1.25 g) are mixed, and a rotating and rotating stirrer (manufactured by Shinky Corporation) is mixed.
  • the process of stirring for 1 minute at a rotational speed of 2000 rpm was performed three times using Awatori Nerita AR-E310).
  • the step of adding N-methyl-2-pyrrolidone (10.0 g) and stirring for 3 minutes at 2000 rpm using the stirrer was performed three times.
  • N-methyl-2-pyrrolidone (2.2 g) and stirring for 3 minutes at a rotational speed of 2000 rpm using the agitator was performed three times. Further, an N-methyl-2-pyrrolidone solution of polyvinylidene fluoride (11% by mass, 10.3 g) was added and stirred for 1 minute at a rotational speed of 2000 rpm using the stirrer to obtain a slurry. The slurry was applied to an aluminum foil having a thickness of 20 ⁇ m to a thickness of 200 ⁇ m, dried, and then punched into a circle having a diameter of 18 mm to obtain a positive electrode (an electrode for evaluation).
  • a styrene-butadiene rubber aqueous dispersion latex binder (0.26 g) adjusted to a solid content concentration of 40% by mass was stirred for 5 minutes at a rotational speed of 2000 rpm using the stirrer to obtain a slurry for electrode coating. .
  • the slurry was applied to a thickness of 150 ⁇ m on a copper foil having a thickness of 20 ⁇ m, dried, and then punched into a circle having a diameter of 19 mm to form a negative electrode.
  • a polypropylene microporous membrane was allowed to exist as a separator between the positive electrode and the negative electrode, and 0.5 mL of the non-aqueous electrolyte was injected therein to produce an evaluation cell.
  • the obtained cell for evaluation was subjected to metal elution evaluation and thermal stability evaluation.
  • Examples 2 to 6 A nonaqueous electrolytic solution was prepared in the same manner as in Example 1 except that the composition of the liquid composition was changed as shown in Table 1. Further, an evaluation cell was produced in the same manner as in Example 1 except that the nonaqueous electrolytic solution was used. The obtained cell for evaluation was subjected to metal elution evaluation and thermal stability evaluation.
  • Table 1 shows the results of metal elution evaluation and thermal stability evaluation for each example.
  • 0 means that no Co elution is observed
  • + means that Co elution is observed.
  • “/” Means not implemented.
  • Example 1 in which the positive electrode containing the compound (1) and the nonaqueous electrolytic solution containing the fluorine-containing solvent ( ⁇ ) and the cyclic carboxylic acid ester compound were combined, the nonaqueous electrolytic solution Compared with Example 3 using EC and EMC, the amount of Co elution was reduced.
  • thermal stability was also superior to Example 3.
  • Example 6 in which the mass ratio of the fluorine-containing solvent ( ⁇ ) to the total mass of the non-aqueous electrolyte is less than 30% and (N A + N B ) / N Li exceeds 7 is excellent in thermal stability but elution of Co The reduction of was not seen.
  • Mass ratio of the fluorine-containing solvent (alpha) is 30% or more, it may be more preferably (N A + N B) / N Li is 7 or less.
  • Examples 7 to 14 A nonaqueous electrolytic solution was prepared in the same manner as in Example 1 except that the composition of the liquid composition was changed as shown in Table 2. Further, an evaluation cell was produced in the same manner as in Example 1 except that the nonaqueous electrolytic solution was used.
  • Example 15 and 16 A positive electrode active material (hereinafter referred to as compound (7)) was prepared in the same manner as in Example 1 except that magnesium carbonate, aluminum maleate aqueous solution, and zirconium ammonium carbonate aqueous solution were not used, and a positive electrode was obtained.
  • a non-aqueous electrolyte was prepared in the same manner as in Example 1 except that the composition of the liquid composition was changed as shown in Table 2. Further, an evaluation cell was produced in the same manner as in Example 1 except that the positive electrode and the non-aqueous electrolyte were used. About the obtained evaluation cell, the discharge capacity maintenance rate was measured. The results are shown in Table 3.
  • the lithium ion secondary battery of the present invention includes a mobile phone, a portable game machine, a digital camera, a digital video camera, an electric tool, a notebook computer, a portable information terminal, a portable music player, an electric vehicle, a hybrid vehicle, a train, an aircraft, an artificial It can be applied to various uses such as satellites, submarines, ships, uninterruptible power supplies, robots, and power storage systems.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • 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 concerne une batterie secondaire à électrolyte non aqueux permettant de conserver de bonnes propriétés de cycle y compris à une tension élevée, présentant une élution de métal davantage réduite à partir d'une électrode positive, une excellente stabilité thermique, et étant par là-même susceptible de présenter un emballement thermique, et présentant une résistance à la flamme élevée. La batterie secondaire à électrolyte non aqueux comporte l'électrode positive, une électrode négative, et un électrolyte non aqueux. L'électrode positive comprend un oxyde composite de métal de transition de lithium spécifique contenant Co. L'électrolyte non aqueux comprend un sel de lithium et une composition liquide. La composition liquide comprend : au moins un type de solvant (α) fluoré sélectionné dans un groupe constitué par un composé d'éther fluoré, un composé d'ester d'acide carboxylique à chaîne fluoré, et un composé de carbonate à chaîne fluoré ; et un composé d'ester d'acide carboxylique cyclique.
PCT/JP2014/075138 2013-09-24 2014-09-22 Batterie secondaire à électrolyte non aqueux WO2015046174A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015539221A JPWO2015046174A1 (ja) 2013-09-24 2014-09-22 非水電解液二次電池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-197591 2013-09-24
JP2013197591 2013-09-24

Publications (1)

Publication Number Publication Date
WO2015046174A1 true WO2015046174A1 (fr) 2015-04-02

Family

ID=52743310

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/075138 WO2015046174A1 (fr) 2013-09-24 2014-09-22 Batterie secondaire à électrolyte non aqueux

Country Status (2)

Country Link
JP (1) JPWO2015046174A1 (fr)
WO (1) WO2015046174A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106169610A (zh) * 2015-05-20 2016-11-30 三星电子株式会社 锂金属电池和用于锂金属电池的电解质
US9673450B2 (en) 2011-09-02 2017-06-06 Solvay Sa Lithium ion battery
US9979050B2 (en) 2011-09-02 2018-05-22 Solvay Sa Fluorinated electrolyte compositions
US10044066B2 (en) 2012-06-01 2018-08-07 Solvary SA Fluorinated electrolyte compositions
US10074874B2 (en) 2012-06-01 2018-09-11 Solvay Sa Additives to improve electrolyte performance in lithium ion batteries
US10686220B2 (en) 2013-04-04 2020-06-16 Solvay Sa Nonaqueous electrolyte compositions
CN111344891A (zh) * 2017-11-10 2020-06-26 三菱化学株式会社 非水电解液及使用该非水电解液的能量设备
CN114976242A (zh) * 2021-05-28 2022-08-30 远景动力技术(江苏)有限公司 一种电化学装置和电子装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008192504A (ja) * 2007-02-06 2008-08-21 Daikin Ind Ltd 非水系電解液
JP2009508304A (ja) * 2005-09-08 2009-02-26 スリーエム イノベイティブ プロパティズ カンパニー 電解質組成物
JP2009212021A (ja) * 2008-03-06 2009-09-17 Hitachi Maxell Ltd 電気化学素子用電極、非水二次電池および電池システム
JP2011181527A (ja) * 2005-11-02 2011-09-15 Agc Seimi Chemical Co Ltd リチウム含有複合酸化物
WO2013073633A1 (fr) * 2011-11-16 2013-05-23 Ａｇｃセイミケミカル株式会社 Procédé pour produire un oxyde composite contenant du lithium
WO2013146359A1 (fr) * 2012-03-27 2013-10-03 旭硝子株式会社 Solution d'électrolyte non aqueux pour batteries secondaires et batterie secondaire au lithium-ion

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009508304A (ja) * 2005-09-08 2009-02-26 スリーエム イノベイティブ プロパティズ カンパニー 電解質組成物
JP2011181527A (ja) * 2005-11-02 2011-09-15 Agc Seimi Chemical Co Ltd リチウム含有複合酸化物
JP2008192504A (ja) * 2007-02-06 2008-08-21 Daikin Ind Ltd 非水系電解液
JP2009212021A (ja) * 2008-03-06 2009-09-17 Hitachi Maxell Ltd 電気化学素子用電極、非水二次電池および電池システム
WO2013073633A1 (fr) * 2011-11-16 2013-05-23 Ａｇｃセイミケミカル株式会社 Procédé pour produire un oxyde composite contenant du lithium
WO2013146359A1 (fr) * 2012-03-27 2013-10-03 旭硝子株式会社 Solution d'électrolyte non aqueux pour batteries secondaires et batterie secondaire au lithium-ion

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9673450B2 (en) 2011-09-02 2017-06-06 Solvay Sa Lithium ion battery
US9979050B2 (en) 2011-09-02 2018-05-22 Solvay Sa Fluorinated electrolyte compositions
US10074874B2 (en) 2012-06-01 2018-09-11 Solvay Sa Additives to improve electrolyte performance in lithium ion batteries
US10044066B2 (en) 2012-06-01 2018-08-07 Solvary SA Fluorinated electrolyte compositions
US10916805B2 (en) 2013-04-04 2021-02-09 Solvay Sa Nonaqueous electrolyte compositions
US10686220B2 (en) 2013-04-04 2020-06-16 Solvay Sa Nonaqueous electrolyte compositions
US9831529B2 (en) 2015-05-20 2017-11-28 Samsung Electronics Co., Ltd. Lithium metal battery
CN106169610A (zh) * 2015-05-20 2016-11-30 三星电子株式会社 锂金属电池和用于锂金属电池的电解质
CN106169610B (zh) * 2015-05-20 2021-01-15 三星电子株式会社 锂金属电池和用于锂金属电池的电解质
EP3118917A1 (fr) * 2015-05-20 2017-01-18 Samsung Electronics Co., Ltd. Batterie au métal lithium et électrolyte
CN111344891A (zh) * 2017-11-10 2020-06-26 三菱化学株式会社 非水电解液及使用该非水电解液的能量设备
US11631895B2 (en) 2017-11-10 2023-04-18 Mitsubishi Chemical Corporation Nonaqueous electrolyte solution and energy device using same
CN114976242A (zh) * 2021-05-28 2022-08-30 远景动力技术(江苏)有限公司 一种电化学装置和电子装置
CN114976242B (zh) * 2021-05-28 2024-01-26 远景动力技术(江苏)有限公司 一种电化学装置和电子装置

Also Published As

Publication number Publication date
JPWO2015046174A1 (ja) 2017-03-09

Similar Documents

Publication Publication Date Title
JP6428631B2 (ja) 二次電池用非水電解液及びリチウムイオン二次電池
JP6299603B2 (ja) 二次電池用非水電解液およびリチウムイオン二次電池
JP5488768B2 (ja) 二次電池用非水電解液およびリチウムイオン二次電池
WO2015046174A1 (fr) Batterie secondaire à électrolyte non aqueux
WO2012011507A1 (fr) Electrolyte non aqueux pour batteries secondaires, et batterie secondaire
WO2013183719A1 (fr) Solution d'électrolyte non aqueux pour batteries secondaires et batterie secondaire au lithium-ion
WO2015046171A1 (fr) Électrolyte liquide non aqueux pour utilisation dans une batterie secondaire, et batterie secondaire lithium-ion
JP2015069704A (ja) 二次電池用非水電解液およびリチウムイオン二次電池
JP2015064990A (ja) 二次電池用非水電解液およびリチウムイオン二次電池
JP2015069705A (ja) 二次電池用非水電解液およびリチウムイオン二次電池
WO2014128940A1 (fr) Solution d'électrolyte non aqueux pour batteries secondaires et batterie secondaire au lithium-ion
WO2015159824A1 (fr) Solution électrolytique non aqueuse pour batterie rechargeable, et batterie rechargeable au lithium-ion
JP2015065131A (ja) 二次電池用非水電解液およびリチウムイオン二次電池
JP2015065130A (ja) 二次電池用非水電解液およびリチウムイオン二次電池
JP2015064991A (ja) 二次電池用非水電解液およびリチウムイオン二次電池
JP2015069703A (ja) 二次電池用非水電解液およびリチウムイオン二次電池
JP2016038997A (ja) 非水電解液二次電池
WO2015046172A1 (fr) Batterie secondaire à électrolyte non aqueux
WO2012173253A1 (fr) Electrolyte non aqueux pour cellule secondaire et cellule secondaire
WO2012115112A1 (fr) Solution électrolytique non aqueuse pour pile secondaire et pile secondaire
JP2013101766A (ja) 二次電池用非水電解液および二次電池
JP2013045728A (ja) 非水電解液、リチウムイオン二次電池、及び、モジュール
JP2016039003A (ja) 非水電解液二次電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14847897

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015539221

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14847897

Country of ref document: EP

Kind code of ref document: A1