WO2013100081A1 - Solution d'électrolyte non aqueux et batterie secondaire à électrolyte non aqueux - Google Patents

Solution d'électrolyte non aqueux et batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2013100081A1
WO2013100081A1 PCT/JP2012/083949 JP2012083949W WO2013100081A1 WO 2013100081 A1 WO2013100081 A1 WO 2013100081A1 JP 2012083949 W JP2012083949 W JP 2012083949W WO 2013100081 A1 WO2013100081 A1 WO 2013100081A1
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general formula
carbonate
aqueous electrolyte
secondary battery
positive electrode
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PCT/JP2012/083949
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English (en)
Japanese (ja)
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川上　大輔
隆道 三井
竹原　雅裕
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三菱化学株式会社
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Priority to KR1020207007062A priority Critical patent/KR20200029625A/ko
Priority to KR1020207027342A priority patent/KR20200113013A/ko
Priority to JP2013551828A priority patent/JP6127980B2/ja
Priority to KR1020147017813A priority patent/KR102206695B1/ko
Priority to CN201280065277.1A priority patent/CN104025366A/zh
Priority to KR1020197014633A priority patent/KR102208587B1/ko
Publication of WO2013100081A1 publication Critical patent/WO2013100081A1/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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 electrolytic solution and a secondary battery including the non-aqueous electrolytic solution, and specifically includes a specific cyclic carbonate, a fluorinated cyclic carbonate, and a fluorinated chain carbonate, and the non-aqueous solvent contains the non-aqueous electrolytic solution.
  • the present invention relates to a nonaqueous electrolytic solution containing more than 20% by volume of cyclic carbonate.
  • a non-aqueous electrolyte solution containing a specific cyclic carbonate, a fluorinated cyclic carbonate, and a fluorinated chain carbonate, and containing more than 15% by volume of the cyclic carbonate in a non-aqueous solvent,
  • This relates to a non-aqueous electrolyte secondary battery whose upper limit operating potential is 4.5 V or more on the basis of Li / Li + .
  • Non-aqueous electrolyte secondary batteries such as lithium secondary batteries are widely used as power sources for so-called portable electronic devices such as mobile phones and notebook computers, to in-vehicle power sources for automobiles and large power sources for stationary applications. It is being put into practical use.
  • the demand for applied secondary batteries is increasing, and the high performance of the battery characteristics of secondary batteries is increasing. For example, it is required to achieve high levels of improvement in capacity, high temperature storage characteristics, cycle characteristics, and the like.
  • the non-aqueous electrolyte used for the non-aqueous electrolyte secondary battery is usually mainly composed of an electrolyte and a non-aqueous solvent.
  • the main components of the non-aqueous solvent include cyclic carbonates such as ethylene carbonate and propylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate; cyclic carboxylic acid esters such as ⁇ -butyrolactone and ⁇ -valerolactone. It is used.
  • Patent Document 3 describes a graphite negative electrode type 5.0 V class battery using a non-aqueous electrolyte mixed with 4,5-difluoroethylene carbonate obtained by fluorinating cyclic carbonate and ethylene carbonate. The effect of suppressing gas generation has been confirmed.
  • the battery characteristics only the improvement in the initial capacity and the initial load characteristics has been confirmed, and the durability battery characteristics are still unclear.
  • electrolytes composed only of such high-viscosity solvents usually not only significantly deteriorate battery characteristics at low temperatures in non-aqueous electrolytes, but also are difficult to handle at the time of injection, and the wettability of the separator is extremely high.
  • there are still problems such as low.
  • Patent Documents 4 and 5 as a technique for improving battery characteristics such as cycle characteristics in a 4.2 to 4.3 V battery based on a graphite negative electrode, that is, a battery having a positive electrode potential of approximately 4.35 V, ethylene carbonate, 4 -Techniques relating to mixed non-aqueous electrolytes of fluoroethylene carbonate and fluorinated chain carbonate are described.
  • Patent Document 6 describes a non-aqueous electrolyte solution in which ethylene carbonate, 4-fluoroethylene carbonate, and fluorinated chain carbonate are mixed for the purpose of suppressing gas generation with little cycle deterioration.
  • ethylene carbonate, 4-fluoroethylene carbonate, and fluorinated chain carbonate are mixed for the purpose of suppressing gas generation with little cycle deterioration.
  • Patent Document 6 only a technique relating to a battery using a low potential region of a specific LiCoO 2 positive electrode is disclosed in the examples.
  • the patent document does not disclose a technique for solving high temperature storage under a high voltage such that the upper limit operating potential of the positive electrode exceeds 4.35 V and deterioration in durability during cycling.
  • Patent Document 7 discloses a capacity deterioration suppression technique using a mixed solvent of cyclic carbonate, fluorinated cyclic carbonate, and fluorinated chain carbonate for a 4.3 V battery using a silicon negative electrode.
  • graphite negative electrodes exemplified as non-silicon negative electrodes only show significant capacity deterioration due to reductive decomposition of fluorinated cyclic carbonate, and this patent document discloses a technique for suppressing deterioration of silicon negative electrodes. Only the features are disclosed. Further, the patent document does not mention or suggest a high voltage battery exceeding 4.3V.
  • Patent Document 8 in a battery of 4.35 V or higher, a mixed solvent of cyclic carbonate, fluorinated cyclic carbonate, and fluorinated chain carbonate is used, and charge / discharge cycle characteristics at high temperature and low swelling due to high-temperature storage gas are reduced. Techniques to do this are disclosed. However, what is actually confirmed is the result at 4.4 V, and the characteristics in the region of higher voltage are not known.
  • the present invention solves the above-mentioned various problems that occur when trying to achieve the performance required for a secondary battery in recent years, and in particular, a low amount of generated gas in a battery having a high positive electrode upper limit operating potential.
  • Another object of the present invention is to provide a non-aqueous electrolyte secondary battery excellent in high-temperature cycle durability.
  • the inventors have determined that the upper limit potential of the positive electrode is Li by using a specific solvent as the non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery.
  • a non-aqueous electrolyte secondary battery excellent in durability characteristics such as a low gas generation amount and a high temperature cycle can be realized in a high voltage design battery of 4.5 V or higher on the basis of / Li + standard. It came. That is, the gist of the present invention is as follows.
  • a non-aqueous electrolyte comprising a lithium salt and a non-aqueous solvent for dissolving the lithium salt, a negative electrode capable of occluding and releasing lithium ions, and a non-aqueous electrolyte secondary battery comprising a positive electrode
  • the upper limit operating potential is 4.5 V or more on the basis of Li / Li +
  • the non-aqueous electrolyte is a cyclic carbonate represented by the following general formula (1), a fluorinated cyclic represented by the following general formula (2) Carbonate and a fluorinated chain carbonate represented by the following general formula (3) are contained, and the cyclic carbonate represented by the general formula (1) is contained more than 15% by volume in the non-aqueous solvent.
  • R 1 represents hydrogen or a hydrocarbon group which may have a substituent, and may be the same or different from each other.
  • R 2 represents hydrogen, fluorine, or a hydrocarbon group that may have a substituent, and may be the same or different from each other.
  • R 3 may have a substituent, a hydrocarbon group containing at least one fluorine
  • R 4 represents a hydrocarbon group that may have a substituent
  • R 3 and R 4 may be the same or different.
  • the total amount of carbonates represented by the general formulas (1) to (3) is 50% by volume or more of the non-aqueous solvent, Water-based electrolyte secondary battery.
  • the fluorinated chain carbonate represented by the general formula (3) is contained in 5% by volume or more in the non-aqueous solvent, a) or b) The non-aqueous electrolyte secondary battery described.
  • the total amount of carbonates represented by the general formulas (1) and (2) is 25% by volume or more of the non-aqueous solvent, a) to c) The non-aqueous electrolyte secondary battery according to any one of the above.
  • the cyclic carbonate represented by the general formula (1) is contained in a non-aqueous solvent in an amount of 20% by volume or more.
  • the positive electrode contains a positive electrode active material containing at least one selected from the group consisting of lithium transition metal compounds represented by the following general formulas (4) to (6): The non-aqueous electrolyte secondary battery according to any one of a) to h).
  • Li [Li a M x Mn 2-xa ] O 4 + ⁇ (4) (In the formula (4), 0 ⁇ a ⁇ 0.3, 0.4 ⁇ x ⁇ 1.1, ⁇ 0.5 ⁇ ⁇ 0.5 is satisfied, and M is Ni, Cr, Fe, Co, and Cu.
  • M1 represents Ni, Co
  • M2 represents Fe, Cr, V, Ti, Cu, Ga, Bi, Sn, B, P, Zn, Mg, Ge, Nb, W, Ta, Be, Al, Ca, Sc and Zr.
  • a non-aqueous electrolyte comprising a lithium salt and a non-aqueous solvent for dissolving the lithium salt, a negative electrode capable of occluding and releasing lithium ions, and a non-aqueous electrolyte secondary battery comprising a positive electrode, wherein the non-aqueous electrolyte
  • the electrolytic solution contains a cyclic carbonate represented by the following general formula (1), a fluorinated cyclic carbonate represented by the following general formula (2), and a fluorinated chain carbonate represented by the following general formula (3).
  • a non-aqueous electrolyte secondary battery comprising a positive electrode active material containing at least one selected from the group consisting of a system compound.
  • R 1 represents hydrogen or a hydrocarbon group which may have a substituent, and may be the same or different from each other.
  • R 2 represents hydrogen, fluorine, or a hydrocarbon group that may have a substituent, and may be the same or different from each other.
  • R 3 may have a substituent, a hydrocarbon group containing at least one fluorine
  • R 4 represents a hydrocarbon group that may have a substituent, and R 3 and R 4 may be the same or different.
  • Li [Li a M x Mn 2-xa ] O 4 + ⁇ (4) In the formula (4), 0 ⁇ a ⁇ 0.3, 0.4 ⁇ x ⁇ 1.1, ⁇ 0.5 ⁇ ⁇ 0.5 is satisfied, and M is Ni, Cr, Fe, Co, and Cu.
  • M1 represents Ni, Co
  • M2 represents Fe, Cr, V, Ti, Cu, Ga, Bi, Sn, B, P, Zn, Mg, Ge, Nb, W, Ta, Be, Al, Ca, Sc and Zr.
  • ⁇ Li 2 MO 3 ⁇ (1- ⁇ ) LiM′O 2 (6) (In Formula (6), 0 ⁇ ⁇ 1 is satisfied, M is at least one metal element having an average oxidation number of +4, and M ′ is a metal element having an average oxidation number of +3. Represents at least one).
  • a non-aqueous electrolyte solution containing a lithium salt and a non-aqueous solvent for dissolving the lithium salt wherein the non-aqueous electrolyte solution is a cyclic carbonate represented by the following general formula (1), and the following general formula (2): 20% by volume of the cyclic carbonate represented by the general formula (1) in the non-aqueous solvent, which contains the fluorinated cyclic carbonate represented by the formula (3) and the fluorinated chain carbonate represented by the following general formula (3).
  • a non-aqueous electrolyte characterized by containing more.
  • R 1 represents hydrogen or a hydrocarbon group which may have a substituent, and may be the same or different from each other.
  • R 2 represents hydrogen, fluorine, or a hydrocarbon group that may have a substituent, and may be the same or different from each other.
  • R 3 may have a substituent, a hydrocarbon group containing at least one fluorine
  • R 4 represents a hydrocarbon group that may have a substituent
  • R 3 and R 4 may be the same or different.
  • non-aqueous electrolyte is a cyclic carbonate represented by the following general formula (1), represented by the following general formula (2) And 15% by volume of the cyclic carbonate represented by the general formula (1) in the non-aqueous solvent, and the fluorinated cyclic carbonate represented by the following general formula (3).
  • R 1 represents hydrogen or a hydrocarbon group which may have a substituent, and may be the same or different from each other.
  • R 2 represents hydrogen, fluorine, or a hydrocarbon group that may have a substituent, and may be the same or different from each other.
  • R 3 may have a substituent, a hydrocarbon group containing at least one fluorine
  • R 4 represents a hydrocarbon group that may have a substituent, and R 3 and R 4 may be the same or different.
  • the cyclic carbonate solvent represented by the general formula (1) has been considered unsuitable for a high voltage system because of its low resistance to the positive electrode oxidation reaction.
  • the cyclic carbonate represented by (1) is introduced into the non-aqueous electrolyte.
  • the present inventors use a cyclic carbonate represented by the general formula (1), which has been considered disadvantageous for a high voltage system, as an essential solvent, and further mix a fluorinated cyclic carbonate and a fluorinated chain carbonate.
  • the aqueous electrolyte has dramatically improved battery durability as compared to a non-aqueous electrolyte composed of a perfluorinated solvent, and has found the knowledge that the above problems can be solved, and has completed the present invention. .
  • a lithium secondary battery designed for a high voltage specification not only has excellent durability characteristics such as battery cycle and storage at high temperatures, but also a non-aqueous electrolyte solution excellent in battery characteristics at low temperatures.
  • An electrolyte for a secondary battery and a non-aqueous electrolyte secondary battery can be provided.
  • a particularly preferable example of the non-aqueous electrolyte secondary battery of the present invention is a lithium secondary battery.
  • the non-aqueous electrolyte secondary battery of the present invention can take a known structure, and typically, a negative electrode and a positive electrode capable of occluding and releasing ions (for example, lithium ions), a non-aqueous electrolyte, A separator is provided.
  • Non-aqueous electrolyte 1-1 Non-aqueous solvent 1-1-1.
  • Solvent The nonaqueous electrolytic solution according to the present invention contains a cyclic carbonate represented by the following general formula (1), and further includes a fluorinated cyclic carbonate represented by the following general formula (2), and the following general formula (3). It contains the fluorinated chain carbonate represented by these.
  • non-aqueous solvent non-fluorinated chain carbonates, cyclic and chain carboxylic esters, ether compounds, sulfone compounds, and the like can be used as the non-aqueous solvent.
  • R 1 represents hydrogen or a hydrocarbon group which may have a substituent, and may be the same or different from each other.
  • R 1 is hydrogen or a hydrocarbon group which may have a substituent.
  • the hydrocarbon group which may have a substituent an alkyl group having 1 to 4 carbon atoms, preferably 1 carbon atom is preferable. ⁇ 3 alkyl groups. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • Examples of the cyclic carbonate represented by the general formula (1) include those having an alkylene group having 2 to 4 carbon atoms.
  • examples of the cyclic carbonate having an alkylene group having 2 to 4 carbon atoms include ethylene carbonate, propylene carbonate, butylene carbonate and the like.
  • ethylene carbonate and propylene carbonate are particularly preferable from the viewpoint of improving battery characteristics resulting from improvement of the degree of lithium ion dissociation and improving battery durability.
  • the cyclic carbonate represented by the general formula (1) may be used alone or in combination of two or more in any combination and ratio.
  • the amount of the cyclic carbonate represented by the general formula (1) is not particularly limited as long as it is more than 15% by volume in 100% by volume of the non-aqueous solvent, and is arbitrary as long as the effect of the present invention is not significantly impaired.
  • the lower limit of the blending amount is preferably 20% by volume or more, more preferably 25% by volume or more, and most preferably 30% by volume or more in 100% by volume of the non-aqueous solvent.
  • the upper limit is preferably 70% by volume or less, more preferably 65% by volume or less, and most preferably 60% by volume or less.
  • R 2 represents hydrogen, fluorine, or a hydrocarbon group that may have a substituent, and may be the same or different from each other.
  • R 2 is hydrogen, fluorine, or a hydrocarbon group which may have a substituent.
  • hydrocarbon group which may have a substituent examples include alkyl groups having 1 to 4 carbon atoms, 4 monofluoroalkyl groups, difluoroalkyl groups having 1 to 4 carbon atoms, and trifluoroalkyl groups having 1 to 4 carbon atoms, preferably alkyl groups having 1 to 2 carbon atoms, monofluoroalkyl having 1 to 2 carbon atoms Group, a C 1-2 difluoroalkyl group, and a C 1-2 trifluoroalkyl group.
  • Specific examples include a methyl group, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, an ethyl group, a monofluoroethyl group, a difluoroethyl group, and a trifluoroethyl group.
  • Examples of the fluorinated cyclic carbonate represented by the general formula (2) include cyclic carbonate derivatives having an alkylene group having 2 to 6 carbon atoms.
  • Specific examples of the fluorinated cyclic carbonate include ethylene carbonate or a fluoride of ethylene carbonate substituted with an alkyl group (for example, an alkyl group having 1 to 4 carbon atoms).
  • the number of fluorine atoms in the fluorinated cyclic carbonate is not particularly limited as long as it is 1 or more, but those having 1 to 8 fluorine atoms are preferable.
  • At least one selected from the group consisting of monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, and 4,5-difluoro-4,5-dimethylethylene carbonate is a high ion It is more preferable in terms of imparting conductivity and suitably forming an interfacial protective film, and more preferably at least one selected from monofluoroethylene carbonate and 4,5-difluoroethylene carbonate. This is preferable because the storage characteristics and cycle characteristics of the aqueous electrolyte secondary battery can be easily set in a favorable range.
  • the fluorinated cyclic carbonate represented by the general formula (2) may be used alone or in combination of two or more in any combination and ratio.
  • the blending amount of the fluorinated cyclic carbonate is not particularly limited and is arbitrary as long as the effects of the present invention are not significantly impaired.
  • 100% by volume of the non-aqueous solvent preferably 1% by volume or more, more preferably 2% by volume or more.
  • the non-aqueous electrolyte secondary battery is likely to exhibit a sufficient cycle characteristics improvement effect, avoiding a decrease in discharge capacity maintenance rate due to a decrease in high-temperature storage characteristics or an increase in the amount of gas generated.
  • Cheap is a sufficient cycle characteristics improvement effect, avoiding a decrease in discharge capacity maintenance rate due to a decrease in high-temperature storage characteristics or an increase in the amount of gas generated.
  • the total amount (blending amount) of the cyclic carbonate represented by the general formula (1) and the fluorinated cyclic carbonate represented by the general formula (2) is 100% by volume in the non-aqueous solvent, preferably from 15% by volume.
  • the amount is more preferably 20% by volume or more, most preferably 25% by volume or more, preferably 98% by volume or less, more preferably 95% by volume or less, and further preferably 90% by volume or less. If it is this range, a non-aqueous electrolyte secondary battery will be easy to express sufficient cycling characteristics improvement effect, and it will be easy to avoid the fall of a high temperature storage characteristic, and the fall of the discharge capacity maintenance factor by the increase in gas generation amount.
  • the cyclic carbonate represented by the general formula (1) is blended.
  • the amount is preferably 50% or more, more preferably 55% or more, and still more preferably 60% or more.
  • the fluorinated cyclic carbonate represented by the general formula (2) exhibits an effective function not only as a solvent but also as an auxiliary agent described in the following 1-3.
  • the fluorinated cyclic carbonate represented by the general formula (2) is used as a solvent and auxiliary agent, there is no clear boundary, and the amount described in the previous paragraph can be followed as it is.
  • R 3 may have a substituent, a hydrocarbon group containing at least one fluorine
  • R 4 represents a hydrocarbon group that may have a substituent
  • R 3 and R 4 may be the same or different.
  • R 3 may have a substituent and is a hydrocarbon group containing at least one fluorine. Examples of the hydrocarbon group include monofluoroalkyl groups having 1 to 4 carbon atoms and difluoro having 1 to 4 carbon atoms.
  • An alkyl group and a trifluoroalkyl group having 1 to 4 carbon atoms are preferably a monofluoroalkyl group having 1 to 2 carbon atoms, a difluoroalkyl group having 1 to 2 carbon atoms, and a trifluoroalkyl group having 1 to 2 carbon atoms. Is mentioned. Specific examples include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, and trifluoroethyl.
  • R 4 is a hydrocarbon group which may have a substituent.
  • Examples of the hydrocarbon group which may have a substituent include an alkyl group having 1 to 4 carbon atoms and a monofluoroalkyl having 1 to 4 carbon atoms.
  • a difluoroalkyl group having 2 to 2 and a trifluoroalkyl group having 1 to 2 carbon atoms preferably an alkyl group having 1 to 2 carbon atoms, a monofluoroalkyl group having 1 to 2 carbon atoms, or 1 carbon atom.
  • a difluoroalkyl group having 2 to 2 and a trifluoroalkyl group having 1 to 2 carbon atoms preferably an alkyl group having 1 to 2 carbon atom
  • Specific examples include a methyl group, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, an ethyl group, a monofluoroethyl group, a difluoroethyl group, and trifluoroethyl.
  • the fluorinated chain carbonate represented by the general formula (3) those having 3 to 7 carbon atoms are preferable.
  • the number of fluorine atoms contained in the fluorinated chain carbonate is not particularly limited as long as it is 1 or more, but is usually 6 or less, preferably 4 or less.
  • the fluorinated chain carbonate has a plurality of fluorine atoms, they may be bonded to the same carbon or may be bonded to different carbons.
  • the fluorinated chain carbonate include a fluorinated dimethyl carbonate derivative, a fluorinated ethyl methyl carbonate derivative, and a fluorinated diethyl carbonate derivative.
  • Fluorinated dimethyl carbonate derivatives include fluoromethyl methyl carbonate, difluoromethyl methyl carbonate, trifluoromethyl methyl carbonate, bis (fluoromethyl) carbonate, bis (difluoromethyl) carbonate, bis (trifluoromethyl) carbonate, and the like.
  • Fluorinated ethyl methyl carbonate derivatives include (2-fluoroethyl) methyl carbonate, ethyl fluoromethyl carbonate, (2,2-difluoroethyl) methyl carbonate, (2-fluoroethyl) fluoromethyl carbonate, ethyl difluoromethyl carbonate, ( 2,2,2-trifluoroethyl) methyl carbonate, (2,2-difluoroethyl) fluoromethyl carbonate, (2-fluoroethyl) difluoromethyl carbonate, ethyl trifluoromethyl carbonate and the like.
  • Fluorinated diethyl carbonate derivatives include ethyl- (2-fluoroethyl) carbonate, ethyl- (2,2-difluoroethyl) carbonate, bis (2-fluoroethyl) carbonate, ethyl- (2,2,2-trifluoro).
  • Ethyl) carbonate 2,2-difluoroethyl-2′-fluoroethyl carbonate, bis (2,2-difluoroethyl) carbonate, 2,2,2-trifluoroethyl-2′-fluoroethyl carbonate, 2,2, Examples include 2-trifluoroethyl-2 ′, 2′-difluoroethyl carbonate, bis (2,2,2-trifluoroethyl) carbonate, and the like.
  • the fluorinated chain carbonate represented by the general formula (3) may be used alone or in combination of two or more in any combination and ratio.
  • the blending amount of the fluorinated chain carbonate represented by the general formula (3) is preferably 1% by volume or more, more preferably 5% by volume or more, and further preferably 10% by volume in 100% by volume of the non-aqueous solvent. As mentioned above, it is 15 volume% or more most preferably.
  • the fluorinated chain carbonate represented by the general formula (3) is preferably 90% by volume or less, more preferably 80% by volume or less, and most preferably 75% by volume or less in 100% by volume of the non-aqueous solvent. It is preferable.
  • the total amount (blending amount) of the cyclic carbonate represented by the general formula (1) and the fluorinated chain carbonate represented by the general formula (3) is preferably 100% by volume in 100% by volume of the non-aqueous solvent. More, more preferably 30% by volume or more, most preferably 50% by volume or more, and preferably 97% by volume or less, more preferably 95% by volume or less. If it is this range, a non-aqueous electrolyte secondary battery will be easy to express sufficient cycling characteristics improvement effect, and it will be easy to avoid the fall of a high temperature storage characteristic, and the fall of the discharge capacity maintenance factor by the increase in gas generation amount.
  • the total amount (blending amount) of the fluorinated cyclic carbonate represented by the general formula (1), the fluorinated cyclic carbonate represented by the general formula (2), and the fluorinated chain carbonate represented by the general formula (3) ) Is 50% by volume or more in 100% by volume of the non-aqueous solvent, preferably 70% by volume or more, more preferably 75% by volume or more, and most preferably 85% by volume or more.
  • the viscosity of the non-aqueous electrolyte is set to an appropriate range, the decrease in ionic conductivity is suppressed, and consequently the large current discharge characteristics of the non-aqueous electrolyte secondary battery It becomes easy to make the battery characteristics at a low temperature and a good range.
  • the upper limit is not particularly set and may be 100% by volume.
  • solvents Other than the cyclic carbonate represented by the general formula (1), the fluorinated cyclic carbonate represented by the general formula (2), and the fluorinated chain carbonate represented by the general formula (3), Various solvents may be mixed and used as long as the effect is not impaired. Examples of these solvents include non-fluorinated chain carbonates, cyclic carboxylic acid esters, chain carboxylic acid esters, ether compounds, and sulfone compounds.
  • the non-fluorinated chain carbonate is preferably one having 3 to 7 carbon atoms. Specifically, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, di-i-propyl carbonate, n-propyl-i-propyl carbonate, ethyl methyl carbonate, methyl-n-propyl carbonate, n-butyl methyl carbonate I-butyl methyl carbonate, t-butyl methyl carbonate, ethyl-n-propyl carbonate, n-butyl ethyl carbonate, i-butyl ethyl carbonate, t-butyl ethyl carbonate and the like.
  • dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, di-i-propyl carbonate, n-propyl-i-propyl carbonate, ethyl methyl carbonate, methyl-n-propyl carbonate are preferable, and dimethyl carbonate is particularly preferable. Diethyl carbonate and ethyl methyl carbonate.
  • the blending amount of the non-fluorinated chain carbonate is usually in 100% by volume of the non-aqueous solvent, preferably 0.1% by volume or more, more preferably 0.3% by volume or more, and further preferably 0.5% by volume or more. is there.
  • the electrical conductivity of the non-aqueous electrolyte solution is improved, and the large current discharge characteristics of the non-aqueous electrolyte secondary battery are easily improved.
  • the compounding quantity of a non-fluorinated chain carbonate becomes like this. Preferably it is 40 volume% or less, More preferably, it is 35 volume% or less.
  • the viscosity of the non-aqueous electrolyte solution is set to an appropriate range, a decrease in electrical conductivity is avoided, an increase in negative electrode resistance is suppressed, and a large current discharge of the non-aqueous electrolyte secondary battery is performed. It becomes easy to make a characteristic into a favorable range.
  • ⁇ Cyclic carboxylic acid ester examples include those having 3 to 12 carbon atoms in the structural formula. Specific examples include gamma butyrolactone, gamma valerolactone, gamma caprolactone, epsilon caprolactone, and the like. Among these, gamma butyrolactone is particularly preferable from the viewpoint of improving battery characteristics resulting from an improvement in the degree of lithium ion dissociation.
  • the compounding amount of the cyclic carboxylic acid ester is usually 0.3% by volume or more, more preferably 0.5% by volume or more, and further preferably 1% by volume or more in 100% by volume of the non-aqueous solvent.
  • the compounding quantity of cyclic carboxylic acid ester becomes like this.
  • it is 15 volume% or less, More preferably, it is 10 volume% or less, More preferably, it is 5 volume% or less.
  • the viscosity of the non-aqueous electrolyte solution is set to an appropriate range, a decrease in electrical conductivity is avoided, an increase in negative electrode resistance is suppressed, and a large current discharge of the non-aqueous electrolyte secondary battery is performed. It becomes easy to make a characteristic into a favorable range.
  • Examples of the chain carboxylic acid ester include those having 3 to 7 carbon atoms in the structural formula. Specifically, methyl acetate, ethyl acetate, acetate n-propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, Isopropyl propionate, n-butyl propionate, isobutyl propionate, t-butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, methyl isobutyrate, ethyl isobutyrate, isobutyric acid-n- Examples include propyl and isopropyl isobutyrate.
  • the compounding amount of the chain carboxylic acid ester is usually 0.3% by volume or more, more preferably 0.5% by volume or more, and further preferably 1% by volume or more in 100% by volume of the non-aqueous solvent.
  • the amount of the chain carboxylic acid ester is preferably 15% by volume or less, more preferably 10% by volume or less, and further preferably 5% by volume or less in 100% by volume of the non-aqueous solvent.
  • ether compound a chain ether having 3 to 10 carbon atoms in which part of hydrogen may be substituted with fluorine and a cyclic ether having 3 to 6 carbon atoms are preferable.
  • chain ether having 3 to 10 carbon atoms include diethyl ether, bis (2-fluoroethyl) ether, bis (2,2-difluoroethyl) ether, bis (2,2,2-trifluoroethyl) ether, ethyl (2-fluoroethyl) ether, ethyl (2,2,2-trifluoroethyl) ether, ethyl (1,1,2,2-tetrafluoroethyl) ether, (2-fluoroethyl) (2,2,2 -Trifluoroethyl) ether, (2-fluoroethyl) (1,1,2,2-tetrafluoroethyl) ether, (1,1,2,2-tetrafluoroethyl)
  • Examples of the cyclic ether having 3 to 6 carbon atoms include tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 1,3-dioxane, 2-methyl-1,3-dioxane, 4-methyl-1,3-dioxane, 1 , 4-dioxane and the like, and fluorinated compounds thereof.
  • dimethoxymethane, diethoxymethane, ethoxymethoxymethane, ethylene glycol di-n-propyl ether, ethylene glycol di-n-butyl ether, and diethylene glycol dimethyl ether have high solvating ability to lithium ions and improve ion dissociation.
  • dimethoxymethane, diethoxymethane, and ethoxymethoxymethane are preferable because they have low viscosity and give high ionic conductivity.
  • the compounding amount of the ether compound is usually 0.3% by volume or more, more preferably 0.5% by volume or more, further preferably 1% by volume or more, and preferably 40% in 100% by volume of the non-aqueous solvent. Volume% or less, More preferably, it is 35 volume% or less, More preferably, it is 30 volume% or less. If it is this range, it is easy to ensure the improvement effect of the lithium ion dissociation degree of chain ether, and the improvement of the ionic conductivity derived from a viscosity fall, and when a negative electrode active material is a carbonaceous material, a chain ether with lithium ion It is easy to avoid a situation where the capacity is reduced due to co-insertion.
  • sulfone compound a cyclic sulfone having 3 to 6 carbon atoms and a chain sulfone having 2 to 6 carbon atoms are preferable.
  • the number of sulfonyl groups in one molecule is preferably 1 or 2.
  • the cyclic sulfone include trimethylene sulfones, tetramethylene sulfones, and hexamethylene sulfones that are monosulfone compounds; trimethylene disulfones, tetramethylene disulfones, and hexamethylene disulfones that are disulfone compounds.
  • tetramethylene sulfones from the viewpoint of dielectric constant and viscosity, tetramethylene sulfones, tetramethylene disulfones, hexamethylene sulfones, and hexamethylene disulfones are more preferable, and tetramethylene sulfones (sulfolanes) are particularly preferable.
  • the sulfolane is preferably sulfolane and / or a sulfolane derivative (hereinafter sometimes abbreviated as “sulfolane” including sulfolane).
  • sulfolane derivative one in which one or more hydrogen atoms bonded to the carbon atom constituting the sulfolane ring are substituted with a fluorine atom or an alkyl group is preferable.
  • chain sulfone dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, methyl-n-propyl sulfone, ethyl-n-propyl sulfone, di-n-propyl sulfone, i-propyl methyl sulfone, isopropyl ethyl sulfone, diisopropyl Sulfone, n-butylmethylsulfone, n-butylethylsulfone, t-butylmethylsulfone, t-butylethylsulfone, fluoromethylmethylsulfone, difluoromethylmethylsulfone, trifluoromethylmethylsulfone, (2-fluoro) ethylmethylsulfone , (2,2-difluoroethyl) methylsulfone, trifluoroethyl
  • the compounding amount of the sulfone compound is usually 0.3% by volume or more, more preferably 0.5% by volume or more, and further preferably 1% by volume or more in 100% by volume of the non-aqueous solvent. Is 40% by volume or less, more preferably 35% by volume or less, and still more preferably 30% by volume or less. Within this range, durability improvement effects such as cycle characteristics and storage characteristics can be easily obtained, and the viscosity of the non-aqueous electrolyte can be set to an appropriate range to avoid a decrease in electrical conductivity. When charging / discharging an aqueous electrolyte secondary battery at a high current density, it is easy to avoid a situation in which the charge / discharge capacity retention rate decreases.
  • Electrolyte As the electrolyte, a lithium salt is usually used.
  • the lithium salt is not particularly limited as long as it is known to be used for this purpose. Any lithium salt can be used, and specific examples include the following.
  • inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiAlF 4 , LiSbF 6 , LiNbF 6 , LiTaF 6 , LiWF 7 ; Lithium fluorophosphates such as LiPO 3 F and LiPO 2 F 2 ; Lithium tungstates such as LiWOF 5 ; HCO 2 Li, CH 3 CO 2 Li, CH 2 FCO 2 Li, CHF 2 CO 2 Li, CF 3 CO 2 Li, CF 3 CH 2 CO 2 Li, CF 3 CF 2 CO 2 Li, CF 3 CF 2 CF 2 Carboxylic acid lithium salts such as CO 2 Li, CF 3 CF 2 CF 2 CO 2 Li; FSO 3 Li, CH 3 SO 3 Li, CH 2 FSO 3 Li, CHF 2 SO 3 Li, CF 3 SO 3 Li, CF 3 CF 2 SO 3 Li, CF 3 CF 2 SO 3 Li, CF 3 CF 2 SO 3 Li, CF 3 CF 2 Sul
  • lithium salts may be used alone or in combination of two or more.
  • a preferable example in the case of using two or more types in combination is the combination of LiPF 6 and LiBF 4 , LiPF 6 and FSO 3 Li, or LiPF 6 and LiPO 2 F 2 , and has an effect of improving load characteristics and cycle characteristics.
  • the combined use of LiPF 6 and FSO 3 Li, or LiPF 6 and LiPO 2 F 2 is preferable because the effect is remarkable.
  • the concentration of LiBF 4 or FSO 3 Li with respect to 100% by mass of the total amount of the non-aqueous electrolyte is not limited, and the effect of the present invention is not significantly impaired.
  • it is usually 0.01% by mass or more, preferably 0.1% by mass or more with respect to the non-aqueous electrolyte, while its upper limit is usually 30% by mass or less, preferably 20% by mass or less.
  • the effect of output characteristics, load characteristics, low temperature characteristics, cycle characteristics, high temperature characteristics, and the like may be improved by setting the content to 10% by mass or less, more preferably 5% by mass or less.
  • the concentration of LiPO 2 F 2 with respect to 100% by mass of the entire non-aqueous electrolyte solution is not limited, and is arbitrary as long as the effects of the present invention are not significantly impaired. However, it is usually 0.001% by mass or more, preferably 0.01% by mass or more with respect to the non-aqueous electrolyte solution, while its upper limit is usually 10% by mass or less, preferably 5% by mass or less. Within this range, effects such as output characteristics, load characteristics, low temperature characteristics, cycle characteristics, and high temperature characteristics are improved. On the other hand, if it is too much, it may be deposited at low temperature to deteriorate the battery characteristics, and if it is too little, the effect of improving the low temperature characteristics, cycle characteristics, high temperature storage characteristics, etc. may be reduced.
  • the active material prepared in the electrolyte solution in the case of incorporating the LiPO 2 F 2 in the electrolyte solution the LiPO 2 F 2 which is separately synthesized by a known method, described later method or be added to the electrolytic solution containing LiPF 6
  • the method for measuring the content of LiPO 2 F 2 in the non-aqueous electrolyte solution and the non-aqueous electrolyte secondary battery is not particularly limited, and any known method can be used. Specific examples include ion chromatography and F nuclear magnetic resonance spectroscopy (hereinafter sometimes abbreviated as NMR). Another example is the combined use of an inorganic lithium salt and an organic lithium salt, and the combined use of both has the effect of suppressing deterioration due to high-temperature storage.
  • CF 3 SO 3 Li LiN (FSO 2 ) 2 , LiN (FSO 2 ) (CF 3 SO 2 ), LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , Lithium cyclic 1,2-perfluoroethanedisulfonylimide, lithium cyclic 1,3-perfluoropropane disulfonylimide, LiC (FSO 2 ) 3 , LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 , lithium bisoxalatoborate, lithium difluorooxalatoborate, lithium tetrafluorooxalatophosphate, lithium difluorobisoxalatophosphate, LiBF 3 CF 3 , LiBF 3 C 2 F 5 , LiPF 3 (CF 3 ) 3, preferably a LiPF 3 (C 2 F 5) 3 , etc.
  • the ratio of the organic lithium salt to 100% by mass of the whole non-aqueous electrolyte is preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, preferably 30% by mass or less, particularly preferably. It is 20 mass% or less.
  • the concentration of these lithium salts in the non-aqueous electrolyte solution is not particularly limited as long as the effects of the present invention are not impaired, but the electric conductivity of the electrolyte solution is in a good range, and good battery performance is ensured. Therefore, the total molar concentration of lithium in the non-aqueous electrolyte is preferably 0.3 mol / L or more, more preferably 0.4 mol / L or more, and further preferably 0.5 mol / L or more. Preferably it is 3 mol / L or less, More preferably, it is 2.5 mol / L or less, More preferably, it is 2.0 mol / L or less.
  • auxiliary agent includes the following compounds having a carbon-carbon triple bond, cyclic carbonates having an unsaturated bond excluding the carbon-carbon triple bond, unsaturated cyclic carbonates having a fluorine atom, cyclic sulfonate esters, cyano groups , Compounds having an isocyanato group, other auxiliaries, and the like.
  • a film having a carbon-carbon triple bond can be contained in order to form a film on the negative electrode surface and achieve a long battery life.
  • the compound having a carbon-carbon triple bond is not particularly limited as long as it is a compound having a carbon-carbon triple bond, but a chain compound having a carbon-carbon triple bond and a cyclic compound having a carbon-carbon triple bond. Classified as a compound.
  • As the chain compound having a carbon-carbon triple bond one or more alkyne derivatives represented by the following general formula (11) or formula (12) are preferably used.
  • R 11 to R 19 are each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms.
  • R 12 and R 13 , R 15 and R 16 , R 17 and R 18 may be bonded to each other to form a cycloalkyl group having 3 to 6 carbon atoms.
  • x and y represent an integer of 1 or 2.
  • Y 1 and Y 2 are each represented by any of the following formulas (13) and may be the same or different.
  • Z 1 represents hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.
  • 2-propynylmethyl carbonate 1-methyl-2-propynylmethyl carbonate, 1,1-dimethyl-2-propynylmethyl carbonate, 2-propynylethyl carbonate, 1-methyl -2-propynyl ethyl carbonate, 1,1-dimethyl-2-propynyl ethyl carbonate, 2-butynyl methyl carbonate, 1-methyl-2-butynyl methyl carbonate, 1,1-dimethyl-2-butynyl methyl carbonate -2-propynyl formate, 1-methyl-2-propynyl formate, 1,1-dimethyl-2-propynyl formate, 2-butynyl formate, 1-methyl-2-butynyl formate, 1,1 formate -Dimethyl-2-butynyl, 2-propynyl acetate, 1-methyl-2-propiyl acetate 1,1-dimethyl-2-propyny
  • 2-propynylmethyl carbonate 1-methyl-2-propynylmethyl carbonate, 1,1-dimethyl-2-propynylmethyl carbonate, 2-propynylethyl carbonate, 2-butynylmethyl carbonate, formic acid-2-propynyl, formic acid-1 -Methyl-2-propynyl, 1,1-dimethyl-2-propynyl formate, 2-butynyl formate, 2-propynyl acetate, 1-methyl-2-propynyl acetate, 1,1-dimethyl-2 acetate -Propynyl, 2-butynyl acetate, 2-propynylmethyl oxalate, 1-methyl-2-propynylmethyl oxalate, 1,1-dimethyl-2-propynylmethyl oxalate, 2-butynylmethyl oxalate, methanesulfone Acid-2-propynyl, methanesulfonic acid-1
  • the most preferred compounds are 2-propynylmethyl carbonate, 2-propynylethyl carbonate, 2-butynylmethyl carbonate, formic acid-2-propynyl, formic acid-2-butynyl, acetic acid-2-propynyl, acetic acid- 2-butynyl, 2-propynylmethyl oxalate, 2-butynylmethyl oxalate, methanesulfonic acid-2-propynyl, methanesulfonic acid-2-butynyl, methanesulfonic acid-1-methyl-2-butynyl, methylsulfuric acid 2-propynyl, methylsulfuric acid-2-butynyl, di (2-propynyl) carbonate, di (2-butynyl) carbonate, di (2-propynyl) oxalate, di (2-butynyl) oxalate, di (2-butynyl) o
  • the compounds represented by the general formulas (11) to (12) may be used alone or in combination of two or more in any combination and ratio. Further, the compounding amount of the compounds represented by the general formulas (11) to (12) is not particularly limited, and is arbitrary as long as the effects of the present invention are not significantly impaired.
  • the compounding amount of the compounds represented by the general formulas (11) to (12) is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably in 100% by mass of the non-aqueous electrolyte solution. It is 0.1 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 4 mass% or less, More preferably, it is 3 mass% or less.
  • the non-aqueous electrolyte secondary battery is likely to exhibit a sufficient cycle characteristics improvement effect, and the high-temperature storage characteristics are reduced, the amount of gas generated is increased, and the discharge capacity maintenance rate is reduced. Easy to avoid. On the other hand, if the amount is too small, the effects of the present invention may not be sufficiently exerted. If the amount is too large, the resistance may increase and the output and load characteristics may decrease.
  • cyclic compound having a carbon-carbon triple bond is preferably a compound represented by the following general formula (14).
  • X and Z represent CR 1 2 , C ⁇ O, C ⁇ N—R 1 , C ⁇ P—R 1 , O, S, N—R 1 , PR 1 , Y may be the same or different, Y represents CR 1 2 , C ⁇ O, S ⁇ O, S ( ⁇ O) 2 , P ( ⁇ O) —R 2 , P ( ⁇ O) —OR 3
  • R and R 1 are hydrogen, halogen, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and may be the same or different from each other, and R 2 represents a substituent.
  • .R 3 is a hydrocarbon group which may having 1 to 20 carbon atoms which may have is, Li, a hydrocarbon group NR 4 4, or a substituent and 1 carbon atoms which may have a 20 .
  • R 4 Is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and may be the same or different from each other, n and m each represents an integer of 0 or more, and W has the same meaning as R above. And And may be the same as or different from R above.
  • X and Z is not particularly limited as long as the scope described in the aforementioned general formula (4), preferably, CR 1 2, O, S , N-R 1 is more preferred.
  • Y is not particularly limited as long as it is within the range described in the general formula (14), but preferably C ⁇ O, S ⁇ O, S ( ⁇ O) 2 , P ( ⁇ O) —R 2 , P ( ⁇ O) —OR 3 is more preferred.
  • R and R 1 are not particularly limited as long as they are within the range described in formula (14), but preferably have hydrogen, fluorine, a saturated aliphatic hydrocarbon group which may have a substituent, or a substituent. Examples thereof may include an unsaturated aliphatic hydrocarbon group which may be substituted, and an aromatic hydrocarbon group which may have a substituent.
  • R 2 and R 4 are not particularly limited as long as they are within the range described in the general formula (14), but are preferably a saturated aliphatic hydrocarbon group that may have a substituent or a substituent. Examples include unsaturated aliphatic hydrocarbons and optionally substituted aromatic hydrocarbons / aromatic heterocycles.
  • R 3 is not particularly limited as long as it is in the range described in the general formula (14), but preferably Li, a saturated aliphatic hydrocarbon which may have a substituent, or an unsaturated which may have a substituent. Examples thereof include an aliphatic hydrocarbon and an aromatic hydrocarbon / aromatic heterocycle which may have a substituent.
  • Substituents of saturated aliphatic hydrocarbons which may have substituents, unsaturated aliphatic hydrocarbons which may have substituents, aromatic hydrocarbons and aromatic heterocycles which may have substituents Is not particularly limited, but preferably has a saturated aliphatic hydrocarbon group, which may have a substituent such as halogen, carboxylic acid, carbonic acid, sulfonic acid, phosphoric acid, phosphorous acid, etc. And an unsaturated aliphatic hydrocarbon group that may be substituted, an ester of an aromatic hydrocarbon group that may have a substituent, and the like, more preferably halogen, and most preferably fluorine.
  • Preferable saturated aliphatic hydrocarbons are specifically methyl group, ethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 1,1-difluoroethyl.
  • a phenyl group, a cyclopentyl group, and a cyclohexyl group are preferred.
  • Preferable unsaturated aliphatic hydrocarbons include ethenyl group, 1-fluoroethenyl group, 2-fluoroethenyl group, 1-methylethenyl group, 2-propenyl group, 2-fluoro-2-propenyl group. 3-fluoro-2-propenyl group, ethynyl group, 2-fluoroethynyl group, 2-propynyl group and 3-fluoro-2-propynyl group are preferable.
  • Preferred aromatic hydrocarbons include phenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 2, 4 , 6-trifluorophenyl group is preferable.
  • Preferred aromatic heterocycles are 2-furanyl group, 3-furanyl group, 2-thiophenyl group, 3-thiophenyl group, 1-methyl-2-pyrrolyl group, 1-methyl-3-pyrrolyl group.
  • methyl, ethyl, fluoromethyl, trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, ethenyl, ethynyl, and phenyl are preferred.
  • the molecular weight is preferably 50 or more. Moreover, Preferably it is 500 or less. If it is this range, it will be easy to ensure the solubility of the unsaturated cyclic carbonate with respect to a non-aqueous electrolyte solution, and the effect of this invention will fully be expressed easily.
  • R is hydrogen, a fluorine, or an ethynyl group from both the reactivity and stability of the compound represented by the general formula (14).
  • the reactivity is lowered, and the expected properties may be lowered.
  • the reactivity is too high, and there is a possibility that side reactions increase.
  • the number of fluorine or ethynyl groups in R is preferably within 2 in total. If the number is too large, the compatibility with the electrolytic solution may be deteriorated, and the reactivity may be too high to increase the side reaction.
  • the molecular weight is more preferably 100 or more, and more preferably 200 or less. If it is this range, it will be easy to ensure further the solubility of General formula (14) with respect to a non-aqueous electrolyte solution, and the effect of this invention will be fully further easily expressed. More preferably, all R are hydrogen. In this case, the side reaction is most likely to be suppressed while maintaining the expected characteristics.
  • the compound represented by the general formula (15) is preferable from the viewpoint of ease of industrial production.
  • Y represents C ⁇ O, S ⁇ O, S ( ⁇ O) 2 , P ( ⁇ O) —R 2 , P ( ⁇ O) —OR 3 . Specific examples of these compounds having preferable conditions are shown below.
  • the compounds having a carbon-carbon triple bond may be used alone or in combination of two or more in any combination and ratio.
  • the compounding amount of the compound having a carbon-carbon triple bond is not particularly limited, and is arbitrary as long as the effects of the present invention are not significantly impaired.
  • the compounding amount of the compound having a carbon-carbon triple bond is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.1% by mass in 100% by mass of the non-aqueous electrolyte solution. Further, it is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.
  • the non-aqueous electrolyte secondary battery is likely to exhibit a sufficient cycle characteristics improvement effect, and the high-temperature storage characteristics are reduced, the amount of gas generated is increased, and the discharge capacity maintenance rate is reduced. Easy to avoid. On the other hand, if the amount is too small, the effects of the present invention may not be sufficiently exerted. If the amount is too large, the resistance may increase and the output and load characteristics may decrease.
  • a cyclic carbonate having an unsaturated bond excluding the compound having a carbon-carbon triple bond is used to form a film on the surface of the negative electrode and achieve a long battery life.
  • unsaturated cyclic carbonate it may be abbreviated as “unsaturated cyclic carbonate”).
  • the unsaturated cyclic carbonate is not particularly limited as long as it is a cyclic carbonate having a carbon-carbon double bond, and any unsaturated carbonate can be used.
  • the cyclic carbonate having an aromatic ring is also included in the unsaturated cyclic carbonate.
  • Examples of the unsaturated cyclic carbonate include vinylene carbonates, ethylene carbonates substituted with a substituent having an aromatic ring or a carbon-carbon double bond, phenyl carbonates, vinyl carbonates, allyl carbonates, catechol carbonates, and the like. It is done.
  • vinylene carbonates vinylene carbonate, methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, phenyl vinylene carbonate, 4,5-diphenyl vinylene carbonate, vinyl vinylene carbonate, 4, 5- vinyl vinylene carbonate, allyl vinylene carbonate, 4 , 5- diallyl vinylene carbonate and the like.
  • ethylene carbonate substituted with a substituent having an aromatic ring or a carbon-carbon double bond examples include vinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, 4-methyl-5-vinyl ethylene carbonate, 4- Allyl-5-vinylethylene carbonate, phenylethylene carbonate, 4,5-diphenylethylene carbonate, 4-phenyl-5-vinylethylene carbonate, 4-allyl-5-phenylethylene carbonate, allylethylene carbonate, 4,5-diallylethylene Examples thereof include carbonate and 4-methyl-5-allylethylene carbonate.
  • unsaturated cyclic carbonates include vinylene carbonate, methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, vinyl vinylene carbonate, 4,5-vinyl vinylene carbonate, allyl vinylene carbonate, 4,5-diallyl vinylene carbonate, Vinylethylene carbonate, 4,5-divinylethylene carbonate, 4-methyl-5-vinylethylene carbonate, allylethylene carbonate, 4,5-diallylethylene carbonate, 4-methyl-5-allylethylene carbonate, 4-allyl-5 Vinylethylene carbonate is more preferably used because it forms a stable interface protective film.
  • the molecular weight of the unsaturated cyclic carbonate is not particularly limited, and is arbitrary as long as the effects of the present invention are not significantly impaired.
  • the molecular weight is preferably 50 or more and 250 or less. If it is this range, it will be easy to ensure the solubility of the unsaturated cyclic carbonate with respect to a non-aqueous electrolyte solution, and the effect of this invention will fully be expressed easily.
  • the molecular weight of the unsaturated cyclic carbonate is more preferably 80 or more, and more preferably 150 or less.
  • the production method of the unsaturated cyclic carbonate is not particularly limited, and can be produced by arbitrarily selecting a known method.
  • An unsaturated cyclic carbonate may be used individually by 1 type, or may have 2 or more types by arbitrary combinations and ratios. Moreover, the compounding quantity of unsaturated cyclic carbonate is not restrict
  • the amount of the unsaturated cyclic carbonate is 100% by mass in the non-aqueous electrolyte solution, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.2% by mass or more. Moreover, Preferably it is 5 mass% or less, More preferably, it is 4 mass% or less, More preferably, it is 3 mass% or less.
  • the non-aqueous electrolyte secondary battery is likely to exhibit a sufficient cycle characteristics improvement effect, and the high-temperature storage characteristics are reduced, the amount of gas generated is increased, and the discharge capacity maintenance rate is reduced. Easy to avoid. On the other hand, if the amount is too small, the effects of the present invention may not be sufficiently exhibited. If the amount is too large, the resistance may increase and the output and load characteristics may decrease.
  • ⁇ Unsaturated cyclic carbonate having a fluorine atom> In the non-aqueous electrolyte secondary battery of the present invention, it is also preferable to use an unsaturated cyclic carbonate having a fluorine atom (hereinafter sometimes abbreviated as “fluorinated unsaturated cyclic carbonate”).
  • fluorinated unsaturated cyclic carbonate The number of fluorine atoms contained in the fluorinated unsaturated cyclic carbonate is not particularly limited as long as it is 1 or more. Among them, the number of fluorine atoms is usually 6 or less, preferably 4 or less, and most preferably 1 or 2 atoms.
  • fluorinated unsaturated cyclic carbonate examples include a fluorinated vinylene carbonate derivative, a fluorinated ethylene carbonate derivative substituted with a substituent having an aromatic ring or a carbon-carbon double bond, and the like.
  • Fluorinated vinylene carbonate derivatives include 4-fluoro vinylene carbonate, 4-fluoro-5-methyl vinylene carbonate, 4-fluoro-5-phenyl vinylene carbonate, 4-allyl-5-fluoro vinylene carbonate, 4-fluoro-5- And vinyl vinylene carbonate.
  • fluorinated ethylene carbonate derivative substituted with a substituent having an aromatic ring or a carbon-carbon double bond examples include 4-fluoro-4-vinylethylene carbonate, 4-fluoro-4-allylethylene carbonate, 4-fluoro-5 -Vinylethylene carbonate, 4-fluoro-5-allylethylene carbonate, 4,4-difluoro-4-vinylethylene carbonate, 4,4-difluoro-4-allylethylene carbonate, 4,5-difluoro-4-vinylethylene carbonate 4,5-difluoro-4-allylethylene carbonate, 4-fluoro-4,5-divinylethylene carbonate, 4-fluoro-4,5-diallylethylene carbonate, 4,5-difluoro-4,5-divinylethylene carbonate , 4,5-Diff Oro-4,5-diallylethylene carbonate, 4-fluoro-4-phenylethylene carbonate, 4-fluoro-5-phenylethylene carbonate, 4,4-difluoro-5-phenyl
  • fluorinated unsaturated cyclic carbonates include 4-fluoro vinylene carbonate, 4-fluoro-5-methyl vinylene carbonate, 4-fluoro-5-vinyl vinylene carbonate, 4-allyl-5-fluoro vinylene carbonate, 4 -Fluoro-4-vinylethylene carbonate, 4-fluoro-4-allylethylene carbonate, 4-fluoro-5-vinylethylene carbonate, 4-fluoro-5-allylethylene carbonate, 4,4-difluoro-4-vinylethylene carbonate 4,4-difluoro-4-allylethylene carbonate, 4,5-difluoro-4-vinylethylene carbonate, 4,5-difluoro-4-allylethylene carbonate, 4-fluoro-4,5-divinylethylene carbonate Bonate, 4-fluoro-4,5-diallylethylene carbonate, 4,5-difluoro-4,5-divinylethylene carbonate, 4,5-difluoro-4,5-diallylethylene
  • the molecular weight of the fluorinated unsaturated cyclic carbonate is not particularly limited, and is arbitrary as long as the effects of the present invention are not significantly impaired.
  • the molecular weight is preferably 50 or more and 250 or less. If it is this range, it will be easy to ensure the solubility of the fluorinated cyclic carbonate with respect to a non-aqueous electrolyte solution, and the effect of this invention will be easy to be expressed.
  • the production method of the fluorinated unsaturated cyclic carbonate is not particularly limited, and can be produced by arbitrarily selecting a known method.
  • the molecular weight is more preferably 100 or more, and more preferably 200 or less.
  • a fluorinated unsaturated cyclic carbonate may be used individually by 1 type, and may have 2 or more types by arbitrary combinations and ratios. Further, the blending amount of the fluorinated unsaturated cyclic carbonate is not particularly limited and is arbitrary as long as the effects of the present invention are not significantly impaired.
  • the compounding amount of the fluorinated unsaturated cyclic carbonate is usually in 100% by mass of the nonaqueous electrolytic solution, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.2% by mass or more. Moreover, it is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.
  • the non-aqueous electrolyte secondary battery is likely to exhibit a sufficient cycle characteristics improvement effect, and the high-temperature storage characteristics are reduced, the amount of gas generated is increased, and the discharge capacity maintenance rate is reduced. Easy to avoid. On the other hand, if the amount is too small, the effects of the present invention may not be sufficiently exhibited. If the amount is too large, the resistance may increase and the output and load characteristics may decrease.
  • a cyclic sulfonate ester In the non-aqueous electrolyte secondary battery of the present invention, it is also preferable to use a cyclic sulfonate ester.
  • the molecular weight of the cyclic sulfonic acid ester compound is not particularly limited and is arbitrary as long as the effects of the present invention are not significantly impaired.
  • the molecular weight is preferably 100 or more and 250 or less. If it is this range, it will be easy to ensure the solubility of the cyclic sulfonic acid ester compound with respect to a non-aqueous electrolyte solution, and the effect of this invention will be easy to be expressed.
  • the production method of the cyclic sulfonate compound is not particularly limited, and can be produced by arbitrarily selecting a known method.
  • Examples of the cyclic sulfonate ester compound that can be used in the non-aqueous electrolyte secondary battery of the present invention include 1,3-propane sultone, 1-fluoro-1,3-propane sultone, 2-fluoro-1, 3-propane sultone, 3-fluoro-1,3-propane sultone, 1-methyl-1,3-propane sultone, 2-methyl-1,3-propane sultone, 3-methyl-1,3-propane sultone, 1 , 4-butane sultone, 1-fluoro-1,4-butane sultone, 2-fluoro-1,4-butane sultone, 3-fluoro-1,4-butane sultone, 4-fluoro-1,4-butane sultone, 1-methyl-1 , 4-butane sultone, 2-methyl-1,4-butane sultone, 3-methyl-1,4-butane sultone
  • 1,3-propane sultone, 1-fluoro-1,3-propane sultone, 2-fluoro-1,3-propane sultone, 3-fluoro-1,3-propane sultone, 1,4-butane sultone, Methylene methane disulfonate and ethylene methane disulfonate are preferable from the viewpoint of improving storage characteristics.
  • 1,3-propane sultone, 1-fluoro-1,3-propane sultone, 2-fluoro-1,3-propane sultone, 3-fluoro 1,3-propane sultone is more preferred.
  • a cyclic sulfonic acid ester having a carbon-carbon double bond examples include 1-propene-1,3-sultone, 2-propene-1,3-sultone, 1-fluoro-1-propene-1,3-sultone, 2 -Fluoro-1-propene-1,3-sultone, 3-fluoro-1-propene-1,3-sultone, 1-methyl-1-propene-1,3-sultone, 2-methyl-1-propene-1 , 3-sultone, 3-methyl-1-propene-1,3-sultone, 1-butene-1,4-sultone, 2-butene-1,4-sultone, 3-butene-1,4-sultone, 1 -Fluoro-1-butene-1,4-sultone, 2-fluoro-1-butene-1,4-sultone, 3-fluoro-1
  • 1-propene-1,3-sultone, 1-butene-1,4-sultone, 2-butene-1,4-sultone, and 3-butene-1,4-sultone are more preferable.
  • a cyclic sulfonic acid ester compound may be used individually by 1 type, and may have 2 or more types by arbitrary combinations and ratios. There is no limit to the amount of the cyclic sulfonic acid ester compound added to the whole non-aqueous electrolyte, and it is optional as long as the effects of the present invention are not significantly impaired. Is contained in a concentration of 0.1% by mass or more, more preferably 0.3% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less. When the above range is satisfied, effects such as output characteristics, load characteristics, low temperature characteristics, cycle characteristics, and high temperature storage characteristics are further improved.
  • ⁇ Compound having a cyano group> In the non-aqueous electrolyte secondary battery of the present invention, it is also preferable to use a compound having a cyano group.
  • the compound having a cyano group is not particularly limited as long as it is a compound having a cyano group in the molecule, but a compound represented by the general formula (9) is more preferable.
  • T represents an organic group composed of an atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and a halogen atom, and U represents a substituent.
  • the molecular weight of the compound having a cyano group is not particularly limited, and is arbitrary as long as the effects of the present invention are not significantly impaired.
  • the molecular weight is preferably 50 or more, more preferably 80 or more, still more preferably 100 or more, and 200 or less. If it is this range, it will be easy to ensure the solubility of the compound which has a cyano group with respect to nonaqueous electrolyte solution, and the effect of this invention will be easy to be expressed.
  • the production method of the compound having a cyano group is not particularly limited, and can be produced by arbitrarily selecting a known method.
  • Specific examples of the compound represented by the general formula (9) include, for example, Acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, lauronitrile, 2-methylbutyronitrile, 2,2-dimethylbutyronitrile, hexanenitrile, cyclopentanecarbonitrile, cyclohexanecarbonitrile , Acrylonitrile, methacrylonitrile, crotononitrile, 3-methylcrotononitrile, 2-methyl-2-butenenitryl, 2-pentenenitrile, 2-methyl-2-pentenenitrile, 3-methyl-2-pentenenitrile 2-hexenenitrile, fluoroacetonitrile, difluoroacetonitrile, trifluoroacetonitrile, 2-fluoropropionitrile, 3-fluoropropionitrile, 2,2-difluoropropionitrile, 2,3 Difluoropropionitrile,
  • Cyanate compounds such as methyl cyanate, ethyl cyanate, propyl cyanate, butyl cyanate, pentyl cyanate, hexyl cyanate, heptyl cyanate;
  • a compound having two groups is more preferred.
  • the compound which has a cyano group may be used individually by 1 type, and may have 2 or more types together by arbitrary combinations and ratios.
  • the compound having an isocyanato group is not particularly limited as long as it is a compound having an isocyanato group in the molecule, but as a specific example, Isocyanatomethane, 1-isocyanatoethane, 1-isocyanato-2-methoxyethane, 3-isocyanato-1-propene, isocyanatocyclopropane, 2-isocyanatopropane, 1-isocyanatopropane, 1-isocyanato-3- Methoxypropane, 1-isocyanato-3-ethoxypropane, 2-isocyanato-2-methylpropane, 1-isocyanatobutane, 2-isocyanatobutane, 1-isocyanato-4-methoxybutane, 1-isocyanato-4-ethoxy
  • a compound represented by the general formula (10-5) is preferable in order to form a good protective film.
  • A represents a C 1-20 organic group composed of an atom selected from the group consisting of a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, and a halogen atom;
  • n ′ is an integer of 2 or more.
  • the organic group having 1 to 20 carbon atoms composed of an atom selected from the group consisting of a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, and a halogen atom is composed of a carbon atom and a hydrogen atom.
  • An organic group which may contain a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, or a halogen atom is an organic group in which a part of the carbon atoms of the skeleton is substituted with these atoms, or these atoms. It is meant to include an organic group having a configured substituent.
  • the molecular weight of the compound represented by the general formula (10-5) is not particularly limited, and is arbitrary as long as the effects of the present invention are not significantly impaired.
  • the molecular weight is preferably 80 or more, more preferably 115 or more, still more preferably 180 or more, and is 400 or less, more preferably 270 or less. Within this range, it is easy to ensure the solubility of the compound represented by the general formula (10-5) in the nonaqueous electrolytic solution, and the effects of the present invention are easily exhibited.
  • the method for producing the compound represented by the general formula (10-5) is not particularly limited, and can be produced by arbitrarily selecting a known method.
  • a in the general formula (10-5) include, for example, Alkylene group or derivative thereof, alkenylene group or derivative thereof, cycloalkylene group or derivative thereof, alkynylene group or derivative thereof, cycloalkenylene group or derivative thereof, arylene group or derivative thereof, carbonyl group or derivative thereof, sulfonyl group or derivative thereof, Sulfinyl group or derivative thereof, phosphonyl group or derivative thereof, phosphinyl group or derivative thereof, amide group or derivative thereof, imide group or derivative thereof, ether group or derivative thereof, thioether group or derivative thereof, borinic acid group or derivative thereof, borane Group or a derivative thereof.
  • an alkylene group or a derivative thereof, an alkenylene group or a derivative thereof, a cycloalkylene group or a derivative thereof, an alkynylene group or a derivative thereof, an arylene group or a derivative thereof is preferable from the viewpoint of improving battery characteristics.
  • B is an organic group having 2 to 14 carbon atoms which may have a substituent.
  • Specific examples of the compound represented by the general formula (10-5) include, for example, monomethylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene.
  • trimethylene diisocyanate hexamethylene diisocyanate (HMDI), 1,3-bis (isocyanatomethyl) cyclohexane (BIMCH), dicyclohexylmethane-4,4′-diisocyanate, formulas (10-1) to (10- Biuret, isocyanurate, adduct, and bifunctional type modified polyisocyanate represented by the basic structure 4) are preferred from the viewpoint of forming a more stable film.
  • HMDI hexamethylene diisocyanate
  • BIMCH 1,3-bis (isocyanatomethyl) cyclohexane
  • dicyclohexylmethane-4,4′-diisocyanate formulas (10-1) to (10- Biuret, isocyanurate, adduct, and bifunctional type modified polyisocyanate represented by the basic structure 4
  • the isocyanate compound mentioned above may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
  • the amount of the compound represented by the general formula (10-5) with respect to the whole non-aqueous electrolyte solution is optional as long as the effects of the present invention are not significantly impaired.
  • 0.001% by mass or more preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and usually 5% by mass or less, preferably 4.0% by mass.
  • it is more preferably 3.0% by mass or less, and further preferably 2% by mass or less.
  • auxiliary auxiliaries In the non-aqueous electrolyte secondary battery of the present invention, other known auxiliary agents can be used.
  • Other auxiliary agents include carbonate compounds such as erythritan carbonate, spiro-bis-dimethylene carbonate, methoxyethyl-methyl carbonate; succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, anhydrous Carboxylic anhydrides such as itaconic acid, diglycolic anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride and phenylsuccinic anhydride; 2,4,8,10-tetraoxaspiro [5.5 ] Spiro compounds such as undecane, 3,9-divinyl-2,4,8,10-tetraoxaspiro [5.5] undecane; ethylene sulfite, methyl fluoros
  • ethylene sulfite methyl fluorosulfonate, methyl methanesulfonate, methyl ethanesulfonate, ethyl methanesulfonate, busulfan, 1,4-butanediol bis (2,2,2-trifluoroethanesulfonate), etc.
  • This sulfur-containing compound is particularly preferable because it has a large effect of improving capacity retention characteristics and cycle characteristics after high-temperature storage.
  • the compounding amount of other auxiliary agents is not particularly limited, and is arbitrary as long as the effects of the present invention are not significantly impaired.
  • the other auxiliary agent is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.2% by mass or more in 100% by mass of the non-aqueous electrolyte solution. It is at most 3% by mass, more preferably at most 3% by mass, even more preferably at most 1% by mass. Within this range, the effects of other auxiliaries can be sufficiently exhibited, and it is easy to avoid a situation in which battery characteristics such as high-load discharge characteristics deteriorate.
  • the non-aqueous electrolyte solution described above includes those existing inside the non-aqueous electrolyte secondary battery of the present invention. Specifically, the components of the non-aqueous electrolyte such as lithium salt, solvent, and auxiliary agent are separately synthesized, and the non-aqueous electrolyte is prepared from the substantially isolated one by the method described below. In the case of a non-aqueous electrolyte solution in a non-aqueous electrolyte secondary battery obtained by pouring into a separately assembled battery, the components of the non-aqueous electrolyte solution according to the present invention are individually placed in the battery.
  • the compound constituting the non-aqueous electrolyte solution according to the present invention is further contained in the non-aqueous electrolyte secondary battery.
  • a case where the same composition as that of the nonaqueous electrolytic solution according to the present invention is obtained is also included.
  • the non-aqueous electrolyte solution according to the present invention is for a secondary battery that is used at an upper limit operating potential of the positive electrode of 4.5 V or higher, preferably 4.55 V or higher, more preferably 4.60 V or higher on the basis of Li / Li + . It is suitably used as an electrolyte solution.
  • the upper limit operating potential of the positive electrode is usually 5.05 V or less on the basis of Li / Li + .
  • the durability of the battery is improved, which may be preferable depending on the usage of the battery.
  • the positive electrode active material used for the positive electrode is described below.
  • the positive electrode active material is not particularly limited as long as it can electrochemically occlude and release lithium ions, but is a transition metal compound containing at least one metal element in addition to Li and Mn, at least Li, Ni. And at least one selected from the group consisting of transition metal compounds containing Co and / or Mn, and mixed valence transition metal compounds containing one or more transition metal elements each having an average oxidation number of +4 and +3 It is preferable to include.
  • transition metal compound examples include lithium transition metal compounds represented by the following general formulas (4) to (6).
  • Li [Li a M x Mn 2-xa ] O 4 + ⁇ (4) (In the formula (4), 0 ⁇ a ⁇ 0.3, 0.4 ⁇ x ⁇ 1.1, ⁇ 0.5 ⁇ ⁇ 0.5 is satisfied, and M is Ni, Cr, Fe, Co, and Cu.
  • M1 represents Ni, Co
  • M2 represents Fe, Cr, V, Ti, Cu, Ga, Bi, Sn, B, P, Zn, Mg, Ge, Nb, W, Ta, Be, Al, Ca, Sc and Zr.
  • LiM′O 2 (6) (In the formula (6), 0 ⁇ ⁇ 1 is satisfied, M is at least one of metal elements having an average oxidation number of +4, and M ′ is a metal element having an average oxidation number of +3. Represents at least one of them.)
  • Ni, Cr, Mn, Fe, Co and Cu are preferable, and specific examples include LiMn 2 O 4 , Li 2 MnO 4 and Li 1 + a.
  • Lithium-manganese composite oxides such as Mn 2 O 4 (a; 0 ⁇ a ⁇ 3.0), LiMn x Ni 2 ⁇ x O 4 , Li 1 + a Mn 1.5 Ni 0.5 O 4 (a; 0 ⁇ and lithium / nickel / manganese composite oxides such as a ⁇ 3.0).
  • transition metal of the lithium transition metal compound represented by the general formula (5) V, Ti, Cr, Mn, Fe, Co, Ni, Cu, and the like are preferable, and specific examples include lithium, such as LiCoO 2 Examples include cobalt composite oxides, lithium / manganese composite oxides such as LiMnO 2 , and lithium / nickel composite oxides such as LiNiO 2 .
  • LiCoO 2 lithium, such as LiCoO 2
  • cobalt composite oxides lithium / manganese composite oxides such as LiMnO 2
  • lithium / nickel composite oxides such as LiNiO 2 .
  • 0 ⁇ y ⁇ 1 and 0 ⁇ z ⁇ 0.3 are satisfied. However, when both y and z are 0, that is, those containing no transition metal, It is not included in the lithium transition metal compound represented by (5).
  • transition metal atoms that are the main components of these lithium transition metal composite oxides are Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Si.
  • Specific examples include lithium-nickel-cobalt-aluminum composite oxides, lithium-cobalt-nickel composite oxides, lithium-cobalt-manganese composite oxides, lithium- Nickel / manganese composite oxide, lithium / nickel / cobalt / manganese composite oxide, and the like can be given.
  • lithium / nickel / manganese composite oxide and lithium / nickel / cobalt / manganese composite oxide are preferable because of good battery characteristics.
  • substituted ones include, for example, Li 1 + a Ni 0.5 Mn 0.5 O 2 , Li 1 + a Ni 0.8 Co 0.2 O 2 , Li 1 + a Ni 0.85 Co 0.10 Al 0. 05 O 2 , Li 1 + a Ni 0.33 Co 0.33 Mn 0.33 O 2 , Li 1 + a Ni 0.45 Mn 0.45 Co 0.1 O 2 , Li 1 + a Ni 0.475 Mn 0.475 Co 0 .05 O 2 , Li 1 + a Mn 1.8 Al 0.2 O 4 , xLi 2 MnO 3.
  • LiM′O 2 can be cited as represented by the general formula (6).
  • M is at least one of metal elements having an average oxidation number of +4, and preferably consists of Mn, Zr, Ti, Ru, Re, and Pt. At least one selected from the group, more preferably at least one selected from the group consisting of Mn, Zr and Ti.
  • M ′ is at least one of metal elements having an average oxidation number of +3, preferably at least one metal element selected from the group consisting of V, Mn, Fe, Co, and Ni. More preferably, it is at least one metal element selected from the group consisting of Mn, Co and Ni.
  • the above general formula (4) and the above general formula (6) as the positive electrode for a battery having a high open circuit voltage between the battery terminals, more preferably the above general formula (4). It is preferable to use from the viewpoint of the stability of the positive electrode active material.
  • the lithium transition metal-based compound represented by the general formula (4) LiMn x Ni 2 -x O 4, Li 1 + a Mn 1.5 Ni 0.5 O 4 (a; 0 ⁇ a Lithium / nickel / manganese composite oxides such as ⁇ 3.0) are preferable from the viewpoints of stability of the positive electrode active material and charge capacity.
  • a lithium-containing transition metal phosphate compound is also preferably used as the positive electrode active material.
  • the transition metal of the lithium-containing transition metal phosphate compound include V, Ti, Cr, Mn, and Fe. , Co, Ni, Cu and the like are preferable.
  • lithium transition metal phosphates such as LiFePO 4 , Li 3 Fe 2 (PO 4 ) 3 and LiFeP 2 O 7
  • cobalt phosphates such as LiCoPO 4
  • Some of the transition metal atoms that are the main components of these lithium transition metal phosphate compounds are Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, and Si. And the like substituted with other elements.
  • lithium phosphate in the positive electrode active material because continuous charging characteristics are improved.
  • the lower limit of the amount of lithium phosphate used is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% by mass with respect to the total of the positive electrode active material and lithium phosphate. %, And the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less.
  • Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate, carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate, and carbon.
  • these surface adhering substances are dissolved or suspended in a solvent, impregnated and added to the positive electrode active material, and dried.
  • the surface adhering substance precursor is dissolved or suspended in a solvent and impregnated and added to the positive electrode active material, It can be made to adhere to the surface of the positive electrode active material by a method of reacting by heating or the like, a method of adding to the positive electrode active material precursor and firing simultaneously.
  • the method of making carbonaceous adhere mechanically later in the form of activated carbon etc. can also be used, for example.
  • the amount of the surface adhering substance is by mass with respect to the positive electrode active material, preferably 0.1 ppm or more, more preferably 1 ppm or more, still more preferably 10 ppm or more, and the upper limit, preferably 20% or less, more preferably, as the lower limit. Is used at 10% or less, more preferably 5% or less.
  • the surface adhering substance can suppress the oxidation reaction of the electrolyte solution on the surface of the positive electrode active material and can improve the battery life. However, when the amount of the adhering quantity is too small, the effect is not sufficiently manifested. If it is too high, the resistance may increase in order to inhibit the entry and exit of lithium ions.
  • the “positive electrode active material” includes a material having a composition different from the surface attached to the surface of the positive electrode active material.
  • shape examples of the shape of the particles of the positive electrode active material include a lump shape, a polyhedron shape, a sphere shape, an oval sphere shape, a plate shape, a needle shape, and a column shape, which are conventionally used. Moreover, primary particles may aggregate to form secondary particles.
  • the tap density of the positive electrode active material is preferably 0.5 g / cm 3 or more, more preferably 0.8 g / cm 3 or more, and further preferably 1.0 g / cm 3 or more.
  • the tap density of the positive electrode active material is lower than the lower limit, the amount of necessary dispersion medium increases when the positive electrode active material layer is formed, and the necessary amount of conductive material and binder increases, and the positive electrode to the positive electrode active material layer The filling rate of the active material is restricted, and the battery capacity may be restricted.
  • a complex oxide powder having a high tap density a high-density positive electrode active material layer can be formed.
  • the tap density is preferably as large as possible, and there is no particular upper limit, but if it is too large, diffusion of lithium ions using the electrolytic solution in the positive electrode active material layer as a medium is rate-limiting, and load characteristics may be easily reduced.
  • the upper limit is preferably 3.0 g / cm 3 or less, more preferably 2.7 g / cm 3 or less, and even more preferably 2.5 g / cm 3 or less.
  • the tap density is defined as the powder packing density (tap density) g / cc when 5 to 10 g of the positive electrode active material powder is put into a 10 ml glass graduated cylinder and tapped 200 times with a stroke of about 20 mm. Ask.
  • the median diameter d 50 of the lithium / nickel / cobalt / manganese composite oxide particles that can be contained in the positive electrode active material is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more, most preferably 1.0 ⁇ m or more, and the upper limit is preferably 30 ⁇ m or less, more preferably 27 ⁇ m or less, and even more preferably 25 ⁇ m or less. Most preferably, it is 22 ⁇ m or less. If the lower limit is not reached, a high tap density product may not be obtained.
  • the median diameter d 50 is measured by a known laser diffraction / scattering particle size distribution measuring apparatus.
  • LA-920 manufactured by HORIBA is used as a particle size distribution meter
  • a 0.1% by mass sodium hexametaphosphate aqueous solution is used as a dispersion medium for measurement, and a measurement refractive index of 1.24 is set after ultrasonic dispersion for 5 minutes. Measured.
  • the median diameter of the lithium / nickel / manganese composite oxide that can be contained in the positive electrode active material is usually 2 ⁇ m or more, preferably 2.5 ⁇ m or more, more preferably 3 ⁇ m or more, still more preferably 3.5 ⁇ m or more, and most preferably 4 ⁇ m or more. Usually, it is 60 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, further preferably 30 ⁇ m or less, and most preferably 20 ⁇ m or less. If the median diameter is less than this lower limit, there is a possibility of causing a problem in applicability at the time of forming the positive electrode active material layer, and if it exceeds the upper limit, battery performance may be lowered.
  • the 90% cumulative diameter (D 90 ) of the secondary particles of lithium / nickel / manganese composite oxide that can be contained in the positive electrode active material is usually 30 ⁇ m or less, preferably 25 ⁇ m or less, more preferably 22 ⁇ m or less, and most preferably 20 ⁇ m. In the following, it is usually 3 ⁇ m or more, preferably 4 ⁇ m or more, more preferably 5 ⁇ m or more, and most preferably 6 ⁇ m or more. If the 90% cumulative diameter (D 90 ) exceeds the above upper limit, the battery performance may be deteriorated, and if it is less than the lower limit, there is a possibility of causing a problem in the coating property when forming the positive electrode active material layer.
  • the median diameter and the 90% cumulative diameter (D 90 ) as the average particle diameter are set to a refractive index of 1.60 by a known laser diffraction / scattering particle size distribution measuring device, and the particle diameter standard is determined. Measured as a volume reference. In this invention, it measured using 0.1 mass% sodium hexametaphosphate aqueous solution as a dispersion medium used in the case of a measurement.
  • the average primary particle size of the positive electrode active material is preferably Is 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, further preferably 0.2 ⁇ m or more, and the upper limit is preferably 5 ⁇ m or less, more preferably 4 ⁇ m or less, still more preferably 3 ⁇ m or less, and most preferably 2 ⁇ m or less. is there.
  • the average diameter (average primary particle diameter) of the lithium / nickel / manganese composite oxide that can be contained in the positive electrode active material is not particularly limited, but the lower limit is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more.
  • the upper limit is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less, still more preferably 1.5 ⁇ m or less, and most preferably 1.2 ⁇ m or less. If the average primary particle size exceeds the above upper limit, it may adversely affect the powder filling property or the specific surface area will decrease, which may increase the possibility that the battery performance such as rate characteristics and output characteristics will decrease. There is sex. If the lower limit is not reached, there is a possibility that problems such as inferior reversibility of charge / discharge due to the undeveloped crystals.
  • the primary particle diameter is measured by observation using a scanning electron microscope (SEM). Specifically, in a photograph at a magnification of 10000 times, the longest value of the intercept by the left and right boundary lines of the primary particles with respect to the horizontal straight line is obtained for any 50 primary particles and obtained by taking the average value. It is done.
  • SEM scanning electron microscope
  • the BET specific surface area of the lithium / nickel / cobalt / manganese composite oxide that can be contained in the positive electrode active material is preferably 0.1 m 2 / g or more, more preferably 0.2 m 2 / g or more, and still more preferably 0.3 m.
  • the upper limit is 50 m 2 / g or less, preferably 40 m 2 / g or less, and more preferably 30 m 2 / g or less. If the BET specific surface area is smaller than this range, the battery performance is likely to be lowered. If the BET specific surface area is larger, the tap density is difficult to increase, and a problem may occur in applicability at the time of forming the positive electrode active material layer.
  • Lithium-nickel-manganese composite oxide may be included in the positive electrode active material also, BET specific surface area is usually 0.2 m 2 / g or more, preferably 0.3 m 2 / g or more, more preferably 0.35 m 2 / g or more, most preferably 0.4 m 2 / g or more, usually 3 m 2 / g or less, preferably 2.5 m 2 / g or less, more preferably 2 m 2 / g or less, most preferably 1.5 m 2 / g. It is as follows. If the BET specific surface area is smaller than this range, the battery performance is likely to be lowered.
  • the BET specific surface area can be measured with a known BET type powder specific surface area measuring device.
  • an OMS Riken: AMS8000 type automatic powder specific surface area measuring device was used, nitrogen was used as an adsorption gas, and helium was used as a carrier gas.
  • the powder sample was heated and deaerated with a mixed gas at a temperature of 150 ° C., then cooled to liquid nitrogen temperature to adsorb the mixed gas, and then heated to room temperature with water to be adsorbed. Nitrogen gas was desorbed, the amount was detected by a heat conduction detector, and the specific surface area of the sample was calculated therefrom.
  • Method for producing positive electrode active material As a manufacturing method of the positive electrode active material, a general method is used as a manufacturing method of the inorganic compound. In particular, various methods are conceivable for preparing a spherical or elliptical active material. For example, a transition metal source material is dissolved or pulverized and dispersed in a solvent such as water, and the pH is adjusted while stirring. And a spherical precursor is prepared and recovered, and dried as necessary. Then, a Li source such as LiOH, Li 2 CO 3 , LiNO 3 is added, and the active material is obtained by baking at a high temperature. .
  • the lithium compound, at least one transition metal compound selected from Mn, Ni, Cr, Fe, Co and Cu, and the additive of the present invention are pulverized in a liquid medium, and these are uniformly dispersed.
  • a lithium transition metal system for a lithium secondary battery positive electrode material of the present invention comprising a slurry preparation step for obtaining a slurry, a spray drying step for spray drying the obtained slurry, and a firing step for firing the obtained spray dried body It is preferably produced by a compound production method.
  • the positive electrode active material may be used alone, or one or more of different compositions may be used in any combination or ratio.
  • a preferred combination in this case is a combination of LiCoO 2 and LiMn 2 O 4 such as LiNi 0.33 Co 0.33 Mn 0.33 O 2 or a part of Mn substituted with another transition metal or the like. Or a combination with LiCoO 2 or a part of this Co substituted with another transition metal or the like.
  • the positive electrode can be produced by forming a positive electrode active material layer containing a positive electrode active material and a binder on a current collector. Manufacture of the positive electrode using a positive electrode active material can be performed by a conventional method.
  • a positive electrode can be obtained by forming a positive electrode active material layer on the current collector by applying it to a positive electrode current collector and drying it as a slurry by dissolving or dispersing in a slurry.
  • the content of the positive electrode active material in the positive electrode active material layer is preferably 80% by mass or more, more preferably 82% by mass or more, and particularly preferably 84% by mass or more. Moreover, an upper limit becomes like this. Preferably it is 99 mass% or less, More preferably, it is 98 mass% or less. If the content of the positive electrode active material in the positive electrode active material layer is low, the electric capacity may be insufficient. Conversely, if the content is too high, the strength of the positive electrode may be insufficient.
  • the positive electrode active material layer obtained by coating and drying is preferably consolidated by a hand press, a roller press or the like in order to increase the packing density of the positive electrode active material.
  • the density of the positive electrode active material layer is preferably 1.5 g / cm 3 or more as a lower limit, more preferably 2 g / cm 3 , still more preferably 2.2 g / cm 3 or more, and the upper limit is preferably 5 g / cm 3. It is 3 or less, more preferably 4.5 g / cm 3 or less, and further preferably 4 g / cm 3 or less.
  • the permeability of the electrolyte solution to the vicinity of the current collector / active material interface decreases, and the charge / discharge characteristics particularly at a high current density may decrease, and a high output may not be obtained.
  • the conductivity between the active materials is lowered, the battery resistance is increased, and a high output may not be obtained.
  • a known conductive material can be arbitrarily used as the conductive material. Specific examples include metal materials such as copper and nickel; graphite such as natural graphite and artificial graphite (graphite); carbon black such as acetylene black; and carbon materials such as amorphous carbon such as needle coke. In addition, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
  • the conductive material is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more in the positive electrode active material layer, and the upper limit is usually 50% by mass or less, preferably It is used so as to contain 30% by mass or less, more preferably 15% by mass or less. If the content is lower than this range, the conductivity may be insufficient. Conversely, if the content is higher than this range, the battery capacity may decrease.
  • the binder used for the production of the positive electrode active material layer is not particularly limited, and in the case of the coating method, any material that can be dissolved or dispersed in the liquid medium used at the time of electrode production may be used.
  • Resin polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, nitrocellulose; SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluorine rubber, isoprene rubber , Rubber polymers such as butadiene rubber and ethylene-propylene rubber; styrene / butadiene / styrene block copolymer or its hydrogenated product, EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene / butadiene / Ethylene copolymer, styrene Thermoplastic e
  • the ratio of the binder in the positive electrode active material layer is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 1.5% by mass or more, and the upper limit is usually 80% by mass or less, preferably Is 60% by mass or less, more preferably 40% by mass or less, and most preferably 10% by mass or less.
  • the ratio of the binder is too low, the positive electrode active material cannot be sufficiently retained and the positive electrode has insufficient mechanical strength, which may deteriorate battery performance such as cycle characteristics. On the other hand, if it is too high, battery capacity and conductivity may be reduced.
  • the solvent for forming the slurry As the solvent for forming the slurry, the positive electrode active material, the conductive material, the binder, and a solvent that can dissolve or disperse the thickener that is used as necessary are particularly suitable for the type. There is no restriction, and either an aqueous solvent or an organic solvent may be used. Examples of the aqueous medium include water, a mixed medium of alcohol and water, and the like.
  • organic medium examples include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene; heterocyclic compounds such as quinoline and pyridine; ketones such as acetone, methyl ethyl ketone, and cyclohexanone.
  • Esters such as methyl acetate and methyl acrylate; amines such as diethylenetriamine and N, N-dimethylaminopropylamine; ethers such as diethyl ether, propylene oxide and tetrahydrofuran (THF); N-methylpyrrolidone (NMP) Amides such as dimethylformamide and dimethylacetamide; and aprotic polar solvents such as hexamethylphosphalamide and dimethylsulfoxide.
  • amines such as diethylenetriamine and N, N-dimethylaminopropylamine
  • ethers such as diethyl ether, propylene oxide and tetrahydrofuran (THF)
  • NMP N-methylpyrrolidone
  • Amides such as dimethylformamide and dimethylacetamide
  • aprotic polar solvents such as hexamethylphosphalamide and dimethylsulfoxide.
  • a thickener is usually used to adjust the viscosity of the slurry.
  • the thickener is not particularly limited, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.
  • the ratio of the thickener to the active material is 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.3% by mass or more.
  • the upper limit is 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. Below this range, applicability may be significantly reduced. If it exceeds, the ratio of the active material in the positive electrode active material layer may decrease, and there may be a problem that the capacity of the battery decreases and a problem that the resistance between the positive electrode active materials increases.
  • the material of the positive electrode current collector is not particularly limited, and a known material can be arbitrarily used. Specific examples include metal materials such as aluminum, stainless steel, nickel plating, titanium, and tantalum; and carbon materials such as carbon cloth and carbon paper. Of these, metal materials, particularly aluminum, are preferred.
  • the shape of the current collector examples include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punch metal, and foam metal in the case of a metal material.
  • a thin film, a carbon cylinder, etc. are mentioned. Of these, metal thin films are preferred.
  • the thickness of the thin film is arbitrary, it is usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and the upper limit is usually 1 mm or less, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less. If the thin film is thinner than this range, the strength required for the current collector may be insufficient. Conversely, if the thin film is thicker than this range, the handleability may be impaired.
  • a conductive additive is applied to the surface of the current collector.
  • the conductive assistant include noble metals such as carbon, gold, platinum, and silver.
  • the ratio of the thickness of the current collector to the positive electrode active material layer is not particularly limited, but the value of (thickness of positive electrode active material layer on one side immediately before electrolyte injection) / (thickness of current collector) is 20
  • the lower limit is preferably 15 or less, most preferably 10 or less, and the lower limit is preferably 0.5 or more, more preferably 0.8 or more, and most preferably 1 or more. Above this range, the current collector may generate heat due to Joule heat during high current density charge / discharge. Below this range, the volume ratio of the current collector to the positive electrode active material may increase and the battery capacity may decrease.
  • the area of the positive electrode active material layer is preferably larger than the outer surface area of the battery outer case from the viewpoint of increasing the stability at high output and high temperature.
  • the sum of the electrode areas of the positive electrode with respect to the surface area of the exterior of the secondary battery is preferably 15 times or more, and more preferably 40 times or more.
  • the outer surface area of the outer case is the total area obtained by calculation from the vertical, horizontal, and thickness dimensions of the case part filled with the power generation element excluding the protruding part of the terminal in the case of a bottomed square shape. .
  • the geometric surface area approximates the case portion filled with the power generation element excluding the protruding portion of the terminal as a cylinder.
  • the total electrode area of the positive electrode is the geometric surface area of the positive electrode mixture layer facing the composite material layer containing the negative electrode active material, and in a structure in which the positive electrode mixture layer is formed on both sides via a current collector foil. , The sum of the areas where each surface is calculated separately.
  • the thickness of the positive electrode plate is not particularly limited, but from the viewpoint of high capacity and high output, the thickness of the composite layer obtained by subtracting the thickness of the metal foil of the core material is preferably set as the lower limit with respect to one side of the current collector. Is 10 ⁇ m or more, more preferably 20 ⁇ m or more, and the upper limit is preferably 500 ⁇ m or less, more preferably 450 ⁇ m or less.
  • Electrode surface coating (Positive electrode surface coating) Moreover, you may use what the substance of the composition different from this adhered to the surface of the said positive electrode plate.
  • Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate, carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate, and carbon.
  • Negative electrode The negative electrode active material used for the negative electrode is described below.
  • the negative electrode active material is not particularly limited as long as it can electrochemically occlude and release lithium ions, and specific examples include carbonaceous materials, alloy-based materials, lithium-containing metal composite oxide materials, and the like.
  • carbonaceous material when used, it is preferable to contain at least one negative electrode active material composed of graphite particles having a rhombohedral crystal ratio of 0% to 35%. One of these may be used alone, or two or more of these may be used in any combination.
  • the negative electrode active material examples include carbonaceous materials, alloy-based materials, lithium-containing metal composite oxide materials, and mixtures thereof.
  • a carbonaceous material used as a negative electrode active material (1) natural graphite, (2) a carbonaceous material obtained by heat-treating an artificial carbonaceous material and an artificial graphite material at least once in the range of 400 to 3200 ° C; (3) a carbonaceous material in which the negative electrode active material layer is made of carbonaceous materials having at least two or more different crystallinities and / or has an interface in contact with the different crystalline carbonaceous materials, (4) A carbonaceous material in which the negative electrode active material layer is made of carbonaceous materials having at least two or more different orientations and / or has an interface in contact with the carbonaceous materials having different orientations, Is preferably a good balance between initial irreversible capacity and high current density charge / discharge characteristics.
  • the carbonaceous materials (1) to (4) may be used alone or in combination of two or more in any
  • Examples of the artificial carbonaceous material and artificial graphite material of (2) above include natural graphite, coal-based coke, petroleum-based coke, coal-based pitch, petroleum-based pitch, those obtained by oxidizing these pitches, needle coke, pitch coke and Carbon materials that are partially graphitized, furnace black, acetylene black, organic pyrolysis products such as pitch-based carbon fibers, carbonizable organic materials and their carbides, or carbonizable organic materials are benzene, toluene, xylene, quinoline And a solution dissolved in a low-molecular organic solvent such as n-hexane, and carbides thereof.
  • the negative electrode active material As an alloy material used as the negative electrode active material, as long as lithium can be occluded / released, lithium alone, simple metals and alloys forming lithium alloys, or oxides, carbides, nitrides, silicides, sulfides thereof Any of compounds such as products or phosphides may be used and is not particularly limited.
  • the single metal and alloy forming the lithium alloy are preferably materials containing group 13 and group 14 metal / metalloid elements (that is, excluding carbon), more preferably aluminum, silicon and tin (hereinafter referred to as “ Simple metals) and alloys or compounds containing these atoms (sometimes abbreviated as “specific metal elements”).
  • a negative electrode active material having at least one kind of atom selected from a specific metal element, a metal simple substance of any one specific metal element, an alloy composed of two or more specific metal elements, one type or two or more specific types Alloys comprising metal elements and one or more other metal elements, as well as compounds containing one or more specific metal elements, and oxides, carbides, nitrides and silicides of the compounds And composite compounds such as sulfides or phosphides.
  • these simple metals, alloys or metal compounds as the negative electrode active material, the capacity of the battery can be increased.
  • compounds in which these complex compounds are complexly bonded to several elements such as simple metals, alloys or non-metallic elements are also included.
  • silicon and tin an alloy of these elements and a metal that does not operate as a negative electrode can be used.
  • tin a complex compound containing 5 to 6 kinds of elements in combination with a metal that acts as a negative electrode other than tin and silicon, a metal that does not operate as a negative electrode, and a nonmetallic element may be used. it can.
  • any one simple metal of a specific metal element, an alloy of two or more specific metal elements, oxidation of a specific metal element In particular, silicon and / or tin metal simple substance, alloy, oxide, carbide, nitride and the like are preferable from the viewpoint of capacity per unit mass and environmental load.
  • the lithium-containing metal composite oxide material used as the negative electrode active material is not particularly limited as long as it can occlude and release lithium, but a material containing titanium and lithium is preferable from the viewpoint of high current density charge / discharge characteristics, A lithium-containing composite metal oxide material containing titanium is more preferable, and a composite oxide of lithium and titanium (hereinafter sometimes abbreviated as “lithium titanium composite oxide”). That is, it is particularly preferable to use a lithium titanium composite oxide having a spinel structure in a negative electrode active material for a non-aqueous electrolyte secondary battery because the output resistance is greatly reduced.
  • lithium or titanium of the lithium titanium composite oxide is at least selected from the group consisting of other metal elements such as Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb. Those substituted with one element are also preferred.
  • the metal oxide is a lithium titanium composite oxide represented by the general formula (A). In the general formula (A), 0.7 ⁇ x ⁇ 1.5, 1.5 ⁇ y ⁇ 2.3, It is preferable that 0 ⁇ z ⁇ 1.6 because the structure at the time of doping / dedoping with lithium ions is stable.
  • M represents at least one element selected from the group consisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb.
  • M represents at least one element selected from the group consisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb.
  • (A) 1.2 ⁇ x ⁇ 1.4, 1.5 ⁇ y ⁇ 1.7, z 0
  • This structure is particularly preferable because of a good balance of battery performance.
  • Particularly preferred representative compositions of the above compounds are Li 4/3 Ti 5/3 O 4 in (a), Li 1 Ti 2 O 4 in (b), and Li 4/5 Ti 11/5 O in (c). 4 .
  • the rhombohedral crystal ratio defined in the present invention is expressed by the following formula from the ratio of the rhombohedral structure graphite layer (ABC stacking layer) and the hexagonal structure graphite layer (AB stacking layer) by X-ray wide angle diffraction (XRD). Can be obtained.
  • Rhombohedral crystal ratio (%) integrated intensity of ABC (101) peak of XRD ⁇ XRD AB (101) peak integrated intensity ⁇ 100
  • the rhombohedral crystal ratio of the graphite particles of the present invention is usually 0% or more, preferably more than 0%, more preferably 3% or more, still more preferably 5% or more, particularly preferably 12% or more, Usually, it is 35% or less, preferably 27% or less, more preferably 24% or less, and particularly preferably 20% or less.
  • the rhombohedral crystal ratio of 0% indicates that no XRD peak derived from the ABC stacking layer is detected.
  • “greater than 0%” means that even a slight XRD peak derived from the ABC stacking layer is detected.
  • the rhombohedral crystal ratio is too large, many defects are included in the crystal structure of the graphite particles, so that the insertion amount of Li tends to be reduced and it is difficult to obtain a high capacity. In addition, since the electrolyte is decomposed during the cycle due to the defects, the cycle characteristics tend to deteriorate. On the other hand, if the rhombohedral crystal ratio is within the range of the present invention, for example, the crystal structure of the graphite particles has few defects and low reactivity with the electrolytic solution, and the consumption of the electrolytic solution during the cycle is small and the cycle characteristics. It is preferable because it is excellent.
  • the XRD measurement method for determining the rhombohedral crystal ratio is as follows. A 0.2 mm sample plate is packed so that the graphite powder is not oriented, and is measured with an X-ray diffraction apparatus (for example, X'Pert Pro MPD manufactured by PANalytical, with CuK ⁇ ray, output 45 kV, 40 mA). Using the obtained diffraction pattern, the peak integrated intensity is calculated by profile fitting using the asymmetric Pearson VII function using analysis software JADE 5.0, and the rhombohedral crystal ratio is obtained from the above formula.
  • an X-ray diffraction apparatus for example, X'Pert Pro MPD manufactured by PANalytical, with CuK ⁇ ray, output 45 kV, 40 mA.
  • the X-ray diffraction measurement conditions are as follows. “2 ⁇ ” indicates a diffraction angle.
  • ⁇ Target Cu (K ⁇ ray) graphite monochromator
  • ⁇ Slit Solar slit 0.04 degree divergence slit 0.5 degree side divergence mask 15mm Anti-scattering slit 1 degree
  • Measurement range and step angle / measurement time (101) plane: 41 ° ⁇ 2 ⁇ ⁇ 47.5 ° 0.3 ° / 60 seconds. Background correction: A line between 42.7 and 45.5 ° is connected by a straight line and subtracted as background.
  • -Peak of rhombohedral-structure graphite particle layer refers to a peak around 43.4 degrees.
  • -Peak of hexagonal structure graphite particle layer It indicates a peak around 44.5 degrees.
  • a method for obtaining graphite particles having a rhombohedral crystal ratio in the above range can employ a method of manufacturing using conventional techniques, and is not particularly limited, but the graphite particles are heat-treated at a temperature of 500 ° C. or higher. It is preferable to manufacture by this. It is also preferable to give the graphite particles mechanical action such as compression, friction, shearing force, etc. including the interaction of particles mainly with impact force.
  • the rhombohedral crystal ratio can be adjusted by changing the strength of the mechanical action, the processing time, the presence or absence of repetition, and the like.
  • a specific device for adjusting the rhombohedral crystal ratio there is a rotor with a large number of blades installed inside the casing, and the rotor rotates at a high speed, thereby impacting the carbon material introduced inside.
  • An apparatus that applies a mechanical action such as compression, friction, shearing force, etc. and performs surface treatment is preferable.
  • a preferable apparatus there can be mentioned a hybridization system manufactured by Nara Machinery Co., Ltd.
  • a heat treatment after applying the mechanical action. Further, it is particularly preferable that after applying the mechanical action, it is combined with a carbon precursor and subjected to heat treatment at a temperature of 700 ° C. or higher.
  • Specific embodiments of the negative electrode active material include, for example, (a) graphite particles having a rhombohedral crystal ratio of 0% to 35% made of a composite and / or mixture of nuclear graphite and carbon, and (b) nuclear graphite and graphite. Graphite particles having a rhombohedral crystal ratio of from 0% to 35%, (c) graphite particles having a rhombohedral crystal ratio of from 0% to 35%, and (a) to (c) ) And the like.
  • examples of the nuclear graphite include the aforementioned natural graphite and artificial graphite.
  • the natural graphite as the core graphite is preferably spherical natural graphite (in this specification, spherical natural graphite is also referred to as spheroidized graphite).
  • the ratio of the complex and / or mixture of (b) to the complex and / or mixture of (a) is usually 5 wt% or more, preferably Is 10 wt% or more, more preferably 15 wt% or more.
  • the mixing ratio of (b) is 95 wt% or less normally, Preferably it is 90 wt% or less, More preferably, it is 85 wt% or less.
  • the mixing ratio of (b) is too small, the irreversible capacity tends to increase and the battery capacity tends to decrease, and when the mixing ratio is too large, the Li acceptability at low temperatures tends to decrease.
  • the ratio of the graphite particles of (c) to the composite and / or mixture of (a) is usually 5 wt% or more, preferably 10 wt% or more. Preferably it is 15 wt% or more. Moreover, it is 70 wt% or less normally, Preferably it is 60 wt% or less, More preferably, it is 50 wt% or less. If the mixing ratio of (c) is too small, there is a concern that when the electrode is pressed at a high density in order to increase the battery capacity, there is a concern that the press load increases and it is difficult to increase the density, and if it is too large, the irreversible capacity increases and the battery capacity increases. May decrease.
  • the ratio of the graphite particles of (c) to the composite and / or mixture of (b) is usually 5 wt% or more, preferably 10 wt% or more. Preferably it is 20 wt% or more. Moreover, it is 70 wt% or less normally, Preferably it is 60 wt% or less, More preferably, it is 50 wt% or less. If the mixing ratio of (c) is too small, the electrode load tends to be high when the electrodes are pressed at a high density in order to increase the battery capacity, and the density tends to be difficult to increase. There is a tendency to decrease.
  • the combination of the composite of (a) and the composite of (b), the combination of the composite of (a) and the graphite particles of (c), the composite of (b) and the graphite particles of (c) make it easy to produce a high-density electrode and secure a conductive path. It is more preferable because it is easily processed and has excellent cycle characteristics.
  • the negative electrode according to the present invention may contain graphite particles whose rhombohedral crystal ratio does not satisfy the above range.
  • the other graphite is usually 2 wt% or more with respect to the graphite particle mass of the present invention.
  • it is 5 wt% or more, More preferably, it is 10 wt% or more.
  • it is 50 wt% or less normally, Preferably it is 45 wt% or less, More preferably, it is 40 wt% or less. If the amount of other graphite is too small, the effect of mixing other graphite tends to be difficult to obtain, and if it is too large, the effect of the present invention tends to be small.
  • the rhombohedral crystal ratio of the nuclear graphite constituting these composites is usually 0% or more, preferably 3% or more, like the graphite particles. More preferably, it is 5% or more, usually 35% or less, preferably 27% or less, more preferably 24% or less, and particularly preferably 20% or less.
  • the rhombohedral crystal ratio of the nuclear graphite constituting these composites can be determined by the same method as that for the graphite particles.
  • a rhombohedral crystal ratio composed of a composite and / or a mixture of nuclear graphite and carbon is 0%.
  • the graphite particles of 35% or less include, for example, coating or bonding a carbon precursor to nuclear graphite and then firing at 600 ° C. to 2200 ° C. or vapor deposition by a CVD (Chemical Vapor Deposition) method. , Etc.
  • the composite refers to graphite particles in which carbon is coated or bonded to nuclear graphite and the rhombohedral crystal ratio is within the above range.
  • the coverage of carbon is usually 1% by mass or more, preferably 2% by mass or more, and usually 15% by mass or less, preferably 10% by mass or less.
  • the mixture refers to, for example, a mixture of graphite particles having a rhombohedral crystal ratio of 0% or more and 35% or less and carbon in an arbitrary ratio without being covered or bonded.
  • a rhombohedral crystal ratio composed of a composite and / or mixture of nuclear graphite and graphite is 0%.
  • the above 35% or less graphite particles can be obtained, for example, by coating or bonding a carbon precursor to nuclear graphite and then graphitizing at a temperature of 2300 ° C. to 3200 ° C.
  • the composite refers to graphite particles in which easy graphite and / or hard graphite is coated or bonded to nuclear graphite and rhombohedral crystallinity is 0% or more and 35% or less.
  • the coverage of graphite is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and usually 50% by mass or less, preferably 30% by mass or less.
  • the coverage referred to in the present invention can be calculated from the mass of nuclear graphite and the mass of graphite derived from the carbon precursor after graphitization using the following formula.
  • Coverage (mass%) precursor-derived graphite mass ⁇ (nuclear graphite mass + precursor-derived graphite mass) ⁇ 100
  • the mixture refers to, for example, a mixture of graphite particles having a rhombohedral crystal ratio of 0% or more and 35% or less and graphite in an arbitrary ratio without being covered or bonded.
  • (C) Graphite particles having a rhombohedral crystal ratio of 0% or more and 35% or less
  • the graphite particles having a rhombohedral crystal ratio of 0% or more and 35% or less do not include the structures (a) and (b). It refers to those composed only of graphite particles having a rhombohedral crystal ratio of 0% to 35%.
  • it is nuclear graphite that has been subjected to mechanical energy treatment, and refers to graphite particles that are not compounded or mixed with carbon and / or graphite.
  • graphite particles obtained by firing graphite particles having a rhombohedral crystal ratio of 0% to 35% at 400 ° C. to 3200 ° C. can be used.
  • the graphite particles may be composed of a single type, or may be composed of a plurality of graphite particles having different forms and particle sizes.
  • the d value (interlayer distance) of the lattice plane (002 plane) determined by X-ray diffraction by the Gakushin method of carbonaceous materials is preferably 0.335 nm or more, and is usually 0.360 nm or less. 350 nm or less is preferable, and 0.345 nm or less is more preferable. Further, the crystallite size (Lc) of the carbonaceous material obtained by X-ray diffraction by the Gakushin method is preferably 1.0 nm or more, and more preferably 1.5 nm or more.
  • the volume-based average particle diameter of the carbonaceous material is a volume-based average particle diameter (median diameter) obtained by a laser diffraction / scattering method, and is usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and 7 ⁇ m.
  • the above is particularly preferable, and is usually 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, further preferably 30 ⁇ m or less, and particularly preferably 25 ⁇ m or less.
  • the volume-based average particle size is measured by dispersing carbon powder in a 0.2% by weight aqueous solution (about 10 mL) of polyoxyethylene (20-mer) sorbitan monolaurate, which is a surfactant, and using a laser diffraction / scattering method. This is performed using a particle size distribution meter (LA-700 manufactured by Horiba, Ltd.). The median diameter determined by the measurement is defined as the volume-based average particle diameter of the carbonaceous material.
  • the Raman R value of the carbonaceous material is a value measured using an argon ion laser Raman spectrum method, and is usually 0.01 or more, preferably 0.03 or more, more preferably 0.1 or more, and usually 1.5 or less, preferably 1.2 or less, more preferably 1 or less, and particularly preferably 0.5 or less.
  • the Raman R value is lower than the above range, the crystallinity of the particle surface becomes too high, and there are cases where the sites where Li enters between layers are reduced along with charge / discharge. That is, charge acceptance may be reduced.
  • the negative electrode is densified by applying it to the current collector and then pressing it, the crystals are likely to be oriented in a direction parallel to the electrode plate, which may lead to a decrease in load characteristics.
  • the Raman R value is 0.1 or more, a suitable film can be formed on the surface of the negative electrode, whereby storage characteristics, cycle characteristics, and load characteristics can be improved.
  • the Raman half-width in the vicinity of 1580 cm ⁇ 1 of the carbonaceous material is not particularly limited, but is usually 10 cm ⁇ 1 or more, preferably 15 cm ⁇ 1 or more, and usually 100 cm ⁇ 1 or less, and 80 cm ⁇ 1 or less. 60 cm ⁇ 1 or less is more preferable, and 40 cm ⁇ 1 or less is particularly preferable.
  • the Raman half-width is less than the above range, the crystallinity of the particle surface becomes too high, and there are cases where the number of sites where Li enters between layers decreases with charge and discharge. That is, charge acceptance may be reduced.
  • the negative electrode is densified by applying it to the current collector and then pressing it, the crystals are likely to be oriented in a direction parallel to the electrode plate, which may lead to a decrease in load characteristics.
  • it exceeds the above range the crystallinity of the particle surface is lowered, the reactivity with the non-aqueous electrolyte is increased, and the efficiency may be lowered and the gas generation may be increased.
  • the measurement of the Raman spectrum using a Raman spectrometer (manufactured by JASCO Corporation Raman spectrometer), the sample is naturally dropped into the measurement cell and filled, and while irradiating the sample surface in the cell with argon ion laser light, This is done by rotating the cell in a plane perpendicular to the laser beam.
  • the resulting Raman spectrum, the intensity I A of the peak P A in the vicinity of 1580 cm -1, and measuring the intensity I B of a peak P B in the vicinity of 1360 cm -1, the intensity ratio R (R I B / I A) Is calculated.
  • the Raman R value calculated by the measurement is defined as the Raman R value of the carbonaceous material of the present invention.
  • the half width of the peak P A in the vicinity of 1580 cm -1 of the resulting Raman spectrum was measured, which is defined as the Raman half-value width of the carbonaceous material.
  • said Raman measurement conditions are as follows. Argon ion laser wavelength: 514.5nm ⁇ Laser power on the sample: 15-25mW ⁇ Resolution: 10-20cm -1 Measurement range: 1100 cm ⁇ 1 to 1730 cm ⁇ 1 ⁇ Raman R value, Raman half width analysis: Background processing ⁇ Smoothing processing: Simple average, 5 points of convolution
  • BET specific surface area of the carbonaceous material is a value of the measured specific surface area using the BET method is usually 0.1 m 2 ⁇ g -1 or more, 0.7 m 2 ⁇ g -1 or more, 1. 0 m 2 ⁇ g -1 or more, and particularly preferably 1.5 m 2 ⁇ g -1 or more, generally not more than 100 m 2 ⁇ g -1, preferably 25 m 2 ⁇ g -1 or less, 15 m 2 ⁇ g ⁇ 1 or less is more preferable, and 10 m 2 ⁇ g ⁇ 1 or less is particularly preferable.
  • the acceptability of lithium is likely to deteriorate during charging when it is used as a negative electrode material, and lithium is likely to precipitate on the electrode surface, which may reduce the stability.
  • the reactivity with the non-aqueous electrolyte increases, gas generation tends to increase, and a preferable battery may be difficult to obtain.
  • the specific surface area was measured by the BET method using a surface area meter (a fully automated surface area measuring device manufactured by Okura Riken), preliminarily drying the sample at 350 ° C. for 15 minutes under nitrogen flow, Using a nitrogen helium mixed gas accurately adjusted so that the value of the relative pressure becomes 0.3, the nitrogen adsorption BET one-point method by the gas flow method is used.
  • the specific surface area determined by the measurement is defined as the BET specific surface area of the carbonaceous material.
  • the circularity is measured as the degree of the sphere of the carbonaceous material, it is preferably within the following range.
  • the degree of circularity of particles having a particle size of 3 to 40 ⁇ m in the range of the carbonaceous material is desirably close to 1, and is preferably 0.1 or more, more preferably 0.5 or more, and more preferably 0.8 or more. 0.85 or more is more preferable, and 0.9 or more is particularly preferable.
  • High current density charge / discharge characteristics improve as the degree of circularity increases. Therefore, when the circularity is below the above range, the filling property of the negative electrode active material is lowered, the resistance between the particles is increased, and the high current density charge / discharge characteristics may be lowered for a short time.
  • the circularity is measured using a flow type particle image analyzer (FPIA manufactured by Sysmex Corporation). About 0.2 g of a sample was dispersed in a 0.2% by mass aqueous solution (about 50 mL) of polyoxyethylene (20) sorbitan monolaurate as a surfactant, and irradiated with 28 kHz ultrasonic waves at an output of 60 W for 1 minute.
  • the detection range is specified as 0.6 to 400 ⁇ m, and the particle size is measured in the range of 3 to 40 ⁇ m.
  • the circularity determined by the measurement is defined as the circularity of the carbonaceous material.
  • the method for improving the degree of circularity is not particularly limited, but a spheroidized sphere is preferable because the shape of the interparticle void when the electrode body is formed is preferable.
  • spheroidizing treatment include a method of mechanically approaching a sphere by applying a shearing force and a compressive force, a mechanical / physical processing method of granulating a plurality of fine particles by the binder or the adhesive force of the particles themselves, etc. Is mentioned.
  • the tap density of the carbonaceous material is usually 0.1 g ⁇ cm ⁇ 3 or more, preferably 0.5 g ⁇ cm ⁇ 3 or more, more preferably 0.7 g ⁇ cm ⁇ 3 or more, and 1 g ⁇ cm ⁇ 3 or more. particularly preferred, and is preferably 2 g ⁇ cm -3 or less, more preferably 1.8 g ⁇ cm -3 or less, 1.6 g ⁇ cm -3 or less are particularly preferred.
  • the tap density is below the above range, the packing density is difficult to increase when used as a negative electrode, and a high-capacity battery may not be obtained.
  • the above range is exceeded, there are too few voids between particles in the electrode, it is difficult to ensure conductivity between the particles, and it may be difficult to obtain preferable battery characteristics.
  • the tap density is measured by passing a sieve having a mesh opening of 300 ⁇ m, dropping the sample onto a 20 cm 3 tapping cell and filling the sample to the upper end surface of the cell, and then measuring a powder density measuring instrument (for example, manufactured by Seishin Enterprise Co., Ltd.). Tapping with a stroke length of 10 mm is performed 1000 times using a tap denser, and the tap density is calculated from the volume and the mass of the sample.
  • the tap density calculated by the measurement is defined as the tap density of the carbonaceous material.
  • the orientation ratio of the carbonaceous material is usually 0.005 or more, preferably 0.01 or more, more preferably 0.015 or more, and usually 0.67 or less. When the orientation ratio is below the above range, the high-density charge / discharge characteristics may deteriorate.
  • the upper limit of the above range is the theoretical upper limit value of the orientation ratio of the carbonaceous material.
  • the orientation ratio is measured by X-ray diffraction after pressure-molding the sample.
  • Set the molded body obtained by filling 0.47 g of the sample into a molding machine with a diameter of 17 mm and compressing it with 58.8 MN ⁇ m -2 so that it is flush with the surface of the sample holder for measurement.
  • X-ray diffraction is measured.
  • From the (110) diffraction and (004) diffraction peak intensities of the obtained carbon a ratio represented by (110) diffraction peak intensity / (004) diffraction peak intensity is calculated.
  • the orientation ratio calculated by the measurement is defined as the orientation ratio of the carbonaceous material.
  • the X-ray diffraction measurement conditions are as follows. “2 ⁇ ” indicates a diffraction angle.
  • ⁇ Target Cu (K ⁇ ray) graphite monochromator
  • Light receiving slit 0.15
  • Scattering slit 0.5 degree / measurement range and step angle / measurement time: (110) plane: 75 degrees ⁇ 2 ⁇ ⁇ 80 degrees 1 degree / 60 seconds (004) plane: 52 degrees ⁇ 2 ⁇ ⁇ 57 degrees 1 degree / 60 seconds
  • the aspect ratio of the carbonaceous material is usually 1 or more and usually 10 or less, preferably 8 or less, and more preferably 5 or less. When the aspect ratio exceeds the above range, streaking or a uniform coated surface cannot be obtained when forming an electrode plate, and the high current density charge / discharge characteristics may deteriorate.
  • the lower limit of the above range is the theoretical lower limit value of the aspect ratio of the carbonaceous material.
  • the aspect ratio is measured by magnifying and observing the carbonaceous material particles with a scanning electron microscope. Carbonaceous material particles when three-dimensional observation is performed by selecting arbitrary 50 graphite particles fixed to the end face of a metal having a thickness of 50 ⁇ m or less, and rotating and tilting the stage on which the sample is fixed. The longest diameter A and the shortest diameter B orthogonal thereto are measured, and the average value of A / B is obtained.
  • the aspect ratio (A / B) obtained by the measurement is defined as the aspect ratio of the carbonaceous material.
  • any known method can be used for producing the electrode as long as the effects of the present invention are not significantly impaired. For example, it is formed by adding a binder, a solvent, and, if necessary, a thickener, a conductive material, a filler, etc. to the negative electrode active material to form a slurry, which is applied to a current collector, dried and then pressed. Can do.
  • the current collector for holding the negative electrode active material As the current collector for holding the negative electrode active material, a known material can be arbitrarily used. Examples of the current collector for the negative electrode include metal materials such as aluminum, copper, nickel, stainless steel, and nickel-plated steel. Copper is particularly preferable from the viewpoint of ease of processing and cost.
  • the shape of the current collector may be, for example, a metal foil, a metal cylinder, a metal coil, a metal plate, a metal thin film, an expanded metal, a punch metal, a foam metal, or the like when the current collector is a metal material.
  • a metal thin film is preferable, a copper foil is more preferable, and a rolled copper foil by a rolling method and an electrolytic copper foil by an electrolytic method are more preferable, and both can be used as a current collector.
  • the thickness of the current collector is usually 1 ⁇ m or more, preferably 5 ⁇ m or more, and is usually 100 ⁇ m or less, preferably 50 ⁇ m or less. This is because if the thickness of the negative electrode current collector is too thick, the capacity of the entire battery may be too low, and conversely if it is too thin, handling may be difficult.
  • the ratio of the thickness of the current collector to the negative electrode active material layer is not particularly limited, but the value of “(the thickness of the negative electrode active material layer on one side immediately before the nonaqueous electrolyte injection) / (thickness of the current collector)”
  • 150 or less is preferable, 20 or less is more preferable, 10 or less is particularly preferable, 0.1 or more is preferable, 0.4 or more is more preferable, and 1 or more is particularly preferable.
  • the ratio of the thickness of the current collector to the negative electrode active material layer exceeds the above range, the current collector may generate heat due to Joule heat during high current density charge / discharge.
  • the volume ratio of the current collector to the negative electrode active material increases, and the battery capacity may decrease.
  • the binder for binding the negative electrode active material is not particularly limited as long as it is a material that is stable with respect to the non-aqueous electrolyte solution and the solvent used in manufacturing the electrode.
  • resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, polyimide, cellulose, and nitrocellulose; SBR (styrene / butadiene rubber), isoprene rubber, butadiene rubber, fluorine rubber, Rubber polymers such as NBR (acrylonitrile / butadiene rubber) and ethylene / propylene rubber; styrene / butadiene / styrene block copolymer or hydrogenated product thereof; EPDM (ethylene / propylene / diene terpolymer), styrene / Thermoplastic elastomeric polymers such as ethylene / butadiene / styrene
  • the ratio of the binder to the negative electrode active material is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 0.6% by mass or more, and preferably 20% by mass or less, 15% by mass. The following is more preferable, 10% by mass or less is further preferable, and 8% by mass or less is particularly preferable.
  • the ratio of the binder with respect to a negative electrode active material exceeds the said range, the binder ratio from which the amount of binders does not contribute to battery capacity may increase, and the fall of battery capacity may be caused.
  • the strength of the negative electrode may be reduced.
  • the ratio of the binder to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, and 0 .6% by mass or more is more preferable, and is usually 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less.
  • the main component contains a fluorine-based polymer typified by polyvinylidene fluoride
  • the ratio to the negative electrode active material is usually 1% by mass or more, preferably 2% by mass or more, and more preferably 3% by mass or more. It is preferably 15% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less.
  • the solvent for forming the slurry is not particularly limited as long as it is a solvent capable of dissolving or dispersing the negative electrode active material, the binder, and the thickener and conductive material used as necessary. Alternatively, either an aqueous solvent or an organic solvent may be used.
  • aqueous solvent examples include water and alcohol
  • examples of the organic solvent include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N, N—
  • examples thereof include dimethylaminopropylamine, tetrahydrofuran (THF), toluene, acetone, diethyl ether, dimethylacetamide, hexamethylphosphalamide, dimethyl sulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene, and hexane.
  • aqueous solvent when used, it is preferable to add a dispersant or the like in addition to the thickener and slurry it using a latex such as SBR.
  • these solvents may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio.
  • a thickener is usually used to adjust the viscosity of the slurry.
  • the thickener is not particularly limited, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios.
  • the ratio of the thickener to the negative electrode active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more, Moreover, it is 5 mass% or less normally, 3 mass% or less is preferable, and 2 mass% or less is more preferable.
  • the ratio of the thickener to the negative electrode active material is less than the above range, applicability may be significantly reduced.
  • it exceeds the said range the ratio of the negative electrode active material which occupies for a negative electrode active material layer will fall, and the problem that the capacity
  • the electrode structure when the negative electrode active material is made into an electrode is not particularly limited, but the density of the negative electrode active material present on the current collector is preferably 1 g ⁇ cm ⁇ 3 or more, and 1.2 g ⁇ cm ⁇ 3 or more. but more preferably, particularly preferably 1.3 g ⁇ cm -3 or more, preferably 2.2 g ⁇ cm -3 or less, more preferably 2.1g ⁇ cm -3 or less, 2.0 g ⁇ cm -3 or less More preferred is 1.9 g ⁇ cm ⁇ 3 or less.
  • the density of the negative electrode active material existing on the current collector exceeds the above range, the negative electrode active material particles are destroyed, and the initial irreversible capacity increases or non-aqueous system near the current collector / negative electrode active material interface. There is a case where high current density charge / discharge characteristics are deteriorated due to a decrease in permeability of the electrolytic solution.
  • the amount is less than the above range, the conductivity between the negative electrode active materials decreases, the battery resistance increases, and the capacity per unit volume may decrease.
  • the thickness of the negative electrode plate is designed according to the positive electrode plate to be used, and is not particularly limited.
  • the thickness of the composite layer obtained by subtracting the thickness of the metal foil of the core is usually 15 ⁇ m or more, preferably 20 ⁇ m or more. More preferably, it is 30 ⁇ m or more, and usually 300 ⁇ m or less, preferably 280 ⁇ m or less, more preferably 250 ⁇ m or less.
  • Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate and carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate.
  • a separator is interposed between the positive electrode and the negative electrode in order to prevent a short circuit.
  • the nonaqueous electrolytic solution of the present invention is usually used by impregnating the separator.
  • the material and shape of the separator are not particularly limited, and known ones can be arbitrarily adopted as long as the effects of the present invention are not significantly impaired.
  • polyolefin resins, other resins, glass fibers, inorganic substances, etc. which are formed of a material that is stable with respect to the non-aqueous electrolyte solution of the present invention can be used as constituent components.
  • As the shape it is preferable to use a porous sheet excellent in liquid retention or a non-woven fabric.
  • the separator used in the present invention preferably has a polyolefin resin as a part of the constituent components.
  • the polyolefin resin include polyethylene resin, polypropylene resin, 1-polymethylpentene, polyphenylene sulfide, and the like.
  • polyethylene resins include low-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, medium-density polyethylene, high-density polyethylene, and copolymers based on ethylene, that is, ethylene and propylene, butene -1, pentene-1, hexene-1, heptene-1, octene-1, etc.
  • ⁇ -olefins having 3 to 10 carbon atoms; vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate, ethyl acrylate, methacryl A copolymer or multi-component copolymer with one or two or more comonomers selected from unsaturated carboxylic acid esters such as methyl acrylate and ethyl methacrylate, and unsaturated compounds such as conjugated and non-conjugated dienes, or The mixed composition is mentioned.
  • the ethylene unit content of the ethylene polymer is usually more than 50% by mass.
  • polyethylene resins at least one polyethylene resin selected from low density polyethylene, linear low density polyethylene, and high density polyethylene is preferable, and high density polyethylene is most preferable.
  • polymerization catalyst of a polyethylene-type resin Any things, such as a Ziegler type catalyst, a Phillips type catalyst, and a Kaminsky type catalyst, may be sufficient.
  • a polymerization method of the polyethylene resin there are a one-stage polymerization, a two-stage polymerization, or a multistage polymerization more than that, and any method of the polyethylene resin can be used.
  • the melt flow rate (MFR) of the polyethylene resin is not particularly limited, but usually the MFR is preferably 0.03 to 15 g / 10 min, and preferably 0.3 to 10 g / 10 min. preferable. If the MFR is in the above range, the back pressure of the extruder does not become too high during the molding process and the productivity is excellent.
  • the MFR in the present invention is a value measured under conditions of a temperature of 190 ° C. and a load of 2.16 kg in accordance with JIS K7210.
  • the production method of the polyethylene resin is not particularly limited, and is a known polymerization method using a known olefin polymerization catalyst, for example, a multisite catalyst represented by a Ziegler-Natta type catalyst or a metallocene catalyst.
  • a polymerization method using a single site catalyst may be mentioned.
  • polypropylene resin As the polypropylene resin in the present invention, homopolypropylene (propylene homopolymer), or propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene or 1-decene And a random copolymer or a block copolymer with an ⁇ -olefin.
  • homopolypropylene is more preferably used from the viewpoint of mechanical strength.
  • the polypropylene resin preferably has an isotactic pentad fraction exhibiting stereoregularity of 80 to 99%, more preferably 83 to 98%, and still more preferably 85 to 97%. use. If the isotactic pentad fraction is too low, the mechanical strength of the battery separator may decrease. On the other hand, the upper limit of the isotactic pentad fraction is defined by the upper limit that can be obtained industrially at present, but this is not the case when a more regular resin is developed in the industrial level in the future. is not.
  • the isotactic pentad fraction is a three-dimensional structure in which five methyl groups that are side chains are located in the same direction with respect to the main chain of carbon-carbon bonds composed of arbitrary five consecutive propylene units. Or the ratio is meant.
  • Signal assignment of the methyl group region is as follows. Zambellietatal. (Macromol. 8, 687 (1975)).
  • the polypropylene resin preferably has a Mw / Mn, which is a parameter indicating a molecular weight distribution, of 1.5 to 10.0. More preferred is 2.0 to 8.0, and still more preferred is 2.0 to 6.0. This means that the smaller the Mw / Mn, the narrower the molecular weight distribution. However, if the Mw / Mn is less than 1.5, problems such as a decrease in extrusion moldability occur, and it is difficult to produce industrially. There are many cases. On the other hand, when Mw / Mn exceeds 10.0, the low molecular weight component increases, and the mechanical strength of the obtained battery separator tends to decrease. Mw / Mn is obtained by GPC (gel per emission chromatography) method.
  • the melt flow rate (MFR) of the polypropylene resin is not particularly limited, but usually the MFR is preferably 0.1 to 15 g / 10 minutes, and preferably 0.5 to 10 g / 10 minutes. It is more preferable. When the MFR is less than 0.1 g / 10 minutes, the melt viscosity of the resin during the molding process is high, and the productivity is lowered. On the other hand, when it exceeds 15 g / 10 minutes, practical problems such as insufficient strength of the obtained battery separator tend to occur. MFR is measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg in accordance with JIS K7210.
  • resin and glass fiber separator materials for example, aromatic polyamide, polytetrafluoroethylene, polyethersulfone, glass filter and the like can be used in combination with the polyolefin resin. These materials may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
  • the thickness of the separator is arbitrary, but is usually 1 ⁇ m or more, preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more, and usually 50 ⁇ m or less, preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less. If the separator is too thin than the above range, the insulating properties and mechanical strength may decrease. On the other hand, if it is thicker than the above range, not only the battery performance such as the rate characteristic may be lowered, but also the energy density of the whole non-aqueous electrolyte secondary battery may be lowered.
  • the porosity of the separator is arbitrary, but is usually 20% or more, preferably 35% or more, more preferably 45% or more, Further, it is usually 90% or less, preferably 85% or less, and more preferably 75% or less. If the porosity is too smaller than the above range, the membrane resistance tends to increase and the rate characteristics tend to deteriorate. Moreover, when larger than the said range, it exists in the tendency for the mechanical strength of a separator to fall and for insulation to fall.
  • the average pore diameter of a separator is also arbitrary, it is 0.5 micrometer or less normally, 0.2 micrometer or less is preferable, and it is 0.05 micrometer or more normally. If the average pore diameter exceeds the above range, a short circuit tends to occur. On the other hand, below the above range, the film resistance may increase and the rate characteristics may deteriorate.
  • inorganic materials for example, oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate are used. Used.
  • a thin film shape such as a nonwoven fabric, a woven fabric, or a microporous film is used.
  • the thin film shape those having a pore diameter of 0.01 to 1 ⁇ m and a thickness of 5 to 50 ⁇ m are preferably used.
  • a separator formed by forming a composite porous layer containing the inorganic particles on the surface layer of the positive electrode and / or the negative electrode using a resin binder can be used.
  • a porous layer may be formed by using alumina particles having a 90% particle size of less than 1 ⁇ m on both surfaces of the positive electrode and using a fluororesin as a binder.
  • the electrode group has a laminated structure in which the positive electrode plate and the negative electrode plate are interposed through the separator, and a structure in which the positive electrode plate and the negative electrode plate are wound in a spiral shape through the separator. Either is acceptable.
  • the ratio of the volume of the electrode group to the internal volume of the battery (hereinafter referred to as the electrode group occupation ratio) is usually 40% or more, preferably 50% or more, and usually 90% or less, preferably 80% or less. .
  • the battery capacity decreases. Also, if the above range is exceeded, the void space is small, the battery expands, and the member expands or the vapor pressure of the electrolyte liquid component increases and the internal pressure rises. In some cases, the gas release valve that lowers various characteristics such as storage at high temperature and the like, or releases the internal pressure to the outside is activated.
  • the current collecting structure is not particularly limited, but in order to more effectively realize the high current density charge / discharge characteristics by the non-aqueous electrolyte solution of the present invention, a structure that reduces the resistance of the wiring part and the joint part is used. It is preferable. Thus, when internal resistance is reduced, the effect of using the non-aqueous electrolyte solution of this invention is exhibited especially favorable.
  • the electrode group has the laminated structure described above, a structure formed by bundling the metal core portions of the electrode layers and welding them to the terminals is preferably used.
  • the area of one electrode increases, the internal resistance increases. Therefore, it is also preferable to provide a plurality of terminals in the electrode to reduce the resistance.
  • the electrode group has the winding structure described above, the internal resistance can be lowered by providing a plurality of lead structures for the positive electrode and the negative electrode, respectively, and bundling the terminals.
  • the material of the outer case is not particularly limited as long as it is a substance that is stable with respect to the non-aqueous electrolyte used. Specifically, a nickel-plated steel plate, stainless steel, aluminum, an aluminum alloy, a metal such as a magnesium alloy, or a laminated film (laminate film) of a resin and an aluminum foil is used. From the viewpoint of weight reduction, an aluminum or aluminum alloy metal or a laminate film is preferably used.
  • the metal is welded together by laser welding, resistance welding, or ultrasonic welding to form a sealed sealed structure, or a caulking structure using the above metals via a resin gasket. Things.
  • the outer case using the laminate film include a case where a resin-sealed structure is formed by heat-sealing resin layers.
  • a resin different from the resin used for the laminate film may be interposed between the resin layers.
  • a resin layer is heat-sealed through a current collecting terminal to form a sealed structure, a metal and a resin are joined, so that a resin having a polar group or a modified group having a polar group introduced as an intervening resin is used.
  • Resins are preferably used.
  • PTC Positive Temperature Coefficient
  • thermal fuse a protective element that shuts off the current flowing through the circuit due to sudden increase in battery internal pressure or internal temperature in case of abnormal occurrence Valves (current cutoff valves, etc.
  • Valves current cutoff valves, etc.
  • a protective element that does not operate under high current normal use, and it will not cause abnormal heat generation or thermal runaway without a protective element. It is better to be.
  • the non-aqueous electrolyte secondary battery of the present invention is usually configured by housing the non-aqueous electrolyte, the negative electrode, the positive electrode, the separator, and the like in an exterior body.
  • This exterior body is not particularly limited, and any known one can be arbitrarily adopted as long as the effects of the present invention are not significantly impaired.
  • the material of the exterior body is arbitrary, but usually, for example, nickel-plated iron, stainless steel, aluminum or an alloy thereof, nickel, titanium, or the like is used.
  • the shape of the outer package is also arbitrary, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.
  • the non-aqueous electrolyte secondary battery of the present invention can be used without particular limitation, but can be preferably used for a battery having a high voltage or a high capacity.
  • the increase in voltage is usually 4.3 V or higher, preferably 4.4 V or higher, more preferably 4.5 V or higher, and still more preferably 4.6 V or higher.
  • the increase in capacity is usually 2600 mAh or more, preferably 2800 mAh or more, more preferably 3000 mAh or more in the case of an 18650 type battery, for example.
  • ethylene carbonate (EC) or propylene carbonate (PC) as the cyclic carbonate represented by the general formula (1)
  • 4-fluoroethylene carbonate (MFEC) as the fluorinated cyclic carbonate represented by the general formula (2)
  • DFEC 4,5-difluoroethylene carbonate
  • TFEMC (2,2,2-trifluoroethyl) methyl carbonate
  • EMC Methyl carbonate
  • DMC dimethyl carbonate
  • HMDI hexamethylene diisocyanate
  • BIMCH 1,3-bis (isocyanatomethyl) cyclohexane
  • BIMCH 1,3,5-tris (6-isocyanatohexyl) ) -1,3,5- Triazine -2,4,6 (1H, 3H, 5H) - trione
  • Example A High-voltage battery with an open circuit voltage between battery terminals of 4.90 V
  • Selection of electrolyte Basic electrolytes 1 to 19, 24, and 25 in which no salt deposition was observed at 0 ° C. were used as Examples 1 to 21, and basic electrolytes 20, 22, and 26 were used in Comparative Examples 1 to 3. An electrolyte was used.
  • the positive electrode, the negative electrode, and the polyethylene separator were laminated in the order of the negative electrode, the separator, and the positive electrode to prepare a battery element.
  • the battery element was inserted into a bag made of a laminate film in which both surfaces of aluminum (thickness: 40 ⁇ m) were coated with a resin layer while projecting positive and negative terminals, and then the basic electrolysis described in Tables 3, 4, and 5 were performed.
  • Each solution was poured into a bag and vacuum-sealed to produce a sheet-like battery, which was used for each of Examples 1 to 21 and Comparative Examples 1 to 3.
  • the non-aqueous electrolytes (Examples 1 to 13) containing more than 15% by volume of EC or a mixed cyclic carbonate of EC and PC according to the present invention (Examples 1 to 13) are non-aqueous electrolytes having a cyclic carbonate of 15% by volume or less. It turns out that it is excellent in the cycle maintenance factor under high voltage with respect to electrolyte solution (Comparative Examples 1 and 2). In Comparative Example 1 that does not contain the cyclic carbonate represented by the general formula (1), the cycle retention rate greatly decreased before 200 cycles of charge / discharge, and charge / discharge was impossible at the time of 200 cycles. (Therefore, the numbers in the table indicate the maintenance rate at 100 cycles).
  • the comparative example 1 which does not contain the cyclic carbonate represented by the general formula (1) has a very large initial gas generation amount, and the stability under a high voltage is insufficient.
  • Comparative Example 2 containing 15% by volume of the cyclic carbonate represented by the general formula (1), the amount of gas generated at the initial stage was reduced and charging / discharging was possible after 200 cycles, but the capacity retention rate was 32% and high. It was suggested that the stability under voltage was insufficient.
  • Examples 1 to 13 containing more than 15% by volume of the cyclic carbonate represented by the general formula (1), gas generation was also suppressed and the cycle retention rate was improved.
  • Example B Upper limit operating potential dependency
  • Example B Upper limit operating potential dependency
  • the positive electrode potential is 4 on the basis of Li / Li + at a constant current corresponding to 0.1 C at 25 ° C. .95V, 4.90V, 4.85V, 4.75V, 4.65V, that is, running-in voltage between battery terminals in the range of 4.90V, 4.85V, 4.80V, 4.70V, 4.60V Went.
  • the above battery was charged at a constant current of 1/3 C and discharged at a constant current of 1/3 C for 4 cycles in the range of 25 ° C., 3.0-open circuit voltages between the battery terminals. .
  • the above process was used as a break-in operation for confirming the discharge capacity.
  • Table 6 shows the discharge current capacity of each sheet-like lithium secondary battery after the break-in operation when discharging at 25 ° C. and 1/3 C constant current.
  • Example B Even in the high positive electrode potential range where the upper limit operating potential is 4.75-4.95V, there was no significant difference in the discharge capacity after the break-in operation, but the discharge capacity at 4.65V was almost halved. This is because if the upper limit operating potential is too low, the battery cannot be charged to a sufficient depth and the capacity cannot be obtained. Therefore, the durability evaluation of Example B was performed in a range where the upper limit operating potential at which a large amount of discharge capacity could be taken out was 4.75V or more.
  • Example B Cycle durability evaluation
  • Selection of electrolyte The basic electrolytic solution 3 in which no salt deposition was observed at 0 ° C. was used as the electrolytic solution used in Examples 22 to 24, the basic electrolytic solution 7 was used as the electrolytic solution used in Examples 25 and 26, and the basic electrolytic solution 27 was compared. The electrolyte used in Example 4 was obtained.
  • Example 22 [Production of negative electrode] A negative electrode used in Example 22 was prepared in the same manner as the negative electrode used in Example A.
  • a positive electrode used in Example 22 was prepared in the same manner as the positive electrode used in Example A.
  • the positive electrode potential is 4.75 V at a constant current corresponding to 0.1 C at 25 ° C., that is, between battery terminals, in a state where the produced sheet-like lithium secondary battery is sandwiched between glass plates in order to enhance the adhesion between the electrodes.
  • the running-in operation was performed in the open circuit voltage range of 4.70V.
  • a process in which the battery is charged at a constant current of 1/3 C and then discharged at a constant current of 1/3 C in the range of 25 ° C. and 3.0-4.70 V as an open circuit voltage between battery terminals is defined as 4 cycles. Cycled.
  • the break-in operation of Example 22 was performed through the above steps.
  • Example 23 Regarding the running-in operation and the evaluation of cycle characteristics, the production, running-in operation, and cycle characteristics were evaluated in the same manner as in Example 22 except that the positive electrode upper limit potential was 4.85 V, that is, the open circuit voltage between the battery terminals was 4.80 V. . Table 7 shows the evaluation results.
  • Example 24 Regarding the running-in operation and the evaluation of cycle characteristics, the production, running-in operation, and cycle characteristics were evaluated in the same manner as in Example 22 except that the positive electrode upper limit potential was 4.90 V, that is, the open circuit voltage between the battery terminals was 4.85 V. . Table 7 shows the evaluation results.
  • Example 25 Regarding the production of the lithium secondary battery, the production, break-in operation, and cycle characteristics were evaluated in the same manner as in Example 23, except that the electrolytic solution 7 shown in Table 1 was used as the basic electrolytic solution. Table 7 shows the evaluation results.
  • Example 26 Regarding the production of the lithium secondary battery, the production, the running-in operation, and the cycle characteristics were evaluated in the same manner as in Example 24 except that the electrolytic solution 7 shown in Table 1 was used as the basic electrolytic solution. Table 7 shows the evaluation results.
  • the high voltage design cell (Examples 22, 23, 24) with the positive electrode upper limit potential set to 4.75V, 4.85V, 4.90V shows a high cycle maintenance ratio.
  • the capacity retention rate after 200 cycles is as high as 82.0%, which is high by applying this design.
  • high durability can be realized in the voltage design cell, in the same cycle test at the positive electrode upper limit potential, when the non-aqueous electrolyte containing no fluorinated solvent according to the present invention is used, the same capacity retention rate is This is greatly reduced to 55.7% (Comparative Example 4).
  • a lithium secondary battery having high durability can be obtained by using the non-aqueous electrolyte according to the present invention. Can be earned.
  • Example C selection of electrolyte
  • the basic electrolyte solution 2 and the basic electrolyte solution 28 in which no salt deposition was observed at 0 ° C. were used as the electrolyte solutions used in Example 27 and Comparative Example 5, respectively.
  • a negative electrode used in Example 27 and Comparative Example 5 was prepared in the same manner as the negative electrode used in Examples A and B.
  • a sheet battery was prepared in the same manner as in Examples A and B except that the above electrolyte, negative electrode, and positive electrode were used, and batteries used in Example 27 and Comparative Example 5 were obtained.
  • Example D Selection of electrolyte
  • the basic electrolytic solution 3 and the basic electrolytic solution 20 in which no salt deposition was observed at 0 ° C. were used as the electrolytic solutions used in Example 28 and Comparative Example 6, respectively.
  • a lithium titanium composite oxide as a negative electrode active material, carbon black as a conductive material, a binder, and a binder were mixed in a solvent to form a slurry.
  • negative electrodes used in Example 28 and Comparative Example 6 were prepared in the same manner as in Examples A, B, and C.
  • a positive electrode used in Examples 28 and Comparative Example 6 was prepared in the same manner as the positive electrode used in Examples A and B.
  • a sheet battery was produced in the same manner as in Examples A, B, and C except that the electrolyte solution, the negative electrode, and the positive electrode were used, and batteries used in Example 28 and Comparative Example 6 were obtained.
  • the non-aqueous electrolyte secondary battery of the present invention can be used for various known applications. Specific examples include, for example, notebook computers, pen input computers, mobile computers, electronic book players, mobile phones, smartphones, mobile faxes, mobile copy, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, Mini-disc, walkie-talkie, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, motor, automobile, motorcycle, motorbike, bicycle, lighting equipment, toy, game machine, watch, electric tool, strobe, camera , Load leveling power source, natural energy storage power source and the like.

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Abstract

La présente invention concerne la fourniture d'une batterie secondaire à électrolyte non aqueux, en particulier d'une batterie comprenant une électrode positive qui a un potentiel de fonctionnement de limite supérieure élevée, dont la quantité de gaz généré est réduite, tout en ayant une excellente durabilité de cycle à haute température. Une batterie secondaire à électrolyte non aqueux est dotée : d'une solution d'électrolyte non aqueux qui contient un sel de lithium et un solvant non aqueux qui dissout le sel de lithium ; d'une électrode négative qui est capable d'absorber et de désorber les ions lithium ; et d'une électrode positive. Cette batterie secondaire a électrolyte non aqueux est caractérisée en ce que : la solution d'électrolyte non aqueux contient un carbonate cyclique qui est représenté par la formule générale (1), un carbonate cyclique fluoré qui est représenté par la formule générale (2) et un carbonate en chaîne fluoré qui est représenté par la formule générale (3) ; et le carbonate cyclique qui est représenté par la formule générale (1) est compris dans le solvant non aqueux dans une quantité de 15 % en volume ou plus. Cette batterie secondaire à électrolyte non aqueux forme une batterie secondaire à électrolyte non aqueux dont la quantité de gaz généré est réduite et la durabilité de cycle à haute température est excellente même dans les cas où le potentiel de fonctionnement de limite supérieure de l'électrode positive est de 4,5 V ou plus par rapport à Li/Li+.
PCT/JP2012/083949 2011-12-28 2012-12-27 Solution d'électrolyte non aqueux et batterie secondaire à électrolyte non aqueux WO2013100081A1 (fr)

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JP2013551828A JP6127980B2 (ja) 2011-12-28 2012-12-27 非水系電解液及び非水系電解液二次電池
KR1020147017813A KR102206695B1 (ko) 2011-12-28 2012-12-27 비수계 전해액 및 비수계 전해액 이차 전지
CN201280065277.1A CN104025366A (zh) 2011-12-28 2012-12-27 非水系电解液和非水系电解液二次电池
KR1020197014633A KR102208587B1 (ko) 2011-12-28 2012-12-27 비수계 전해액 및 비수계 전해액 이차 전지

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CN112531209A (zh) * 2019-09-18 2021-03-19 三星Sdi株式会社 添加剂、电解质和包括该电解质的可再充电锂电池
CN113945627A (zh) * 2021-09-27 2022-01-18 中国科学院深圳先进技术研究院 二次电池电极锂枝晶在线监测方法及系统、二次电池

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