WO2013183673A1 - Batterie secondaire à électrolyte non aqueux et solution d'électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux et solution d'électrolyte non aqueux Download PDF

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WO2013183673A1
WO2013183673A1 PCT/JP2013/065597 JP2013065597W WO2013183673A1 WO 2013183673 A1 WO2013183673 A1 WO 2013183673A1 JP 2013065597 W JP2013065597 W JP 2013065597W WO 2013183673 A1 WO2013183673 A1 WO 2013183673A1
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group
secondary battery
positive electrode
formula
hydrogen atom
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PCT/JP2013/065597
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Japanese (ja)
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郁雄 木下
吉憲 金澤
児玉　邦彦
洋平 石地
智則 石野
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富士フイルム株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte.
  • lithium ion batteries secondary batteries
  • lithium metal secondary batteries secondary batteries
  • These realize charging and discharging with a large energy density compared to lead batteries and nickel cadmium batteries.
  • application to portable electronic devices such as a camera-integrated VTR (video tape recorder), a mobile phone, or a notebook personal computer has become widespread using this characteristic.
  • VTR video tape recorder
  • a mobile phone or a notebook personal computer has become widespread using this characteristic.
  • secondary batteries that are lighter and have higher energy density as power sources for portable electronic devices is being promoted.
  • miniaturization, long life, and high safety have been strongly demanded.
  • a lithium ion secondary battery and a lithium metal secondary battery have a problem of overcharging as an inherent problem to be solved. .
  • the ignition of the latter battery is a problem peculiar to a lithium secondary battery using an organic electrolyte, and a sufficient response has been desired from the viewpoint of ensuring safety in use.
  • a lithium secondary battery is usually designed so that the charging voltage is set in a positive electrode potential range in which electrode deterioration does not occur and does not exceed the set voltage.
  • Patent Document 1 there is a method of suppressing excessive release of lithium by adding a compound that is oxidized at the positive electrode during overcharge to form a high resistance film on the positive electrode during overcharge.
  • Patent Document 2 a method of suppressing excessive release of lithium by adding a compound that is oxidized at the positive electrode during overcharge to form a high resistance film on the positive electrode during overcharge.
  • the battery voltage rapidly rises as the resistance rises, so that it is easy to detect like an electric device, and it is possible to cut off the supply of electricity by cutting off the circuit and avoid a dangerous state.
  • Patent Document 2 a method of suppressing excessive release of lithium by adding a compound that is oxidized at the positive electrode during overcharge to form a high resistance film on the positive electrode during overcharge.
  • the lithium secondary battery has been greatly improved since ten years before the overcharge prevention measure was taken in Patent Document 1.
  • the structure and operating conditions of the battery are greatly different.
  • One example is the positive electrode.
  • LiCoO 2 positive electrode potential: 4.1 V
  • LiMn 2 O 4 or the like has been used as another general positive electrode active material.
  • the battery is generally designed so that the positive electrode potential during charging is 4.2 V or less from the viewpoint of deterioration of the positive electrode.
  • a LiNiMnO-based positive electrode active material or the like has been developed, and the usable positive electrode potential has reached 4.25 V or more. According to the confirmation of the present inventors, it has been found that, in the positive electrode having such a high potential, the previously proposed biphenyl cannot ensure sufficient overcharge prevention.
  • the present invention aims to provide a non-aqueous electrolyte secondary battery exhibiting good battery performance and high overcharge-preventing property, and a non-aqueous electrolyte used therein, particularly under the condition of having a positive electrode with a high electrode potential. To do.
  • a non-aqueous electrolyte secondary battery having a positive electrode, a negative electrode, and a non-aqueous electrolyte
  • the positive electrode has a material showing a positive electrode potential (Li / Li + reference) of 4.25 V or more as an active material
  • the non-aqueous electrolyte is a non-aqueous electrolyte secondary battery containing an electrolyte and a pyrazole derivative represented by the following formula (I) in an organic solvent.
  • R 1 to R 3 each represent a hydrogen atom or a monovalent substituent.
  • a 1 represents an aryl group or a heteroaryl group.
  • R 1 to R 8 are each a hydrogen atom, alkyl group, alkenyl group, alkoxyl group, aryl group, amino group, fluorine atom, cyano group, heteroaryl group, alkylsulfonyl group, arylsulfonyl
  • R 4 to R 8 are each a hydrogen atom, a fluorine atom, a cyano group, or a trifluoromethyl group
  • R 1 to R 3 are a hydrogen atom, a fluorine atom, a cyano group
  • the nonaqueous electrolyte secondary battery according to [5] which is a phenyl group, a pyridyl group, or a pyrimidyl group substituted with a fluoroalkyl group or an electron withdrawing group.
  • the nonaqueous electrolyte secondary battery according to [5] wherein the pyrazole derivative represented by the formula (III) is a compound represented by the following formula (V).
  • R 1 , R 3 , R 6 and R 7 are each a hydrogen atom or a monovalent substituent.
  • R 1 to R 8 are each a hydrogen atom, alkyl group, alkenyl group, alkoxyl group, aryl group, amino group, fluorine atom, cyano group, heteroaryl group, alkylsulfonyl group, arylsulfonyl
  • R 4 to R 8 are each a hydrogen atom, a fluorine atom, a cyano group, or a trifluoromethyl group
  • R 1 to R 3 are each a hydrogen atom, a fluorine atom, a cyano group
  • the nonaqueous electrolyte secondary battery according to [5] which is a phenyl group, a pyridyl group, or a pyrimidyl group substituted with a fluoroalkyl group or an electron withdrawing group.
  • R 4 to R 13 are each a hydrogen atom, a fluorine atom, a cyano group, or a trifluoromethyl group.
  • R 1 is a hydrogen atom, a fluorine atom, a cyano group, a trifluoroalkyl group, or an electron withdrawing group.
  • X 11 to X 20 are a methine group or a nitrogen atom, and one of them is a nitrogen atom, and when X 11 to X 20 is a nitrogen atom, And there is no corresponding R 4 to R 13.
  • a non-aqueous electrolyte used in a secondary battery having a positive electrode, a negative electrode, and a non-aqueous electrolyte The positive electrode has a material showing a positive electrode potential (Li / Li + reference) of 4.25 V or more as an active material, A nonaqueous electrolytic solution containing an electrolyte and a pyrazole derivative represented by the following formula (I) in an organic solvent.
  • R 1 to R 3 each represent a hydrogen atom or a monovalent substituent.
  • a 1 represents an aryl group or a heteroaryl group.
  • R 4 to R 13 are each a hydrogen atom, a fluorine atom, a cyano group, or a trifluoromethyl group.
  • R 1 is a hydrogen atom, a fluorine atom, a cyano group, a trifluoroalkyl group, or an electron withdrawing group.
  • a 1 represents an aryl group or a heteroaryl group.
  • Resistance increase rate (resistance after charging to positive electrode potential 5V) / (Resistance after charging to positive electrode potential 4.25V)
  • a nonaqueous electrolyte secondary battery comprising the electrolyte for a nonaqueous secondary battery according to any one of [17] to [20], a positive electrode, and a negative electrode, wherein the positive electrode is used as an active material thereof 4.
  • a non-aqueous electrolyte secondary battery comprising a material exhibiting a positive electrode potential (Li / Li + reference) of 4.25 V or higher.
  • the nonaqueous electrolyte secondary battery according to [21], wherein the rate of increase in resistance of the following formula calculated by impedance measurement is 5 or more. Resistance increase rate (resistance after charging to positive electrode potential 5V) / (Resistance after charging to positive electrode potential 4.25V)
  • non-aqueous electrolyte and the non-aqueous electrolyte secondary battery of the present invention even under conditions having a positive electrode with a high electrode potential, good battery performance can be achieved and high overcharge prevention can be realized. Can do.
  • the electrolyte used for the non-aqueous electrolyte secondary battery of the present invention contains a specific pyrazole derivative (aryl pyrazole compound) in an organic solvent. Thereby, especially high overcharge prevention property is exhibited on the conditions using the positive electrode which shows high potential.
  • the reason for this includes unclear points, but including the estimation is as follows.
  • An overcharge inhibitor proposed in a conventional secondary battery to which a relatively low potential positive electrode is applied that is, biphenyl or the like is oxidized at a positive electrode potential of 4.2 V or less to prevent overcharge. Therefore, in terms of the relationship with the oxidation potential, charging up to a higher potential cannot be performed.
  • the specific arylpyrazole compound employed in the present invention has an increased oxidation potential, the positive electrode can be charged to a higher potential than the conventional one.
  • at the time of overcharge it is presumed that it rapidly decomposes at the oxidation potential derived from arylpyrazole, and forms a resistance film on the electrode to suppress problems due to overcharge.
  • the present invention will be described in detail based on preferred embodiments thereof.
  • Specific pyrazole derivatives In the present invention, a specific pyrazole derivative (arylpyrazole compound) represented by the following formula (I) is used.
  • R 1 to R 3 each represent a hydrogen atom or a monovalent substituent.
  • the monovalent substituent include the substituent T described later.
  • substituents an alkyl group (preferably 1 to 5 carbon atoms), an alkenyl group (preferably 2 to 6 carbon atoms), an alkoxyl group (preferably 1 to 6 carbon atoms), an aryl group (preferably 6 to 12 carbon atoms). More preferably 6 to 10), amino group (preferably 0 to 4 carbon atoms, more preferably 1 to 4), fluorine atom, cyano group, heteroaryl group (preferably 2 to 12 carbon atoms, more preferably 3 carbon atoms).
  • a pyridyl group preferably having a carbon number of 1 to 5
  • an arylsulfonyl group preferably having a carbon number of 6 to 10
  • an alkylsulfonyloxy group preferably Is an arylsulfonyloxy group (preferably 6 to 10 carbon atoms)
  • an alkoxysulfonyl group preferably 1 to 5 carbon atoms.
  • Etc. are preferred.
  • the alkyl group may further have a substituent T (a halogen atom is preferable, and a fluorine atom is more preferable).
  • each of R 1 to R 3 is preferably a hydrogen atom, a fluorine atom, a cyano group, an alkyl group (including a fluoroalkyl group), an alkoxyl group, a phenyl group, a pyridyl group, a pyrazolyl group, or a pyrimidyl group
  • R 1 to R 3 are each a hydrogen atom, a fluorine atom, a cyano group, a trifluoroalkyl group (preferably having 1 to 3 carbon atoms), a phenyl group substituted with an electron withdrawing group, a pyridyl group, or a pyrimidyl group. It is more preferable.
  • the electron withdrawing group is preferably a fluorine atom, a cyano group, a trifluoromethyl group, or a trifluoromethoxy group.
  • the electron withdrawing group typically means a group having a positive value in the Hammett's rule ⁇ p value.
  • ⁇ p value For the definition and example values of the ⁇ p value, see Chem. Rev. Reference may be made to 1991.91.165-195.
  • a 1 represents an aryl group or a heteroaryl group.
  • the heteroaryl group is preferably a 5-membered or 6-membered nitrogen-containing heteroaryl group.
  • a phenyl group, a pyridyl group, a pyrimidyl group, and a pyrazyl group are preferable. These groups may further have a substituent T. Note that when A 1 is a nitrogen-containing heterocyclic ring, which is preferably substituted to the nitrogen atom of the pyrazole portion at its carbon atom.
  • the pyrazole derivative represented by the formula (I) is preferably a compound represented by the following formula (II).
  • R 1 to R 3 are as defined in the formula (I).
  • X 1 to X 5 are a methine group or a nitrogen atom.
  • the methine group may have a substituent.
  • the substituent include an example of the substituent T described later. Of these, unsubstituted (—CH ⁇ ) is preferable.
  • the pyrazole derivative represented by the formula (II) is more preferably a compound represented by the following formula (III) or (IV).
  • R 1 to R 3 are each a hydrogen atom or a monovalent substituent.
  • the preferable ones are the same as those described as R 1 to R 3 .
  • R 4 to R 8 are groups having the same meanings as R 1 to R 3 , and their preferred ranges are also the same. Of these, a fluorine atom, a cyano group, or a trifluoromethyl group is preferable.
  • X 11 to X 15 are a methine group or a nitrogen atom, and any one of them is a nitrogen atom. At this time, the methine group may have a substituent. Preferred examples of the methine group which may have a substituent are the same as those described for X 1 to X 3 above, and preferably unsubstituted (—CH ⁇ ). When X 11 to X 15 are nitrogen atoms, there is no corresponding R 4 to R 8 .
  • the pyrazole derivative represented by the formula (III) is preferably a compound represented by the following formula (V).
  • R 1 and R 3 to R 8 are each a hydrogen atom or a monovalent substituent.
  • the preferred range is the same as described above.
  • the pyrazole derivative represented by the formula (III) is preferably a compound represented by the following formula (VI).
  • R 1 , R 3 , R 6 and R 7 are each a hydrogen atom or a monovalent substituent.
  • the preferred range is the same as described above.
  • the pyrazole derivative is preferably a compound represented by the following formula (VII).
  • R 1 and R 4 to R 13 have the same meanings as the groups defined for R 1 to R 3 .
  • R 4 to R 13 are each a hydrogen atom, a fluorine atom, a cyano group, or a trifluoromethyl group.
  • R 1 is preferably a hydrogen atom, a fluorine atom, a cyano group, a trifluoroalkyl group (preferably having 1 to 3 carbon atoms), a phenyl group, a pyridyl group or a pyrimidyl group substituted with an electron withdrawing group.
  • X 11 to X 20 are a methine group or a nitrogen atom, and any one of them is a nitrogen atom.
  • Preferred examples of the electron withdrawing group have the same meanings as described above. When X 11 to X 20 are nitrogen atoms, there is no corresponding R 4 to R 13 .
  • the specific pyrazole derivative is preferably contained in the nonaqueous electrolytic solution at 0.005 mol / L or more, more preferably 0.01 mol / L or more, and 0.02 mol / L or more. It is particularly preferable to contain it. Although there is no upper limit in particular, it is preferably contained at 3 mol / L or less, more preferably 2 mol / L or less, and particularly preferably 1.5 mol / L or less. By setting it to the above lower limit value or more, the effect of preventing overcharge in the present invention can be sufficiently enhanced, which is preferable. On the other hand, it is preferable to make it not more than the above upper limit value, since the battery performance is not deteriorated and both overcharge prevention and good battery performance can be achieved.
  • a substituent that does not specify substitution / non-substitution means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution.
  • Preferred substituents include the following substituent T.
  • substituent T examples include the following.
  • An alkyl group preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl A group preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like
  • a cycloalkyl group preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohex
  • the compound or substituent / linking group contains an alkyl group / alkylene group, alkenyl group / alkenylene group, etc.
  • these may be cyclic or chain-like, and may be linear or branched, and substituted as described above. It may be substituted or unsubstituted.
  • an aryl group, a heterocyclic group, etc. may be monocyclic or condensed and may be similarly substituted or unsubstituted.
  • organic solvent examples include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, 1,2-dimethoxyethane.
  • ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate is preferable.
  • a high viscosity (high dielectric constant) solvent such as ethylene carbonate or propylene carbonate (for example, ratio A combination of a dielectric constant ⁇ ⁇ 30) and a low viscosity solvent such as dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate (for example, viscosity ⁇ 1 mPa ⁇ s) is more preferable. This is because the dissociation property of the electrolyte salt and the ion mobility are improved.
  • organic solvent (nonaqueous solvent) used in the present invention is not limited to the above examples.
  • the solvent may contain a cyclic carbonate having an unsaturated bond. This is because the chemical stability of the electrolytic solution is further improved.
  • the cyclic carbonate having an unsaturated bond include at least one selected from the group consisting of vinylene carbonate compounds, vinyl ethylene carbonate compounds, and methylene ethylene carbonate compounds.
  • vinylene carbonate compounds include vinylene carbonate (1,3-dioxol-2-one), methyl vinylene carbonate (4-methyl-1,3-dioxol-2-one), and ethyl vinylene carbonate (4-ethyl- 1,3-dioxol-2-one), 4,5-dimethyl-1,3-dioxol-2-one, 4,5-diethyl-1,3-dioxol-2-one, 4-fluoro-1,3 And -dioxol-2-one and 4-trifluoromethyl-1,3-dioxol-2-one.
  • Examples of the vinyl ethylene carbonate compound include vinyl ethylene carbonate (4-vinyl-1,3-dioxolan-2-one), 4-methyl-4-vinyl-1,3-dioxolan-2-one, and 4-ethyl.
  • Examples of the methylene ethylene carbonate compound include 4-methylene-1,3-dioxolan-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one, and 4,4-diethyl-5-one. And methylene-1,3-dioxolan-2-one.
  • vinylene carbonate is preferable.
  • an electrolyte and a pyrazole derivative represented by the formula (I) are contained in an organic solvent, and the pyrazole derivative is oxidized during overcharge to increase battery resistance.
  • the pyrazole derivative preferably does not act below the normal charge positive electrode potential of the battery.
  • the normal charge positive electrode potential (positive electrode potential of the positive electrode active material) of this battery is preferably 4.25 V (Li / Li + reference) or more, and more preferably 4.3 V or more. Although there is no upper limit in particular, it is practical that it is 5V or less.
  • the rate of increase in resistance calculated by impedance measurement is preferably 5 or more, and more preferably 15 or more. There is no particular upper limit, but it is preferably 1000 or less. Note that the rate of increase in resistance by the above impedance measurement can also characterize the present invention as a performance when a secondary battery is obtained.
  • Measurement method of resistance increase rate As a method for observing the resistance of the battery, there is a method for measuring the AC impedance of the battery. When the frequency is changed from a low frequency to a high frequency and the change in impedance at that time is plotted on a complex plane, the resistance of the battery can be measured by obtaining a graph called “Cole-Cole Plot”. The rate of increase in resistance is obtained from the resistance when overcharged and the resistance when charged at a normal potential.
  • the specific measurement method can refer to those employed in the examples.
  • Normal charging means a state in which charging is performed within the design voltage of the battery.
  • a method is used in which a constant current charge is performed until a set voltage is reached, and then a full charge is performed while the set voltage is maintained.
  • the positive electrode potential during normal charging in the present application represents the positive electrode potential at the set voltage.
  • overcharge refers to a state in which the battery is charged at a voltage exceeding the design voltage of the battery due to some factor.
  • Examples of the electrolyte that can be used in the electrolytic solution of the present invention include metal ions or salts thereof, and metal ions or salts thereof belonging to Group 1 or Group 2 of the periodic table are preferred. Specifically, it is appropriately selected depending on the purpose of use of the electrolytic solution, and examples thereof include lithium salt, potassium salt, sodium salt, calcium salt, magnesium salt and the like. Of these, lithium salts are preferred from the viewpoint of output.
  • a lithium salt may be selected as a metal ion salt.
  • the lithium salt is preferably a lithium salt usually used for an electrolyte of a non-aqueous electrolyte solution for a lithium secondary battery, and for example, those described below are preferable.
  • Inorganic lithium salts inorganic fluoride salts such as LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 ; perhalogenates such as LiClO 4 , LiBrO 4 , LiIO 4 ; inorganic chloride salts such as LiAlCl 4 etc.
  • Oxalatoborate salt lithium bis (oxalato) borate, lithium difluorooxalatoborate and the like.
  • Rf 1 and Rf 2 each represent a perfluoroalkyl group.
  • electrolyte used for electrolyte solution may be used individually by 1 type, or may combine 2 or more types arbitrarily.
  • the content of the electrolyte in the electrolytic solution is added in such an amount that a preferable salt concentration described below in the method for preparing the electrolytic solution is obtained.
  • the salt concentration is appropriately selected depending on the intended use of the electrolytic solution, but is generally 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 30% by mass or less, based on the total mass of the electrolytic solution.
  • concentration when evaluating as an ion density
  • the electrolytic solution of the present invention may contain at least one selected from a negative electrode film forming agent, a flame retardant, and an overcharge inhibitor.
  • the content ratio of these functional additives in the nonaqueous electrolytic solution is not particularly limited, but is preferably 0.001% by mass to 10% by mass with respect to the whole nonaqueous electrolytic solution.
  • the non-aqueous electrolyte solution is prepared by a conventional method by dissolving the above components in the non-aqueous electrolyte solvent, including an example in which a lithium salt is used as a metal ion salt.
  • non-water means substantially not containing water, and may contain a small amount of water as long as the effect of the invention is not hindered.
  • the water content is preferably 200 ppm (mass basis) or less, and more preferably 100 ppm or less. Although there is no particular lower limit, it is practical that it is 10 ppm or more considering inevitable mixing.
  • the viscosity of the electrolytic solution of the present invention is not particularly limited, but it is preferably 10 to 0.1 mPa ⁇ s, more preferably 5 to 0.5 mPa ⁇ s at 25 ° C.
  • the electrolytic solution of the present invention may be a kit composed of a plurality of liquids or powders.
  • the first agent (first liquid) is composed of an electrolyte and an organic solvent
  • the second agent (second liquid) is composed of a pyrazole derivative and an organic solvent
  • the two liquids are mixed before use. It may be in a form to do.
  • other additives and the like may be contained in the first agent, the second agent, and / or the other agent (third agent).
  • the lithium ion secondary battery 10 of the present embodiment includes the non-aqueous electrolyte 5 of the present invention, a positive electrode C (positive electrode current collector 1, positive electrode active material layer 2) capable of inserting and releasing lithium ions, and lithium ions.
  • Negative electrode A negative electrode current collector 3, negative electrode active material layer 4.
  • a separator 9 disposed between the positive electrode and the negative electrode, a current collecting terminal (not shown), an outer case, etc. (Not shown).
  • a protective element may be attached to at least one of the inside of the battery and the outside of the battery. With this structure, lithium ions are transferred a and b in the electrolyte 5, charging ⁇ and discharging ⁇ can be performed, and the operating mechanism 6 is operated or stored via the circuit wiring 7. be able to.
  • the battery shape to which the lithium secondary battery of the present embodiment is applied is not particularly limited, and examples thereof include a bottomed cylindrical shape, a bottomed square shape, a thin shape, a sheet shape, and a paper shape. Any of these may be used. Further, it may be of a different shape such as a horseshoe shape or a comb shape considering the shape of the system or device to be incorporated. Among them, from the viewpoint of efficiently releasing the heat inside the battery to the outside, a square shape such as a bottomed square shape or a thin shape having at least one relatively flat and large surface is preferable.
  • the lithium secondary battery of the present embodiment is configured to include an electrolytic solution 5, positive and negative electrode composites C and A, and a separator basic member 9, based on FIG. 1. Hereinafter, each of these members will be described.
  • the electrode mixture is formed by applying a dispersion such as an active material, a conductive agent, a binder, and a filler on a current collector (electrode base material) and forming it into a sheet shape.
  • a positive electrode mixture whose active material is a positive electrode active material and a negative electrode mixture whose active material is a negative electrode active material are usually used.
  • each component in the dispersion (mixture, electrode composition) constituting the electrode mixture will be described.
  • -Positive electrode active material In this invention, it is preferable to use the material which can maintain normal use with the positive electrode potential (Li / Li + reference
  • being able to maintain normal use means that even when charging is performed at that voltage, the electrode material does not deteriorate and cannot be used, and this potential is also referred to as a normal usable potential.
  • This potential may be simply referred to as a positive electrode potential.
  • the positive electrode potential (usually usable potential) is more preferably 4.3 V or more. Although there is no upper limit in particular, it is practical that it is 5V or less.
  • Examples of the positive electrode active material having the specific electrode potential include the following.
  • (I) LiNi x Mn y Co z O 2 (x> 0.2, y> 0.2, z ⁇ 0, x + y + z 1), Representative: LiNi 1/3 Mn 1/3 Co 1/3 O 2 (also described as LiNi 0.33 Mn 0.33 Co 0.33 O 2 ) LiNi 1/2 Mn 1/2 O 2 (also described as LiNi 0.5 Mn 0.5 O 2 )
  • the following can also be used as the positive electrode active material having the specific electrode potential.
  • (A) LiCoMnO 4 (B) Li 2 FeMn 3 O 8 (C) Li 2 CuMn 3 O 8 (D) Li 2 CrMn 3 O 8 (E) Li 2 NiMn 3 O 8
  • a particulate positive electrode active material may be used.
  • the average particle size of the positive electrode active material used is not particularly limited, but is preferably 0.1 ⁇ m to 50 ⁇ m.
  • the specific surface area is not particularly limited, but is preferably 0.01 m 2 / g to 50 m 2 / g by the BET method.
  • the pH of the supernatant when 5 g of the positive electrode active material is dissolved in 100 ml of distilled water is preferably 7 or more and 12 or less.
  • a pulverizer or a classifier commonly used to make the positive electrode active substance have a predetermined particle size can be used.
  • a mortar, a ball mill, a vibration ball mill, a vibration mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill, a sieve, or the like is used.
  • the positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the amount of the positive electrode active material is not particularly limited, but is preferably 60 to 98% by mass in 100% by mass of the solid component in the dispersion (mixture) forming the electrode mixture. More preferably, it is 70 to 95% by mass.
  • a negative electrode active material can insert and discharge
  • the material carbonaceous materials, metal oxides such as tin oxide and silicon oxide, metal composite oxides, lithium alloys such as simple lithium and lithium aluminum alloys, and alloys with lithium such as Sn and Si Possible metals and the like.
  • carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of safety.
  • the metal composite oxide is preferably capable of inserting and extracting lithium. Although it does not restrict
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • Examples thereof include carbonaceous materials obtained by baking various synthetic resins such as artificial pitches such as petroleum pitch, natural graphite, and vapor-grown graphite, and PAN-based resins and furfuryl alcohol resins.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA-based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, mesophase micro
  • Examples thereof include spheres, graphite whiskers, and flat graphite.
  • carbonaceous materials can be divided into non-graphitizable carbon materials and graphite-based carbon materials depending on the degree of graphitization.
  • the carbonaceous material preferably has a face spacing, density, and crystallite size described in JP-A-62-222066, JP-A-2-6856, and 3-45473.
  • the carbonaceous material does not have to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, or the like is used. You can also.
  • the metal oxide and metal composite oxide which are negative electrode active materials used in the nonaqueous electrolyte secondary battery, need only contain at least one of them.
  • amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used.
  • chalcogenite which is a reaction product of a metal element and an element of Group 16 of the periodic table.
  • amorphous as used herein means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2 ⁇ , and is a crystalline diffraction line. You may have.
  • the strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
  • an amorphous oxide of a semi-metal element and a chalcogenide are more preferable, and elements of Groups 13 (IIIB) to 15 (VB) of the periodic table, Particularly preferred are oxides and chalcogenides composed of one kind of Al, Ga, Si, Sn, Ge, Pb, Sb, Bi or a combination of two or more kinds thereof.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 , such as SnSiS 3 may preferably be mentioned. Moreover, these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
  • the average particle size of the negative electrode active material used is preferably 0.1 ⁇ m to 60 ⁇ m.
  • a well-known pulverizer or classifier is used.
  • a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve is preferably used.
  • wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary.
  • classification is preferably performed.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.
  • the chemical formula of the compound obtained by the firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method and a mass difference between powders before and after firing as a simple method.
  • ICP inductively coupled plasma
  • Examples of the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, and Ge include carbon materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloys, lithium A metal that can be alloyed with is preferable.
  • lithium titanate more specifically, lithium-titanium oxide (Li [Li 1/3 Ti 5/3 ] O 4 ) as the negative electrode active material.
  • the amount of the negative electrode active material in the dispersion (mixture) forming the electrode mixture is not particularly limited, but it is preferably 60 to 98% by mass, and 70 to 95% by mass in 100% by mass of the solid component. Is more preferable.
  • an electrically conductive material is an electronically conductive material which does not cause a chemical change in the comprised secondary battery. Any material may be used as the material, and a known conductive material can be arbitrarily used. Usually, natural graphite (scale-like graphite, scale-like graphite, earth-like graphite, etc.), artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber and metal powder (copper, nickel, aluminum, silver (Japanese Patent Laid-Open No.
  • conductive fibers such as metal fibers or polyphenylene derivatives (described in JP-A-59-20971) can be included as a single kind or a mixture thereof.
  • the amount of the conductive agent added is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass in 100% by mass of the solid component in the dispersion (mixture) forming the electrode mixture.
  • carbon or graphite 0.5 to 15% by mass is particularly preferable in the dispersion.
  • binder examples include polysaccharides, thermoplastic resins, and polymers having rubber elasticity. Among them, for example, starch, carboxymethyl cellulose, cellulose, diacetyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium alginate, polyacrylic acid, sodium polyacrylate, polyvinyl phenol, polyvinyl methyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, poly Water-soluble polymers such as acrylonitrile, polyacrylamide, polyhydroxy (meth) acrylate, styrene-maleic acid copolymer, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene furo Ride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polyethylene (
  • Binders can be used alone or in combination of two or more.
  • the amount of the binder added is small, the holding power and cohesive force of the electrode mixture are weakened. If the amount is too large, the electrode volume increases and the capacity per electrode unit volume or unit mass decreases.
  • the amount of the binder added is preferably 1 to 30% by mass, more preferably 2 to 10% by mass in 100% by mass of the solid component in the dispersion (mixture) forming the electrode mixture.
  • the electrode compound material may contain the filler.
  • the material forming the filler is preferably a fibrous material that does not cause a chemical change in the secondary battery of the present invention. Any material can be used for the material. Usually, fibrous fillers made of materials such as olefin polymers such as polypropylene and polyethylene, glass, and carbon are used.
  • the addition amount of the filler is not particularly limited, but is preferably 0 to 30% by mass in 100% by mass of the solid component in the dispersion (mixture) forming the electrode mixture.
  • the positive / negative current collector an electron conductor that does not cause a chemical change in the non-aqueous electrolyte secondary battery of the present invention is used.
  • the current collector of the positive electrode in addition to aluminum, stainless steel, nickel, titanium, etc., the surface of aluminum or stainless steel is preferably treated with carbon, nickel, titanium, or silver. Among them, aluminum and aluminum alloys are preferable. More preferred.
  • the negative electrode current collector aluminum, copper, stainless steel, nickel and titanium are preferable, and aluminum, copper and copper alloy are more preferable.
  • a film sheet shape is usually used, but a net, a punched material, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 ⁇ m to 500 ⁇ m.
  • the current collector surface is roughened by surface treatment.
  • the electrode mixture of the lithium secondary battery is formed by a member appropriately selected from these materials.
  • the separator is preferably a material having mechanical strength for electrically insulating the positive electrode and the negative electrode, ion permeability, and oxidation / reduction resistance at the contact surface between the positive electrode and the negative electrode.
  • a material a porous polymer material, an inorganic material, an organic-inorganic hybrid material, glass fiber, or the like is used.
  • These separators preferably have a shutdown function for ensuring safety, that is, a function of closing the gap at 80 ° C. or higher to increase resistance and blocking current, and the closing temperature is 90 ° C. or higher and 180 ° C. or lower. It is preferable.
  • the shape of the holes of the separator is usually circular or elliptical, and the size is 0.05 ⁇ m to 30 ⁇ m, preferably 0.1 ⁇ m to 20 ⁇ m. Furthermore, it may be a rod-like or irregular-shaped hole as in the case of making by a stretching method or a phase separation method.
  • the ratio of these gaps, that is, the porosity, is 20% to 90%, preferably 35% to 80%.
  • the polymer material may be a single material such as a cellulose nonwoven fabric, polyethylene, or polypropylene, or may be a material using two or more composite materials. What laminated
  • 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, and those having a particle shape or fiber shape are used.
  • a thin film shape such as a non-woven fabric, a woven fabric, or a microporous film is used.
  • the thin film shape those having a pore diameter of 0.01 ⁇ m to 1 ⁇ m and a thickness of 5 ⁇ m 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.
  • alumina particles having a 90% particle diameter of less than 1 ⁇ m are formed on both surfaces of the positive electrode as a porous layer using a fluororesin binder.
  • the lithium secondary battery can be applied to any shape such as a sheet shape, a square shape, and a cylinder shape.
  • the (dispersion) mixture containing the positive electrode active material and the negative electrode active material is mainly used after being applied (coated), dried and compressed on the current collector.
  • FIG. 2 shows an example of a bottomed cylindrical lithium secondary battery 100.
  • This battery is a bottomed cylindrical lithium secondary battery 100 in which a positive electrode sheet 14 and a negative electrode sheet 16 stacked with a separator 12 interposed therebetween are wound and accommodated in an outer can 18.
  • 20 is an insulating plate
  • 22 is a sealing plate
  • 24 is a positive current collector
  • 26 is a gasket
  • 28 is a pressure sensitive valve element
  • 30 is a current interrupting element.
  • each member corresponds to the whole drawing by reference numerals.
  • a negative electrode active material is mixed with a binder or filler used as desired in an organic solvent to prepare a slurry or paste negative electrode mixture.
  • the obtained negative electrode mixture is uniformly applied over the entire surface of both surfaces of the metal core as a current collector, and then the organic solvent is removed to form a negative electrode active material layer.
  • the laminated body (mixed material) of a collector and a negative electrode active material layer is rolled with a roll press etc., and it adjusts to predetermined thickness and obtains a negative electrode sheet (electrode sheet).
  • the coating method of each agent, the drying of the coated material, and the method of forming the positive and negative electrodes may be in accordance with conventional methods.
  • a cylindrical battery is taken as an example, but the present invention is not limited to this.
  • the positive and negative electrode sheets (compounds) produced by the above method are stacked via a separator. After being assembled, it is processed into a sheet battery as it is, or after being folded and inserted into a rectangular can, the can and the sheet are electrically connected, the electrolyte is injected, and the opening is opened using a sealing plate.
  • the prismatic battery may be formed by sealing.
  • the safety valve can be used as a sealing plate for sealing the opening.
  • the sealing member may be provided with various conventionally known safety elements.
  • a fuse, bimetal, PTC element, or the like is preferably used as the overcurrent prevention element.
  • a method of cutting the battery can a method of cracking the gasket, a method of cracking the sealing plate, or a method of cutting the lead plate can be used.
  • the charger may be provided with a protection circuit incorporating measures against overcharge and overdischarge, or may be connected independently.
  • a metal or alloy having electrical conductivity can be used.
  • metals such as iron, nickel, titanium, chromium, molybdenum, copper, and aluminum, or alloys thereof are preferably used.
  • a known method eg, direct current or alternating current electric welding, laser welding, ultrasonic welding
  • a welding method for the cap, can, sheet, and lead plate can be used as a welding method for the cap, can, sheet, and lead plate.
  • the sealing agent for sealing a conventionally known compound or mixture such as asphalt can be used.
  • non-aqueous electrolyte secondary battery of the present invention Since the nonaqueous electrolyte secondary battery of the present invention has good cycle performance, it is applied to various applications.
  • a notebook computer pen input personal computer, mobile personal computer, electronic book player, mobile phone, cordless phone, pager, handy terminal, mobile fax, mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, electric shaver, walkie-talkie, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, memory card, etc.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.
  • the metal ion used for charge transport in the secondary battery is not particularly limited, but is preferably a metal ion belonging to Group 1 or Group 2 of the periodic table. Among these, it is preferable to use lithium ions, sodium ions, magnesium ions, calcium ions, aluminum ions, and the like.
  • lithium ions sodium ions, magnesium ions, calcium ions, aluminum ions, and the like.
  • Journal of Electrochemical Society; Electrochemical Science and Technology, USA, 1980, Vol. 127, pages 2097-2099, and the like can be referred to.
  • magnesium ions see Nature 407, p. 724-727 (2000) and the like can be referred to.
  • For calcium ions see J.H. Electrochem.
  • Example 1 (Example 1 / Comparative Example 1) ⁇ Preparation of electrolyte 1M LiPF 6 ethylene carbonate / ethyl methyl carbonate volume ratio 1: 2 To the electrolyte, the additive (compound) shown in Table 1 was added in the amount shown in Table 1, and the test electrolyte was added. Prepared.
  • the positive electrode is an active material: lithium nickel manganese cobaltate (LiNi 1/3 Mn 1/3 Co 1/3 O 2 ) or lithium manganate (LiMn 2 O 4 ), lithium cobaltate (LiCoO 2) ) 85% by mass, conductive auxiliary agent: carbon black 7% by mass, binder: PVDF (polyvinylidene fluoride) 8% by mass, the negative electrode is active material: Gr (natural graphite) 92% by mass, binder: PVDF 8% by mass It was made with.
  • the separator is made of polypropylene and has a thickness of 25 ⁇ m.
  • Discharge capacity maintenance rate (%) (Discharge capacity at the 300th cycle / discharge capacity at the first cycle) ⁇ 100
  • the cycle test evaluated the result of the discharge capacity maintenance rate as follows. A: 70% or more B: 60% or more and less than 70% C: 50% or more and less than 60% D: 40% or more and less than 50% E: Less than 40%
  • the resistance increase rate was evaluated as follows. AA: 20 or more A: 15 or more and less than 20 B: 5 or more and less than 15 C: Less than 5
  • Discharge capacity retention rate after storage (%) (Discharge capacity after storage at 45 ° C. for 2 weeks / discharge capacity before storage) ⁇ 100
  • the positive electrode, the negative electrode, and the electrolytic solution are shown in Table 1 below. The one described in 1. was used.
  • NMC LiNi 0.33 Mn 0.33 Co 0.33 O 2
  • LMO LiMn 2 O 4
  • Example 2 and Comparative Example 2 Preparation of electrolyte solution
  • Additives (compounds) shown in Table 2 in the amounts shown in Table 2 to the volume ratio of 2: 1 to 7 of ethylene carbonate / propylene carbonate / ethyl methyl carbonate of 1M LiBF 4 were added.
  • a test electrolyte was prepared.
  • the positive electrode is an active material: lithium nickel manganese cobaltate (LiNi 1/3 Mn 1/3 Co 1/3 O 2 ) or lithium manganate (LiMn 2 O 4 ), lithium cobaltate (LiCoO 2) ) 85% by mass, conductive auxiliary agent: carbon black 7% by mass, binder: PVDF (polyvinylidene fluoride) 8% by mass, the negative electrode is active material: lithium titanate (Li 4 Ti 5 O 12 ) 92% by mass, Binder: Made with 8% by mass of PVDF.
  • the separator is made of polypropylene and has a thickness of 25 ⁇ m.
  • Discharge capacity maintenance rate (%) (Discharge capacity at the 300th cycle / discharge capacity at the first cycle) ⁇ 100
  • the cycle test evaluated the result of the discharge capacity maintenance rate as follows. A: 70% or more B: 60% or more and less than 70% C: 50% or more and less than 60% D: 40% or more and less than 50% E: Less than 40%
  • the resistance increase rate was evaluated as follows. AA: 20 or more A: 15 or more and less than 20 B: 5 or more and less than 15 C: Less than 5
  • ⁇ Preservation test> Using a 2032 type battery produced by the above method, charging at a constant current of 2 mA (1 C) in a constant temperature bath at 30 ° C. until the battery voltage reaches 2.7 V (positive electrode potential 4.25 V), followed by constant voltage charging. It was carried out for 2 hours, and was discharged at a constant current of 2 mA (1 C) until the battery voltage reached 1.2 V, and the discharge capacity (mAh) was measured. Next, the battery was charged at a constant current of 2 mA (1 C) until the battery voltage reached 2.7 V, then charged at a constant voltage for 2 hours, and left in a 45 ° C. constant temperature bath for 2 weeks. Thereafter, the battery was discharged at a constant current of 2 mA (1 C) until the battery voltage reached 1.2 V, and the discharge capacity (mAh) was measured.
  • Discharge capacity retention rate after storage (%) (Discharge capacity after storage at 45 ° C. for 2 weeks / discharge capacity before storage) ⁇ 100
  • the positive electrode, the negative electrode, and the electrolytic solution are shown in Table 2 below. The one described in 1. was used.
  • NMC LiNi 0.33 Mn 0.33 Co 0.33 O 2
  • LMO LiMn 2 O 4
  • LCO LiCoO 2
  • LTO Li 4 Ti 5 O 12
  • the present invention in a secondary battery using a positive electrode having a high potential, good cycle characteristics can be exhibited, and further excellent storability and overcharge prevention can be exhibited (see Table 1). ).
  • the high effect is particularly suitably exhibited in a high potential positive electrode (NMC), and further in a battery combining this with LTO (see Table 2).
  • NMC high potential positive electrode
  • the composition of the present application exhibits cycle characteristics equivalent to those without additive in the cycle test, It can be seen that the additive used in the present application does not act at the normal charge positive electrode potential, but acts only during overcharge.
  • Example 3 Preparation of electrolyte solution Addition (compound) shown in Table 3 to 1M LiPF 6 ethylene carbonate / ethyl methyl carbonate volume ratio 1 to 2 electrolyte solution in the amount shown in Table 3 and add test electrolyte solution Prepared.
  • the positive electrode is active material: nickel manganese lithium cobaltate (LiNi 1/3 Mn 1/3 Co 1/3 O 2 ) 85% by mass, conductive auxiliary agent: carbon black 7% by mass, binder: PVDF (Polyvinylidene fluoride) 8% by mass, and the negative electrode was made of active material: lithium titanate (Li 4 Ti 5 O 12 ) 92% by mass, binder: PVDF 8% by mass.
  • the separator is made of polypropylene and has a thickness of 25 ⁇ m.

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Abstract

L'invention concerne une batterie secondaire à électrolyte non aqueux qui comprend une électrode positive, une électrode négative et une solution d'électrolyte non aqueux, et l'électrode positive contenant, en tant que matériau actif de celle-ci, un matériau qui possède un potentiel d'électrode positive de 4,25 V ou plus (sur la base de Li/Li+), et la solution d'électrolyte non aqueux contenant un électrolyte et un dérivé de pyrazole représenté par la formule (I) dans un solvant organique. (Dans la formule, chacun de R1 à R3 représente un atome d'hydrogène ou un substituant monovalent ; et A1 représente un groupement aryle).
PCT/JP2013/065597 2012-06-08 2013-06-05 Batterie secondaire à électrolyte non aqueux et solution d'électrolyte non aqueux WO2013183673A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014123074A1 (fr) * 2013-02-05 2014-08-14 富士フイルム株式会社 Électrolyte pour pile secondaire non aqueuse, pile secondaire non aqueuse et additif pour solution électrolytique
US10683293B2 (en) 2014-08-04 2020-06-16 Nuevolution A/S Optionally fused heterocyclyl-substituted derivatives of pyrimidine useful for the treatment of inflammatory, metabolic, oncologic and autoimmune diseases
WO2020262670A1 (fr) 2019-06-28 2020-12-30 旭化成株式会社 Solution d'électrolyte non aqueuse et batterie secondaire non aqueuse
US11447479B2 (en) 2019-12-20 2022-09-20 Nuevolution A/S Compounds active towards nuclear receptors
US11613532B2 (en) 2020-03-31 2023-03-28 Nuevolution A/S Compounds active towards nuclear receptors
US11780843B2 (en) 2020-03-31 2023-10-10 Nuevolution A/S Compounds active towards nuclear receptors

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107845832A (zh) * 2017-10-27 2018-03-27 山东大学 一种低阻抗不可燃的锂离子电池电解液及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002305022A (ja) * 2001-04-04 2002-10-18 Tomiyama Pure Chemical Industries Ltd 二次電池用非水電解液
JP2003123834A (ja) * 2001-10-17 2003-04-25 Nec Tokin Corp 電解液、並びにこれを用いた電気化学セル
JP2008027833A (ja) * 2006-07-25 2008-02-07 Sanyo Electric Co Ltd 非水電解質二次電池
JP2008218381A (ja) * 2007-02-05 2008-09-18 Sony Corp 非水電解液電池
JP2009512148A (ja) * 2005-10-10 2009-03-19 ゾルファイ フルーオル ゲゼルシャフト ミット ベシュレンクテル ハフツング リチウムイオン電池用のフッ素化添加剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002305022A (ja) * 2001-04-04 2002-10-18 Tomiyama Pure Chemical Industries Ltd 二次電池用非水電解液
JP2003123834A (ja) * 2001-10-17 2003-04-25 Nec Tokin Corp 電解液、並びにこれを用いた電気化学セル
JP2009512148A (ja) * 2005-10-10 2009-03-19 ゾルファイ フルーオル ゲゼルシャフト ミット ベシュレンクテル ハフツング リチウムイオン電池用のフッ素化添加剤
JP2008027833A (ja) * 2006-07-25 2008-02-07 Sanyo Electric Co Ltd 非水電解質二次電池
JP2008218381A (ja) * 2007-02-05 2008-09-18 Sony Corp 非水電解液電池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
D.KAM ET AL.: "Studies on film formation on cathodes using pyrazole derivatives as electrolyte additives in the Li-ion battery", ELECTROCHEMISTRY COMMUNICATIONS, vol. 11, 2009, pages 1657 - 1660 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014123074A1 (fr) * 2013-02-05 2014-08-14 富士フイルム株式会社 Électrolyte pour pile secondaire non aqueuse, pile secondaire non aqueuse et additif pour solution électrolytique
JP2014154247A (ja) * 2013-02-05 2014-08-25 Fujifilm Corp 非水二次電池用電解液および非水二次電池、電解液用添加剤
US10683293B2 (en) 2014-08-04 2020-06-16 Nuevolution A/S Optionally fused heterocyclyl-substituted derivatives of pyrimidine useful for the treatment of inflammatory, metabolic, oncologic and autoimmune diseases
US10689383B2 (en) 2014-08-04 2020-06-23 Nuevolution A/S Optionally fused heterocyclyl-substituted derivatives of pyrimidine useful for the treatment of inflammatory, metabolic, oncologic and autoimmune diseases
US11254681B2 (en) 2014-08-04 2022-02-22 Nuevolution A/S Optionally fused heterocyclyl-substituted derivatives of pyrimidine useful for the treatment of inflammatory, metabolic, oncologic and autoimmune diseases
WO2020262670A1 (fr) 2019-06-28 2020-12-30 旭化成株式会社 Solution d'électrolyte non aqueuse et batterie secondaire non aqueuse
KR20210011441A (ko) 2019-06-28 2021-02-01 아사히 가세이 가부시키가이샤 비수계 전해액 및 비수계 이차 전지
US11447479B2 (en) 2019-12-20 2022-09-20 Nuevolution A/S Compounds active towards nuclear receptors
US11613532B2 (en) 2020-03-31 2023-03-28 Nuevolution A/S Compounds active towards nuclear receptors
US11780843B2 (en) 2020-03-31 2023-10-10 Nuevolution A/S Compounds active towards nuclear receptors

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