WO2011025016A1 - 非水系電解液及びそれを用いた非水系電解液電池 - Google Patents
非水系電解液及びそれを用いた非水系電解液電池 Download PDFInfo
- Publication number
- WO2011025016A1 WO2011025016A1 PCT/JP2010/064752 JP2010064752W WO2011025016A1 WO 2011025016 A1 WO2011025016 A1 WO 2011025016A1 JP 2010064752 W JP2010064752 W JP 2010064752W WO 2011025016 A1 WO2011025016 A1 WO 2011025016A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbonate
- group
- sulfone
- aqueous electrolyte
- substituted
- Prior art date
Links
Classifications
-
- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
-
- 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 and a non-aqueous electrolyte battery using the same.
- Lithium secondary batteries have the advantages of high energy density and less self-discharge. Therefore, in recent years, it has been widely used as a power source for consumer mobile devices such as mobile phones, notebook computers and PDAs.
- An ordinary electrolyte solution for a lithium secondary battery has a lithium salt as a supporting electrolyte and a nonaqueous solvent as main components.
- the non-aqueous solvent used is required to have a high dielectric constant in order to dissociate the lithium salt, to exhibit high ionic conductivity in a wide temperature range, and to be stable in the battery.
- lithium secondary batteries have been evaluated for various characteristics such as initial capacity, rate characteristics, cycle characteristics, high temperature storage characteristics, low temperature characteristics, continuous charge characteristics, self-discharge characteristics, and overcharge prevention characteristics, and these characteristics have been improved.
- characteristics such as initial capacity, rate characteristics, cycle characteristics, high temperature storage characteristics, low temperature characteristics, continuous charge characteristics, self-discharge characteristics, and overcharge prevention characteristics, and these characteristics have been improved.
- many methods have been reported so far in which various auxiliary agents are contained in the electrolyte solution in small amounts.
- Patent Document 1 discloses a non-aqueous electrolyte secondary battery using an electrolytic solution containing a phosphate ester compound and an ether or ester compound having a halogen-substituted phenyl group. Specifically, the use of an electrolyte containing trimethyl phosphate (TMP) and 3-fluoroanisole improves self-discharge characteristics when stored at 45 ° C.
- TMP trimethyl phosphate
- 3-fluoroanisole improves self-discharge characteristics when stored at 45 ° C.
- Patent Document 2 describes that aromatic compounds such as 1-acetoxy-2-fluorobenzene, 1-acetoxy-3-fluorobenzene and 1-acetoxy-4-fluorobenzene are effective as an additive for batteries. However, it has not been clarified as to which specific characteristics to improve.
- Patent Document 3 proposes to protect the battery by increasing the internal resistance of the battery by mixing an additive that polymerizes at a battery voltage higher than the maximum operating voltage of the battery in the electrolyte.
- Patent Document 4 discloses an internal electrical disconnection device provided for overcharge protection by mixing an additive that generates gas and pressure by polymerizing in an electrolytic solution at a battery voltage equal to or higher than the maximum operating voltage of the battery. It has been proposed to operate reliably.
- aromatic compounds such as biphenyl, thiophene, and furan, are disclosed as those additives.
- Patent Document 5 discloses a non-aqueous system in which phenylcyclohexane is added in a range of 0.1 to 20 parts by weight in a non-aqueous electrolyte solution in order to suppress deterioration of battery characteristics when biphenyl or thiophene is used.
- a non-aqueous electrolyte secondary battery system including an electrolyte secondary battery and a charge control system that senses an increase in battery temperature and disconnects a charging circuit has been proposed.
- Patent Document 6 in order to improve the cycle characteristics of a non-aqueous electrolyte secondary battery including a negative electrode active material having at least one atom selected from the group consisting of Si atom, Sn atom and Pb atom, non-aqueous electrolysis It has been proposed to include a carbonate having at least one of an unsaturated bond and a halogen atom in the liquid and a chain compound having a sulfur-containing functional group represented by a specific structure.
- Japanese Unexamined Patent Publication No. 2003-282055 Japan Special Table 2009-512418 Japanese Unexamined Patent Publication No. 9-106835 Japanese Laid-Open Patent Publication No. 9-171840 Japanese Unexamined Patent Publication No. 2002-50398 Japanese Unexamined Patent Publication No. 2007-317654
- the present invention was devised in view of the above problems, and provides a non-aqueous electrolyte solution and a non-aqueous electrolyte battery with improved overcharge characteristics and improved storage characteristics and high-temperature continuous charge characteristics. Objective.
- the gist of the present invention is as follows. 1.
- a non-aqueous electrolyte solution comprising a lithium salt and a non-aqueous organic solvent, wherein the non-aqueous organic solvent comprises at least one selected from the group consisting of a saturated cyclic carbonate, a chain carbonate and an aliphatic carboxylic acid ester in a total ratio of 90
- the fluorine-containing aromatic ester compound represented by the following general formula (1) is contained in an amount of 0.01 to 10% by weight based on the total weight of the non-aqueous electrolyte solution.
- Non-aqueous electrolyte Non-aqueous electrolyte.
- R 1 is a hydrocarbon group having 1 to 12 carbon atoms and may be substituted with a fluorine atom.
- X is a fluorine atom or a fluorine-substituted alkyl group having 1 to 12 carbon atoms, and n is an integer of 1 to 4.
- 2. The non-aqueous electrolyte solution according to item 1, wherein the saturated cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, monofluoroethylene carbonate, and difluoroethylene carbonate. 3. 3.
- the non-aqueous electrolyte according to item 1 or 2 wherein the chain carbonate is at least one selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, and ethyl propyl carbonate. 4).
- the chain carbonate is at least one selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, and ethyl propyl carbonate. 4).
- the aliphatic carboxylic acid ester is at least one selected from the group of compounds represented by the following general formula (2).
- R 2 is an alkyl group having 1 to 4 carbon atoms and may be substituted with a fluorine atom.
- R 3 is an alkyl group having 1 to 4 carbon atoms and may be substituted with a fluorine atom.
- at least one selected from the group consisting of unsaturated cyclic carbonate, monofluorophosphate, difluorophosphate, sultone and sulfite is contained in an amount of 0.01 to 10% by weight based on the total weight of the non-aqueous electrolyte. 5.
- the nonaqueous electrolytic solution according to any one of items 1 to 4 above, wherein 6).
- a non-aqueous electrolyte battery comprising a negative electrode and a positive electrode capable of inserting and extracting lithium ions, and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution is the non-aqueous electrolyte solution according to any one of the preceding items 1 to 5.
- R 1 represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a fluorine atom
- R 2 to R 6 each independently represents a hydrogen atom, a fluorine atom, a fluorine atom, Represents an alkyl group having 1 to 12 carbon atoms which may be substituted with an atom; However, at least one of R 2 to R 6 represents an alkyl group having 2 or more carbon atoms which may be substituted with a fluorine atom.
- n represents an integer of 0 or 1. However, when n is 1, at least one of R 2 to R 6 represents an alkyl group having 5 or more carbon atoms which may be substituted with a fluorine atom. ] 8).
- R 1 represents a group selected from the group consisting of a methyl group, an ethyl group, a vinyl group, a phenyl group, and a trifluoromethyl group
- R 2 to R 6 are each independently a hydrogen atom.
- the non-aqueous electrolyte according to item 7 above which represents an alkyl group having 2 to 6 carbon atoms which may be substituted with a fluorine atom.
- the non-aqueous electrolysis according to 7 or 8 wherein in general formula (3), at least one of R 2 to R 6 represents an alkyl group having 5 or more carbon atoms which may be substituted with a fluorine atom. liquid. 10. 10.
- the non-aqueous system according to any one of 7 to 9 above, wherein the compound represented by the general formula (3) is contained in an amount of 0.001 to 10% by mass with respect to the total weight of the non-aqueous electrolyte solution.
- Electrolytic solution. 11 Further comprising at least one compound selected from the group consisting of a cyclic carbonate compound having a carbon-carbon unsaturated bond, a cyclic carbonate compound having a fluorine atom, a monofluorophosphate and a difluorophosphate, The non-aqueous electrolyte solution according to any one of 7 to 10.
- a non-aqueous electrolyte battery comprising a negative electrode and a positive electrode capable of inserting and extracting lithium ions, and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution is the non-aqueous electrolyte solution according to any one of items 7 to 11 above.
- the overcharge characteristics when used in a lithium secondary battery, the overcharge characteristics can be greatly improved, and the storage characteristics and the continuous charge characteristics can be improved.
- An excellent nonaqueous electrolyte battery can be provided.
- the non-aqueous electrolyte battery of the present invention includes a non-aqueous electrolyte, a positive electrode, and a negative electrode. Moreover, the non-aqueous electrolyte battery of the present invention may include other components.
- non-aqueous electrolyte in the present invention is a non-aqueous electrolyte containing a lithium salt and a non-aqueous organic solvent, and the non-aqueous organic solvent is a saturated cyclic carbonate.
- a fluorine-substituted aromatic ester compound represented by the following general formula (1) containing at least one selected from the group consisting of a chain carbonate and an aliphatic carboxylic acid ester in a total ratio of more than 90% by volume.
- a non-aqueous electrolyte solution containing 0.01 to 10% by weight of “the fluorine-substituted aromatic ester compound in the present invention” as appropriate) based on the weight of the non-aqueous electrolyte solution.
- R 1 is a hydrocarbon group having 1 to 12 carbon atoms and may be substituted with a fluorine atom.
- X is a fluorine atom or a fluorine-substituted alkyl group having 1 to 12 carbon atoms, and n is an integer of 1 to 4.
- R 1 is a hydrocarbon group and may be substituted with fluorine.
- preferred hydrocarbon groups for R 1 include alkyl groups, aryl groups, alkenyl groups, and aralkyl groups. Of these, an alkyl group and an aryl group are preferable, and an alkyl group is more preferable.
- R 1 is an alkyl group
- the alkyl group usually has 1 to 12 carbon atoms, preferably 1 to 8, more preferably 1 to 4, particularly preferably 1 to 2, and most preferably 1.
- alkyl group preferable as R 1 examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group.
- a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable
- a methyl group and an ethyl group are more preferable
- a methyl group is most preferable.
- R 1 is an alkenyl group
- the carbon number of the alkenyl group is usually preferably 2 to 12, more preferably 2 to 8, still more preferably 2 to 4, particularly preferably 2 to 3, and most preferably 2.
- preferred alkenyl groups for R 1 include vinyl, isopropenyl and allyl groups. Among these, a vinyl group is more preferable.
- R 1 is an aryl group
- the aryl group preferably has 6 to 12 carbon atoms.
- Specific examples include phenyl group, tolyl group, ethylphenyl group, dimethylphenyl group, isopropyl group, t-butylphenyl group, t-amylphenyl group, cyclohexylphenyl group, ⁇ -naphthyl group and ⁇ -naphthyl group. It is done.
- a phenyl group, a t-butylphenyl group, and a t-amylphenyl group are more preferable.
- R 1 is an aralkyl group
- the aralkyl group preferably has 7 to 12 carbon atoms. Specific examples include benzyl group, ⁇ -phenethyl group and ⁇ -phenethyl group. Among these, a benzyl group is more preferable.
- R 1 some or all of the hydrogen atoms constituting the hydrocarbon group may be substituted with fluorine atoms. Specific examples include monofluoromethyl group, difluoromethyl group, trimethylfluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, monofluorophenyl group and pentafluorophenyl group.
- X is a fluorine atom or a fluorine-substituted alkyl group having 1 to 12 carbon atoms, preferably a fluorine atom.
- the carbon number of the alkyl group is usually preferably 1 to 12, more preferably 1 to 8, still more preferably 1 to 4, particularly preferably 1 to 2, and most preferably 1.
- preferred fluorine-substituted alkyl groups as X include monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, perfluorobutyl group, perfluoro An octyl group, a perfluoro dodecyl group, etc. are mentioned.
- a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a pentafluoroethyl group are preferable, and a monofluoromethyl group, a difluoromethyl group, and a trifluoromethyl group are more preferable.
- n is an integer of 1 to 4, preferably 1 to 3, and more preferably 1.
- n number is larger than 4, it becomes expensive and difficult to obtain, and tends to be difficult to use in a lithium secondary battery.
- the molecular weight of the fluorine-substituted aromatic ester compound is preferably 150 or more. Further, it is usually preferably 400 or less, and more preferably 250 or less. By setting it to be equal to or lower than the upper limit of the range, the solubility in the non-aqueous electrolyte is sufficient, and the effects of the present invention can be sufficiently exhibited.
- fluorine-substituted aromatic ester compounds include fluorine-substituted phenyl acetates, fluorine-substituted alkylphenyl acetates, fluorine-substituted phenylpropionates, fluorine-substituted alkylphenylpropionates, fluorine-substituted phenylbutyrates, and fluorine-substituted phenylbenzoates.
- fluorine-substituted phenyl acetates fluorine-substituted alkylphenyl acetates, fluorine-substituted phenylpropionates and fluorine-substituted phenyl trifluoroacetates are preferable, and fluorine-substituted phenyl acetates are more preferable.
- fluorine-substituted phenyl acetates examples include 2-fluorophenyl acetate, 3-fluorophenyl acetate, 4-fluorophenyl acetate, 2,3-difluorophenyl acetate, 2,4-difluorophenyl acetate, and 2,5-difluorophenyl.
- fluorine-substituted alkylphenyl acetates examples include 2-trifluoromethyl phenyl acetate, 3-trifluoromethyl phenyl acetate, 4-trifluoromethyl phenyl acetate, 2,3-bis (trifluoromethyl) phenyl acetate, 2, 4-bis (trifluoromethyl) phenyl acetate, 2,5-bis (trifluoromethyl) phenyl acetate, 2,6-bis (trifluoromethyl) phenyl acetate, 3,4-bis (trifluoromethyl) phenyl acetate and 3,5-bis (trifluoromethyl) phenyl acetate and the like.
- 2-trifluoromethylphenyl acetate 2-trifluoromethylphenyl acetate
- 3-trifluoromethylphenyl acetate 2-trifluoromethylphenyl acetate
- 4-trifluoromethylphenyl acetate 2-trifluoromethylphenyl acetate
- fluorine-substituted phenylpropionates examples include 2-fluorophenylpropionate, 3-fluorophenylpropionate, 4-fluorophenylpropionate, 2,3-difluorophenylpropionate, 2,4-difluorophenylpropionate, 2,5-difluorophenylpropionate, 2,6-difluorophenylpropionate, 3,4-difluorophenylpropionate, 3,5-difluorophenylpropionate, 2,3,4-trifluorophenylpropionate, 2, 3,5-trifluorophenylpropionate, 2,3,6-trifluorophenylpropionate, 2,4,5-trifluorophenylpropionate, 2,4,6-trifluorophenylpropionate, 3,4, 5- Li fluoro-phenylpropionate and 2,3,4,5-tetrafluoro-phenylpropionate, and the like.
- fluorine-substituted alkylphenylpropionates examples include 2-trifluoromethylphenylpropionate, 3-trifluoromethylphenylpropionate, 4-trifluoromethylphenylpropionate, and 2,3-bis (trifluoromethyl) phenylpropionate.
- 2,4-bis (trifluoromethyl) phenylpropionate 2,5-bis (trifluoromethyl) phenylpropionate
- 2,6-bis (trifluoromethyl) phenylpropionate 3,4-bis (Trifluoromethyl) phenylpropionate, 3,5-bis (trifluoromethyl) phenylpropionate and the like.
- fluorine-substituted phenyl butyrate examples include 2-fluorophenyl butyrate, 3-fluorophenyl butyrate, 4-fluorophenyl butyrate, 2,3-difluorophenyl butyrate, 2,4-difluorophenyl butyrate, 2,5-difluorophenyl butyrate, 2,6-difluorophenyl butyrate, 3,4-difluorophenyl butyrate, 3,5-difluorophenyl butyrate, 2,3,4-trifluorophenyl butyrate, 2, 3,5-trifluorophenyl butyrate, 2,3,6-trifluorophenyl butyrate, 2,4,5-trifluorophenyl butyrate, 2,4,6-trifluorophenyl butyrate, 3,4, 5-trifluorophenylbutyrate and 2,3,4,5-tetraph Oro phenylbutyrate, and the like.
- fluorine-substituted phenyl benzoates examples include 2-fluorophenyl benzoate, 3-fluorophenyl benzoate, 4-fluorophenyl benzoate, 2,3-difluorophenyl benzoate, 2,4-difluorophenyl benzoate, and 2,5-difluorophenyl.
- fluorine-substituted phenyl acrylates examples include 2-fluorophenyl acrylate, 3-fluorophenyl acrylate, 4-fluorophenyl acrylate, 2,3-difluorophenyl acrylate, 2,4-difluorophenyl acrylate, and 2,5-difluorophenyl.
- fluorine-substituted phenyl difluoroacetates examples include 2-fluorophenyl difluoroacetate, 3-fluorophenyl difluoroacetate, 4-fluorophenyl difluoroacetate, 2,3-difluorophenyl difluoroacetate, 2,4-difluorophenyl difluoroacetate, 2,5-difluorophenyl difluoroacetate, 2,6-difluorophenyl difluoroacetate, 3,4-difluorophenyl difluoroacetate, 3,5-difluorophenyl difluoroacetate, 2,3,4-trifluorophenyl difluoroacetate, 2, 3,5-trifluorophenyl difluoroacetate, 2,3,6-trifluorophenyl difluoroacetate, 2,4,5-trifluoropheny Difluoroacetate, 2,4,6-trifluorophenyl difluor
- fluorine-substituted phenyl trifluoroacetates examples include 2-fluorophenyl trifluoroacetate, 3-fluorophenyl trifluoroacetate, 4-fluorophenyl trifluoroacetate, 2,3-difluorophenyl trifluoroacetate, 2,4- Difluorophenyl trifluoroacetate, 2,5-difluorophenyl trifluoroacetate, 2,6-difluorophenyl trifluoroacetate, 3,4-difluorophenyl trifluoroacetate, 3,5-difluorophenyl trifluoroacetate, 2,3 4-trifluorophenyl trifluoroacetate, 2,3,5-trifluorophenyl trifluoroacetate, 2,3,6-trifluorophenyl trifluoroacetate, 2, , 5-trifluorophenyl trifluoroacetate, 2,4,6-trifluorophenyl triflu
- fluorine-substituted phenyl pentafluoropropionates examples include 2-fluorophenyl pentafluoropropionate, 3-fluorophenyl pentafluoropropionate, 4-fluorophenyl pentafluoropropionate, and 2,3-difluorophenyl.
- Pentafluoropropionate 2,4-difluorophenyl pentafluoropropionate, 2,5-difluorophenyl pentafluoropropionate, 2,6-difluorophenyl pentafluoropropionate, 3,4-difluorophenyl pentafluoro Propionate, 3,5-difluorophenyl pentafluoropropionate, 2,3,4-trifluorophenyl pentafluoropropionate, 2,3,5-trifluorophenyl pentafluoropro Onate, 2,3,6-trifluorophenyl pentafluoropropionate, 2,4,5-trifluorophenyl pentafluoropropionate, 2,4,6-trifluorophenyl pentafluoropropionate, 3,4 , 5-trifluorophenyl pentafluoropropionate and 2,3,4,5-tetrafluorophenyl pent
- fluorine-substituted aromatic ester compound described above may be used alone or in combination of two or more in any combination and ratio.
- the addition amount of the fluorine-substituted aromatic ester compound is usually preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and more preferably 0.3% by weight or more based on the total weight of the non-aqueous electrolyte solution. More preferred is 1% by weight or more, most preferred is 2% by weight or more. Further, it is usually preferably 10% by weight or less, more preferably 7% by weight or less, further preferably 5% by weight or less, and particularly preferably 4% by weight or less.
- the fluorine-substituted aromatic ester compound By making the addition amount of the fluorine-substituted aromatic ester compound to the non-aqueous electrolyte below the above upper limit, it exhibits excellent high-temperature storage characteristics, suppresses gas generation during normal battery use, and improves capacity maintenance rate. be able to. Moreover, the effect of this invention can fully be exhibited by making addition amount more than the said minimum.
- the saturated cyclic carbonate used in the present invention is a cyclic carbonate having no carbon-carbon unsaturated bond, and can be arbitrarily selected as long as the effects of the present invention are not significantly impaired.
- saturated cyclic carbonate examples include carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethylethylene carbonate, diethylethylene carbonate, monopropylethylene carbonate, dipropylethylene carbonate, phenylethylene carbonate, diphenylethylene carbonate, and catechol carbonate; Monofluoroethylene carbonate, difluoroethylene carbonate, trifluoroethylene carbonate, tetrafluoroethylene carbonate, monofluoromethyl ethylene carbonate, trifluoromethyl ethylene carbonate, monochloroethylene carbonate, dichloroethylene carbonate, trichloroethylene carbonate, tetrachloro Ji Ren carbonate, halogen substituted carbonates such as monochloromethyl methyl ethylene carbonate and trichloromethyl ethylene carbonate.
- carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethylethylene carbonate, diethylethylene carbonate, monopropylethylene carbonate, dipropylethylene
- At least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, monofluoroethylene carbonate and difluoroethylene carbonate is preferable. Furthermore, at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and monofluoroethylene carbonate is particularly preferable in order to improve storage characteristics.
- the chain carbonate used in the present invention can be arbitrarily selected as long as the effects of the present invention are not significantly impaired.
- carbonates such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propyl methyl carbonate, dipropyl carbonate, methyl phenyl carbonate, ethyl phenyl carbonate, diphenyl carbonate; bis (trifluoromethyl) carbonate, methyl trifluoromethyl carbonate, bis Halogen-substituted carbonates such as (monofluoroethyl) carbonate, methyl monofluoroethyl carbonate, bis (trifluoroethyl) carbonate and methyl trifluoroethyl carbonate.
- it is preferably at least one selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, and ethyl propyl carbonate, and more preferably at least one of dimethyl carbonate and ethyl methyl carbonate. It is particularly preferred.
- the aliphatic carboxylic acid ester used in the present invention can be arbitrarily selected as long as the effects of the present invention are not significantly impaired. Among them, it contains at least one selected from the group of compounds represented by the following general formula (2). Is preferred.
- R 2 is an alkyl group having 1 to 4 carbon atoms and may be substituted with a fluorine atom.
- R 3 is an alkyl group having 1 to 4 carbon atoms and may be substituted with a fluorine atom.
- R 2 is an alkyl group and may be substituted with fluorine.
- R 2 usually has 1 to 4 carbon atoms, preferably 1 to 3, more preferably 1 to 2, and most preferably 2. If the number of carbon atoms exceeds 4, the viscosity of the non-aqueous electrolyte increases, and lithium ion migration is hindered and performance may deteriorate.
- R 2 is an alkyl group
- R 2 is an alkyl group
- R 2 is an alkyl group
- a methyl group, an ethyl group, and a propyl group are more preferable
- a methyl group and an ethyl group are more preferable
- an ethyl group is most preferable.
- R 2 is a fluorine-substituted alkyl group
- Preferred examples when R 2 is a fluorine-substituted alkyl group include monofluoromethyl group, difluoromethyl group, trimethylfluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group and hepta Examples include a fluoropropyl group.
- a monofluoromethyl group, a difluoromethyl group, a trimethylfluoromethyl group, a 2,2,2-trifluoroethyl group and a pentafluoroethyl group are preferable, and a 2,2,2-trifluoroethyl group and a pentafluoroethyl group are preferable. Is most preferred.
- R 3 is an alkyl group, which may be substituted with fluorine.
- R 3 usually has 1 to 4 carbon atoms, preferably 1 to 3, and more preferably 1 to 2. If the number of carbon atoms exceeds 4, the viscosity of the non-aqueous electrolyte increases, and lithium ion migration is hindered and performance may deteriorate.
- R 3 is an alkyl group
- R 3 is an alkyl group
- a methyl group, an ethyl group, and a propyl group are more preferable, and a methyl group and an ethyl group are more preferable.
- R 3 is a fluorine-substituted alkyl group
- examples include a fluoropropyl group.
- a monofluoromethyl group, a difluoromethyl group, a trimethylfluoromethyl group, a 2,2,2-trifluoroethyl group, and a pentafluoroethyl group are preferable.
- Specific examples of the compound represented by the general formula (2) include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, and isobutyric acid.
- Aliphatic carboxylic acid esters such as methyl, ethyl isobutyrate and propyl isobutyrate; methyl monofluoroacetate, methyl difluoroacetate, methyl trifluoroacetate, ethyl monofluoroacetate, ethyl difluoroacetate, ethyl trifluoroacetate, trifluoroethyl acetate
- fluorine-substituted aliphatic carboxylic acid esters such as trifluoroethyl propionate, trifluoroethyl butyrate and trifluoroethyl isobutyrate.
- methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl isobutyrate and ethyl isobutyrate are preferred, methyl propionate, ethyl propionate, methyl butyrate and ethyl butyrate are more preferred, Most preferred are methyl propionate and ethyl propionate.
- the non-aqueous electrolyte solution of the present invention contains a non-aqueous organic solvent containing at least one selected from the group consisting of saturated cyclic carbonates, chain carbonates and aliphatic carboxylic acid esters in a total ratio exceeding 90% by volume.
- a non-aqueous organic solvent containing at least one selected from the group consisting of saturated cyclic carbonates, chain carbonates and aliphatic carboxylic acid esters in a total ratio exceeding 90% by volume.
- the said fluorine-substituted aromatic ester compound and the film formation agent and auxiliary agent mentioned later shall not be included in the sum total of the said non-aqueous organic solvent.
- the total ratio is usually preferably 91% or more, more preferably 93% or more, still more preferably 95% or more, still more preferably 97% or more, and 99% or more. Particularly preferred is 100%, and most preferred is 100%.
- a saturated cyclic carbonate and a chain carbonate in combination, or to use a saturated cyclic carbonate and an aliphatic carboxylic acid ester in combination.
- the composition ratio (capacity ratio) of the saturated cyclic carbonate and the chain carbonate is usually 5:95 to 50 from the viewpoint of achieving both conductivity and liquid injection property to the electrode. : 50 is preferred, 10:90 to 40:60 is more preferred, and 15:85 to 35:55 is even more preferred.
- the composition ratio (volume ratio) of the saturated cyclic carbonate and the aliphatic carboxylic acid ester is usually preferably 5:95 to 50:50, and 10:90 to 45. : 55 is more preferable, and 15:85 to 40:60 is more preferable.
- the non-aqueous electrolyte of the present invention may contain a solvent other than the above-mentioned cyclic carbonate and chain carbonate having no carbon-carbon unsaturated bond within a range of less than 10% by volume.
- the solvent examples include ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -valerolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, , 3-dioxolane, 4-methyl-1,3-dioxolane, N-methylpyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, sulfolane, dimethyl sulfoxide, acetonitrile, trimethyl phosphate, triethyl phosphate, fluorobenzene, 2, Mention may be made of at least one selected from 4-difluorobenzene and trifluoromethylbenzene.
- the lithium salt is used as an electrolyte, and the kind thereof is not particularly limited, and either an inorganic lithium salt or an organic lithium salt may be used.
- inorganic lithium salt examples include inorganic fluoride salts such as LiPF 6 , LiAsF 6 , LiBF 4 and LiSbF 6 ; inorganic chloride salts such as LiAlCl 4 ; perhalogenates such as LiClO 4 , LiBrO 4 and LiIO 4. Is mentioned.
- organic lithium salt examples include perfluoroalkane sulfonates such as CF 3 SO 3 Li and C 4 F 9 SO 3 Li; perfluoroalkane carboxylates such as CF 3 COOLi; (CF 3 CO) 2 Perfluoroalkanecarbonimide salts such as NLi; perfluoroalkanesulfonimide salts such as (CF 3 SO 2 ) 2 NLi and (C 2 F 5 SO 2 ) 2 NLi; lithium bis (oxalato) borate (abbreviation: LiBOB) and Examples thereof include oxalate salts such as lithium difluorooxalatoborate (abbreviation: LiFOB).
- perfluoroalkane sulfonates such as CF 3 SO 3 Li and C 4 F 9 SO 3 Li
- perfluoroalkane carboxylates such as CF 3 COOLi
- Perfluoroalkanecarbonimide salts such as
- LiPF 6 , LiBF 4 , CF 3 SO 3 Li and (CF 3 SO 2 ) 2 NLi are preferable because they are easily soluble in non-aqueous organic solvents and exhibit a high degree of dissociation.
- lithium salt may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
- the combined use of LiPF 6 and LiBF 4 and the combined use of LiPF 6 and (CF 3 SO 2 ) 2 NLi are preferable because they are effective in improving the continuous charge characteristics.
- the concentration of the lithium salt in the non-aqueous electrolyte solution is arbitrary as long as the effects of the present invention are not significantly impaired, but it is usually preferably 0.5 mol / L or more, more preferably 0.75 mol / L or more with respect to the non-aqueous electrolyte solution. Is more preferable. Moreover, 2 mol / L or less is preferable normally and 1.75 mol / L or less is more preferable.
- the concentration of the lithium salt By making the concentration of the lithium salt equal to or higher than the lower limit, the electrical conductivity of the non-aqueous electrolyte is improved. On the other hand, by making the concentration of the lithium salt not more than the above upper limit, the increase in the viscosity of the non-aqueous electrolyte solution is suppressed, the electrical conductivity is prevented from lowering, the precipitation at low temperature is suppressed, and the lithium secondary battery Performance can be improved.
- the nonaqueous electrolytic solution of the present invention is further selected from unsaturated cyclic carbonate, monofluorophosphate, difluorophosphate, sultone and sulfite for the purpose of forming a film on the negative electrode and improving battery characteristics.
- it contains seeds.
- the unsaturated cyclic carbonate is not particularly limited as long as it is a cyclic carbonate having a carbon-carbon unsaturated bond, and any one can be used.
- vinylene carbonate derivatives such as vinylene carbonate, methyl vinylene carbonate and 1,2-dimethyl vinylene carbonate
- vinyl ethylene carbonate derivatives such as vinyl ethylene carbonate and 1,2-divinyl ethylene carbonate are preferable.
- vinylene carbonate and vinyl ethylene carbonate are more preferable.
- unsaturated cyclic carbonate may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
- the carbon number of the unsaturated cyclic carbonate is usually preferably 3 or more. Moreover, 20 or less is preferable normally and 15 or less is more preferable. By setting the carbon number to be equal to or lower than the upper limit of the range, sufficient solubility in the electrolytic solution is exhibited.
- the molecular weight of the unsaturated cyclic carbonate is usually preferably 80 or more. Moreover, 250 or less is preferable normally and 150 or less is more preferable. By setting the molecular weight to be equal to or lower than the upper limit, sufficient solubility in the electrolytic solution can be exhibited, and the effect of the present invention of improving high-temperature storage characteristics can be sufficiently exhibited.
- the concentration of the unsaturated cyclic carbonate is usually preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and further preferably 0.3% by weight or more with respect to the entire electrolytic solution. Further, it is usually preferably 10% by weight or less, more preferably 7% by weight or less, further preferably 5% by weight or less, and particularly preferably 3% by weight or less.
- the concentration of the unsaturated cyclic carbonate By setting the concentration of the unsaturated cyclic carbonate below the upper limit, the high-temperature storage characteristics are excellent, the amount of gas generated when the battery is used can be suppressed, and the capacity retention rate can be improved. Moreover, the effect of this invention can fully be exhibited by making the density
- lithium monofluorophosphate sodium monofluorophosphate, lithium monofluorophosphate and potassium monofluorophosphate are preferable, and lithium monofluorophosphate is particularly preferable.
- difluorophosphate sodium difluorophosphate, lithium difluorophosphate and potassium difluorophosphate are preferable, and lithium difluorophosphate is particularly preferable.
- the concentration of monofluorophosphate and difluorophosphate is generally preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and more preferably 0.2% by weight or more in total with respect to the whole non-aqueous electrolyte. Is more preferable. Further, it is usually preferably 10% by weight or less, more preferably 3% by weight or less, further preferably 2% by weight or less, and particularly preferably 1% by weight or less.
- the concentrations of monofluorophosphate and difluorophosphate By setting the concentrations of monofluorophosphate and difluorophosphate to the upper limit or less, the reaction resistance of the negative electrode can be suppressed and the capacity can be improved. Moreover, the effect of this invention can fully be exhibited by making the density
- 1,3-propane sultone, 1,3-propene sultone and 1,4-butane sultone are preferable, and 1,3-propane sultone and 1,3-propene sultone are particularly preferable.
- the total concentration of sultone is generally preferably 0.01% by weight or more, more preferably 0.2% by weight or more, and even more preferably 0.5% by weight or more based on the total electrolyte solution. Further, it is usually preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 3% by weight or less, and particularly preferably 2% by weight or less.
- the concentration of sultone By setting the concentration of sultone below the upper limit, the reaction resistance of the negative electrode can be suppressed and the capacity can be improved. Moreover, the effect of this invention can fully be exhibited by making the density
- sulfite dimethyl sulfite, ethyl methyl sulfite, diethyl sulfite, ethylene sulfite and propylene sulfite are preferable, and ethylene sulfite and propylene sulfite are particularly preferable.
- the concentration of the sulfite is generally preferably 0.01% by weight or more, more preferably 0.2% by weight or more, and further preferably 0.5% by weight or more based on the total amount of the electrolytic solution. Further, it is usually preferably 10% by weight or less, more preferably 5% by weight or less, further preferably 3% by weight or less, and particularly preferably 2% by weight or less.
- the concentration of sulfite By keeping the concentration of sulfite below the upper limit, the high temperature storage characteristics can be improved. Moreover, the effect of this invention can fully be exhibited by making the density
- the non-aqueous electrolyte solution of the present invention may contain other auxiliary agents for the purpose of improving the wettability, overcharge characteristics, etc. of the non-aqueous electrolyte solution as long as the effects of the present invention are not significantly impaired.
- auxiliary agent examples include acid anhydrides such as maleic anhydride, succinic anhydride, and glutaric anhydride; diphenyl disulfide, dimethyl sulfone, divinyl sulfone, 1,4-butanediol dimethanesulfonate, methyl methanesulfonate, and methanesulfone.
- acid anhydrides such as maleic anhydride, succinic anhydride, and glutaric anhydride
- diphenyl disulfide dimethyl sulfone, divinyl sulfone, 1,4-butanediol dimethanesulfonate, methyl methanesulfonate, and methanesulfone.
- Sulfur-containing compounds such as acid-2-propynyl; aromatic compounds such as t-butylbenzene, t-amylbenzene, biphenyl, o-terphenyl, 4-fluorobiphenyl, cyclohexylbenzene, diphenyl ether and 2,4-difluoroanisole; What substituted this aromatic compound with the fluorine atom etc. are mentioned.
- one type of auxiliary agent may be used alone, or two or more types may be used in any combination and ratio.
- the concentration of the auxiliary agent in the non-aqueous electrolyte is usually preferably 0.01% by weight or more, and more preferably 0.05% by weight or more. Moreover, 5 weight% or less is preferable normally and 3 weight% or less is more preferable.
- Non-aqueous electrolyte state The nonaqueous electrolytic solution of the present invention usually exists in a liquid state when used in the lithium secondary battery of the present invention. For example, it may be gelled with a polymer to form a semi-solid electrolyte.
- the polymer used for the gelation is arbitrary, and examples thereof include polyvinylidene fluoride, a copolymer of polyvinylidene fluoride and hexafluoropropylene, polyethylene oxide, polyacrylate, and polymethacrylate.
- polymer used for gelation may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
- the ratio of the non-aqueous electrolyte in the semi-solid electrolyte is arbitrary as long as the effects of the present invention are not significantly impaired.
- the ratio of the non-aqueous electrolyte to the total amount of the semisolid electrolyte is usually preferably 30% by weight or more, more preferably 50% by weight or more, and further preferably 75% by weight or more. Moreover, 99.95 weight% or less is preferable normally, 99 weight% or less is more preferable, More preferably, 98 weight% or less is further more preferable.
- the ratio of the non-aqueous electrolyte is set to the upper limit or less, the electrolyte can be easily retained and the liquid leakage is less likely to occur. Moreover, sufficient charging / discharging efficiency and capacity
- capacitance can be obtained by making the ratio of non-aqueous electrolyte solution more than the said minimum.
- Nonaqueous electrolyte production method The method for producing the non-aqueous electrolyte solution of the present invention is not particularly limited.
- a lithium salt is added to a non-aqueous organic solvent in which the total proportion of cyclic carbonate and / or chain carbonate having no carbon-carbon unsaturated bond is 95% by volume or more, and further the fluorine-substituted aromatic in the present invention.
- a group ester compound can be prepared by adding 0.01 to 10% by weight with respect to the weight of the non-aqueous electrolyte.
- each raw material of the non-aqueous electrolyte solution that is, the lithium salt, the non-aqueous solvent, the fluorine-substituted aromatic ester compound, and other auxiliary agents be dehydrated in advance.
- the degree of dehydration it is preferable to dehydrate until the water content is usually 50 ppm or less, preferably 30 ppm or less.
- ppm means a ratio based on weight.
- Dehydration means is not particularly limited.
- the object to be dehydrated is a liquid such as a non-aqueous solvent, a molecular sieve or the like may be used.
- the object to be dehydrated is a solid such as an electrolyte, it may be dried at a temperature lower than the temperature at which decomposition occurs.
- a part of the fluorine-substituted aromatic ester compound contained in the non-aqueous electrolyte of the present invention is reduced during the initial charge of battery production, and a protective film is formed on the negative electrode.
- the protective film has high thermal stability with respect to the carbonate solvent. Therefore, when the non-aqueous organic solvent in the non-aqueous electrolyte is mainly carbonate and / or aliphatic carboxylic acid ester as in the present invention, the storage characteristics of the battery are improved.
- the protective coating is non-aqueous organic. Since it becomes easy to dissolve in the solvent and the solvent decomposition reaction proceeds on the negative electrode, the storage characteristics deteriorate.
- the fluorine-substituted aromatic ester compound of the present invention is decomposed at the positive electrode at an early stage of overcharge to generate hydrogen fluoride and / or an oxidation reactant, and a gas such as carbon dioxide. Is generated.
- the hydrogen fluoride and / or oxidation reactant produced here act as a catalyst to decompose the carbonate solvent and / or the aliphatic carboxylic acid ester solvent to generate carbon dioxide.
- the non-aqueous organic solvent in the non-aqueous electrolyte is mainly a carbonate and / or an aliphatic carboxylic acid ester solvent as in the present invention
- the amount of gas generation is reduced in the initial stage of overcharge (voltage 5 V). Therefore, in a battery equipped with a device that detects the internal pressure and cuts off the current, the current supply can be stopped at a safer stage, so that smoke or fire does not occur.
- the non-aqueous electrolyte of the present invention usually contains an electrolyte and a non-aqueous solvent that dissolves the electrolyte as a main component, similarly to a general non-aqueous electrolyte, and is further represented by the general formula (3). Contains compounds.
- R 1 represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a fluorine atom
- R 2 to R 6 each independently represent a hydrogen atom, a fluorine atom or a fluorine atom.
- at least one of R 2 to R 6 represents an alkyl group having 2 or more carbon atoms which may be substituted with a fluorine atom.
- n represents an integer of 0 or 1. However, when n is 1, at least one of R 2 to R 6 represents an alkyl group having 5 or more carbon atoms which may be substituted with a fluorine atom.
- examples of the hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a fluorine atom represented by R 1 include an alkyl group having 1 to 12 carbon atoms and 2 to 2 carbon atoms. Examples include 12 alkenyl groups, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 12 carbon atoms.
- alkyl group having 1 to 12 carbon atoms examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, and pentyl. Group, cyclopentyl group, cyclohexyl group and the like.
- the carbon number of the alkyl group is 1 to 12, preferably 1 to 6, and more preferably 1 to 4.
- the alkyl group is preferably a chain or cyclic alkyl group, more preferably a chain alkyl group.
- alkenyl group having 2 to 12 carbon atoms examples include a vinyl group and a propenyl group.
- the alkenyl group has 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 4 carbon atoms.
- Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a cyclohexylphenyl group, and a t-butylphenyl group. Of these, a phenyl group, a cyclohexylphenyl group, and a t-butylphenyl group are preferable.
- Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group and a phenethyl group, and among them, a benzyl group is preferable.
- alkyl group, alkenyl group, aryl group and aralkyl group may be substituted with a fluorine atom.
- fluorine-substituted alkyl group examples include fluorinated alkyl groups such as a trifluoromethyl group, a trifluoroethyl group, and a pentafluoroethyl group, a 2-fluorovinyl group, and a 3-fluoro-2-propenyl group. It is done.
- fluorine-substituted aryl group examples include fluorinated aryl groups such as 2-fluorophenyl group, 3-fluorophenyl group, and 4-fluorophenyl group.
- Examples of the fluorine-substituted aralkyl group include a 2-fluorobenzyl group, a 3-fluorobenzyl group, and a 4-fluorobenzyl group.
- R 1 is more preferably a group selected from the group consisting of a methyl group, an ethyl group, a vinyl group, a phenyl group and a trifluoromethyl group, and is selected from the group consisting of a methyl group, an ethyl group and a trifluoromethyl group. More preferably, it is a group.
- examples of the alkyl group having 1 to 12 carbon atoms which may be substituted with a fluorine atom represented by R 2 to R 6 include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, t-amyl group, n-hexyl group, 1,1-dimethylbutyl group, cyclobutyl group, A cyclopentyl group, a cyclohexyl group, a 1-methylcyclohexyl group, a 1-ethylcyclohexyl group and the like can be mentioned. Among these, a linear or cyclic alkyl group having 1 to 6 carbon atoms is preferable.
- fluorine-substituted group examples include a trifluoromethyl group, a trifluoroethyl group, and a pentafluoroethyl group.
- R 2 to R 6 are each independently an alkyl group having 2 to 6 carbon atoms which may be substituted with a hydrogen atom or a fluorine atom.
- R 2 to R 6 when n is 0, at least one of R 2 to R 6 represents an alkyl group having 2 or more carbon atoms, and when n is 1, at least one of R 2 to R 6 is carbon number Represents 5 or more alkyl groups.
- At least one of R 2 to R 6 is preferably an alkyl group having 3 or more carbon atoms, and preferably an alkyl group having 4 or more carbon atoms. More preferably, it is an alkyl group having 5 or more carbon atoms.
- the alkyl group may be substituted with a fluorine atom.
- alkyl group having 4 or more carbon atoms examples include n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, t-amyl group, n-hexyl group, 1,1 -Dimethylbutyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group and the like.
- the alkyl group having 4 or more carbon atoms is preferably a secondary alkyl group or a tertiary alkyl group.
- a sec-butyl group, a t-butyl group, a t-amyl group, a 1,1-dimethylbutyl group, a cyclopentyl group More preferred are a cyclohexyl group, a 1-methylcyclohexyl group and a 1-ethylcyclohexyl group, a t-butyl group, a t-amyl group, a 1,1-dimethylbutyl group, a cyclopentyl group, a cyclohexyl group, a 1-methylcyclohexyl group and a 1-methylcyclohexyl group.
- An ethylcyclohexyl group is more preferable, and a t-amyl group, 1,1-dimethylbutyl group, cyclopentyl group, cyclohexyl group, 1-methylcyclohexyl group and 1-methyl secondary alkyl group or tertiary alkyl group having 5 or more carbon atoms.
- An ethylcyclohexyl group is particularly preferred.
- Specific examples of the compound represented by the general formula (3) include the following compounds.
- Examples of the compound in which R 1 is an alkyl group having 1 to 12 carbon atoms include methanesulfonic acid (2-n-pentylphenyl), methanesulfonic acid (3-n-pentylphenyl), methanesulfonic acid (4-n -Pentylphenyl), methanesulfonic acid (2,4-di-n-pentylphenyl), methanesulfonic acid (3,5-di-n-pentylphenyl), methanesulfonic acid (2-t-amylphenyl), methane Sulfonic acid (3-t-amylphenyl), methanesulfonic acid (4-t-amylphenyl), methanesulfonic acid (2,4-di-t-amylphenyl), methanesulfonic acid (3,5-di-t -Amylphenyl), methanesulfonic acid (2-cyclopenty
- R 1 is an alkenyl group having 2 to 12 carbon atoms
- examples of the compound in which R 1 is an alkenyl group having 2 to 12 carbon atoms include, for example, vinyl sulfonic acid (2-n-pentylphenyl), vinyl sulfonic acid (3-n-pentylphenyl), vinyl sulfonic acid (4-n -Pentylphenyl), vinylsulfonic acid (2,4-di-n-pentylphenyl), vinylsulfonic acid (3,5-di-n-pentylphenyl), vinylsulfonic acid (2-t-amylphenyl), vinyl Sulfonic acid (3-t-amylphenyl), vinylsulfonic acid (4-t-amylphenyl), vinylsulfonic acid (2-cyclopentylphenyl), vinylsulfonic acid (3-cyclopentylphenyl), vinylsulfonic acid (4-cyclopentyl) Phenyl
- R 1 is an aryl group having 6 to 12 carbon atoms
- examples of the compound in which R 1 is an aryl group having 6 to 12 carbon atoms include benzenesulfonic acid (2-n-pentylphenyl), benzenesulfonic acid (3-n-pentylphenyl), and benzenesulfonic acid (4-n -Pentylphenyl), benzenesulfonic acid (2,4-di-n-pentylphenyl), benzenesulfonic acid (3,5-di-n-pentylphenyl), benzenesulfonic acid (2-t-amylphenyl), benzene Sulfonic acid (3-t-amylphenyl), benzenesulfonic acid (4-t-amylphenyl), benzenesulfonic acid (2-cyclopentylphenyl), benzenesulfonic acid (3-cyclopentyl
- R 1 is an aralkyl group having 7 to 12 carbon atoms
- examples of the compound in which R 1 is an aralkyl group having 7 to 12 carbon atoms include benzylsulfonic acid (2-n-pentylphenyl), benzylsulfonic acid (3-n-pentylphenyl), benzylsulfonic acid (4-n -Pentylphenyl), benzylsulfonic acid (2,4-di-n-pentylphenyl), benzylsulfonic acid (3,5-di-n-pentylphenyl), benzylsulfonic acid (2-t-amylphenyl), benzyl Sulfonic acid (3-t-amylphenyl), benzylsulfonic acid (4-t-amylphenyl), benzylsulfonic acid (2-cyclopentylphenyl), benzylsulfonic acid (3-cyclopen
- Examples of the compound in which R 1 is a fluorine-substituted alkyl group having 1 to 12 carbon atoms include, for example, trifluoromethanesulfonic acid (2-n-pentylphenyl), trifluoromethanesulfonic acid (3-n-pentylphenyl), Trifluoromethanesulfonic acid (4-n-pentylphenyl), trifluoromethanesulfonic acid (2,4-di-n-pentylphenyl), trifluoromethanesulfonic acid (3,5-di-n-pentylphenyl), trifluoromethanesulfone Acid (2-t-amylphenyl), trifluoromethanesulfonic acid (3-t-amylphenyl), trifluoromethanesulfonic acid (4-t-amylphenyl), trifluoromethanesulfonic acid (2-cyclopentylphenyl), trifluorome
- Examples of the compound in which R 1 is an alkyl group having 1 to 12 carbon atoms include methyl (2-ethylphenyl) sulfone, methyl (3-ethylphenyl) sulfone, methyl (4-ethylphenyl) sulfone, methyl (2- n-propylphenyl) sulfone, methyl (3-n-propylphenyl) sulfone, methyl (4-n-propylphenyl) sulfone, methyl (2-i-propylphenyl) sulfone, methyl (3-i-propylphenyl) sulfone Methyl (4-i-propylphenyl) sulfone, methyl (2-n-butylphenyl) sulfone, methyl (3-n-butylphenyl) sulfone, methyl (4-n-butylphenyl) sulfone, methyl (2-
- Examples of the compound wherein R 1 is an alkenyl group having 2 to 12 carbon atoms include vinyl (2-ethylphenyl) sulfone, vinyl (3-ethylphenyl) sulfone, vinyl (4-ethylphenyl) sulfone, vinyl (2- n-propylphenyl) sulfone, vinyl (3-n-propylphenyl) sulfone, vinyl (4-n-propylphenyl) sulfone, vinyl (2-i-propylphenyl) sulfone, vinyl (3-i-propylphenyl) sulfone Vinyl (4-i-propylphenyl) sulfone, vinyl (2-n-butylphenyl) sulfone, vinyl (3-n-butylphenyl) sulfone, vinyl (4-n-butylphenyl) sulfone, vinyl (2-i -Butylphenyl) sulf
- R 1 is an aryl group having 6 to 12 carbon atoms
- examples of the compound in which R 1 is an aryl group having 6 to 12 carbon atoms include phenyl (2-ethylphenyl) sulfone, phenyl (3-ethylphenyl) sulfone, phenyl (4-ethylphenyl) sulfone, phenyl (2- n-propylphenyl) sulfone, phenyl (3-n-propylphenyl) sulfone, phenyl (4-n-propylphenyl) sulfone, phenyl (2-i-propylphenyl) sulfone, phenyl (3-i-propylphenyl) sulfone Phenyl (4-i-propylphenyl) sulfone, phenyl (2-n-butylphenyl) sulfone, phenyl (3-
- R 1 is an aralkyl group having 7 to 12 carbon atoms
- examples of the compound in which R 1 is an aralkyl group having 7 to 12 carbon atoms include benzyl (2-ethylphenyl) sulfone, benzyl (3-ethylphenyl) sulfone, benzyl (4-ethylphenyl) sulfone, benzyl (2- n-propylphenyl) sulfone, benzyl (3-n-propylphenyl) sulfone, benzyl (4-n-propylphenyl) sulfone, benzyl (2-i-propylphenyl) sulfone, benzyl (3-i-propylphenyl) sulfone Benzyl (4-i-propylphenyl) sulfone, benzyl (2-n-butylphenyl) sulfone, benz
- Examples of the compound in which R 1 is a fluorine-substituted alkyl group having 1 to 12 carbon atoms include trifluoromethyl (2-ethylphenyl) sulfone, trifluoromethyl (3-ethylphenyl) sulfone, trifluoromethyl ( 4-ethylphenyl) sulfone, trifluoromethyl (2-n-propylphenyl) sulfone, trifluoromethyl (3-n-propylphenyl) sulfone, trifluoromethyl (4-n-propylphenyl) sulfone, trifluoromethyl ( 2-i-propylphenyl) sulfone, trifluoromethyl (3-i-propylphenyl) sulfone, trifluoromethyl (4-i-propylphenyl) sulfone, trifluoromethyl (2-n-butylphenyl) sulfone, trifluoro
- At least one of R 2 to R 6 in the general formula (3) is a secondary alkyl group having 4 or more carbon atoms or 3 in terms of improving safety during overcharge and improving high-temperature continuous charge characteristics.
- a compound that is a secondary alkyl group is preferred, and at least one of R 2 to R 6 in the general formula (3) is a compound that is any one of a t-butyl group, a t-amyl group, a cyclopentyl group, and a cyclohexyl group. More preferably it is.
- n in the general formula (3) is 1, and at least one of R 2 to R 6 is any one of a t-amyl group, a cyclopentyl group, and a cyclohexyl group. Particularly preferred is a compound in which n in 3) is 1, and R 4 is any one of a t-amyl group, a cyclopentyl group and a cyclohexyl group.
- a compound in which n is 1, R 1 is a methyl group, R 2 , R 3 , R 5 and R 6 are hydrogen atoms, and R 4 is a cyclohexyl group or a t-amyl group is more Particularly preferred. Of these, compounds in which R 1 is a methyl group, R 2 , R 3 , R 5 and R 6 are hydrogen atoms, and R 4 is a cyclohexyl group are most preferred.
- the compound represented by the general formula (3) may be used alone or in combination of two or more. *
- the proportion of the compound represented by the general formula (3) in the nonaqueous electrolytic solution is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, and 0 .1% by mass or more is particularly preferable. Moreover, 10 mass% or less is preferable, 5 mass% or less is more preferable, 3 mass% or less is further more preferable, 2 mass% or less is especially preferable, and 1.5 mass% or less is the most preferable.
- the ratio of the compound represented by the general formula (3) By setting the ratio of the compound represented by the general formula (3) to the above lower limit or more, the effects of the present invention can be sufficiently exhibited. Moreover, the capacity
- Electrolytes There is no restriction
- a lithium salt is usually used as an electrolyte.
- LiClO 4, LiAsF 6, LiPF 6, LiBF 4 and inorganic lithium salts LiFSO 3 such; LiCF 3 SO 3, LiN ( CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2 , lithium cyclic 1,2-tetrafluoroethanedisulfonylimide, lithium cyclic 1,3-hexafluoropropane disulfonylimide, LiN (CF 3 SO 2) (C 4 F 9 SO 2) , LiC (CF 3 SO 2 ) 3 , LiPF 4 (CF 3 ) 2 , LiPF 4 (C 2 F 5 ) 2 , LiPF 4 (CF 3 SO 2) 2 , LiPF 4 (C 2 F 5 SO 2) 2 , LiBF 2 (CF 3 ) 2 , LiBF 2 (C 2 F 5 ) 2, LiBF 2 (CF 3 SO 2) 2 and LiBF 2 (C 2 F 5 SO 2) Fluorine-containing organic lithium salt and the like; lithium bis (oxalato) borate, lithium
- LiPF 6 and LiBF 4 are preferable.
- lithium salts may be used alone or in combination of two or more in any combination and ratio.
- the combined use of specific inorganic lithium salts and the combined use of inorganic lithium salts with fluorine-containing organic lithium salts or carboxylic acid complex lithium salts suppresses gas generation during high-temperature storage or suppresses deterioration after high-temperature storage. Therefore, it is preferable.
- the combined use of the inorganic lithium salt is particularly preferable.
- an inorganic lithium salt such as LiPF 6 and LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , Fluorine-containing organic lithium salts such as LiN (C 2 F 5 SO 2 ) 2 , lithium cyclic 1,2-tetrafluoroethanedisulfonylimide and lithium cyclic 1,3-hexafluoropropanedisulfonylimide, and lithium bis (oxalato) )
- dicarboxylic acid complex lithium salts such as borate, lithium difluorooxalatoborate, lithium tris (oxalato) phosphate, lithium difluorobis (oxalato) phosphate
- LiPF 6 and LiBF 4 When used in combination LiPF 6 and LiBF 4 are the content of LiBF 4 to the total of LiPF 6 and LiBF 4 is preferably not less than 0.01 wt%, more preferably at least 0.05 wt%, 0.1 The mass% or more is more preferable. Moreover, 20 mass% or less is preferable, 10 mass% or less is more preferable, 5 mass% or less is further more preferable, and 3 mass% or less is especially preferable.
- the content of LiBF 4 to the total of LiPF 6 and LiBF 4 and the lower limit or more it is possible to obtain the effect of the present invention sufficiently. Further, the content ratio of LiBF 4 to the total of LiPF 6 and LiBF 4 to the upper limit or less, it is possible to improve the characteristics of the battery such as high-load discharge characteristics.
- the content of the inorganic lithium salt in the total of both is preferably 70% by mass or more, more preferably 80% by mass or more. 85 mass% or more is more preferable. Moreover, 99 mass% or less is preferable and 95 mass% or less is more preferable.
- the concentration of the electrolyte in the non-aqueous electrolytic solution is not particularly limited in order to exhibit the effect of the present invention, but is preferably 0.5 mol / liter or more, more preferably 0.8 mol / liter or more. More preferably, it is 0.0 mol / liter or more. Further, it is preferably 3 mol / liter or less, more preferably 2 mol / liter or less, still more preferably 1.8 mol / liter or less, and particularly preferably 1.6 mol / liter or less.
- the electrical conductivity of the non-aqueous electrolyte can be improved by setting the concentration of the electrolyte in the non-aqueous electrolyte to the lower limit or more. Further, by setting the concentration of the electrolyte in the non-aqueous electrolyte below the upper limit, the viscosity of the non-aqueous electrolyte can be prevented from increasing, the electrical conductivity can be improved, and the battery performance can be improved.
- Nonaqueous solvent can also be appropriately selected from conventionally known solvents for non-aqueous electrolyte solutions.
- solvents for non-aqueous electrolyte solutions for example, cyclic carbonates, chain carbonates, cyclic carboxylic acid esters, chain carboxylic acid esters, cyclic ethers, chain ethers, sulfur-containing organic solvents, phosphorus-containing organic solvents, and aromatic fluorine-containing solvents.
- cyclic carbonates, chain carbonates, cyclic carboxylic acid esters, chain carboxylic acid esters, cyclic ethers, chain ethers, sulfur-containing organic solvents, phosphorus-containing organic solvents, and aromatic fluorine-containing solvents Can be mentioned.
- cyclic carbonates examples include alkylene carbonates having an alkylene group having 2 to 4 carbon atoms such as ethylene carbonate, propylene carbonate, and butylene carbonate.
- alkylene carbonates having an alkylene group having 2 to 4 carbon atoms such as ethylene carbonate, propylene carbonate, and butylene carbonate.
- ethylene carbonate and propylene carbonate are preferable from the viewpoint of improving battery characteristics, and ethylene carbonate is particularly preferable.
- a part of hydrogen of these compounds may be substituted with fluorine.
- Examples of cyclic carbonates substituted with fluorine include fluoroethylene carbonate, 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate, tetrafluoroethylene carbonate, 1- Fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-difluoro-1-methylethylene carbonate, 1,1,2-trifluoro-2-methylethylene carbonate and trifluoromethylethylene carbonate
- alkylene carbonates having an alkylene group substituted with fluorine having 2 to 4 carbon atoms such as Of these, fluoroethylene carbonate, 1,2-difluoroethylene carbonate and trifluoromethylethylene carbonate are preferred.
- dialkyl carbonates are preferable, and the number of carbon atoms of the constituting alkyl group is preferably 1 to 5, and particularly preferably 1 to 4.
- symmetric chain alkyl carbonates such as dimethyl carbonate, diethyl carbonate and di-n-propyl carbonate; asymmetric chain such as ethyl methyl carbonate, methyl-n-propyl carbonate and ethyl-n-propyl carbonate
- alkyl carbonates examples include alkyl carbonates.
- dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are preferable from the viewpoint of improving battery characteristics.
- a part of hydrogen of the alkyl group may be substituted with fluorine.
- chain carbonates substituted with fluorine include bis (fluoromethyl) carbonate, bis (difluoromethyl) carbonate, bis (trifluoromethyl) carbonate, bis (2-fluoroethyl) carbonate, and bis (2,2- Difluoroethyl) carbonate, bis (2,2,2-trifluoroethyl) carbonate, 2-fluoroethyl methyl carbonate, 2,2-difluoroethyl methyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, etc. .
- cyclic carboxylic acid esters examples include ⁇ -butyrolactone, ⁇ -valerolactone, and the like, and compounds in which part of hydrogen of these compounds is substituted with fluorine.
- chain carboxylates examples include, for example, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, isobutyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, prol propionate Isopropyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl valerate, ethyl valerate, etc. Can be mentioned.
- methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate and methyl valerate are preferable.
- cyclic ethers examples include tetrahydrofuran, 2-methyltetrahydrofuran, and the like, and compounds in which part of hydrogen of these compounds is substituted with fluorine.
- chain ethers examples include dimethoxyethane and diethoxyethane. Further, as a compound in which part of hydrogen of these compounds is substituted with fluorine, bis (trifluoroethoxy) ethane, ethoxytrifluoroethoxyethane, methoxytrifluoroethoxyethane, 1,1,1,2,2,3, 4,5,5,5-decafluoro-3-methoxy-4-trifluoromethyl-pentane, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-ethoxy- 4-trifluoromethyl-pentane, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-propoxy-4-trifluoromethyl-pentane, 1,1,2,2 -Tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether and 2,2-difluoroethyl-2,2,3,3-tetrafluoropropyl ether.
- sulfur-containing organic solvent examples include sulfolane, 2-methylsulfolane, 3-methylsulfolane, diethylsulfone, ethylmethylsulfone, and methylpropylsulfone, and compounds obtained by substituting a part of hydrogen of these compounds with fluorine. .
- Examples of the phosphorus-containing organic solvent include trimethyl phosphate, triethyl phosphate, dimethyl ethyl phosphate, methyl diethyl phosphate, ethylene methyl phosphate, ethylene ethyl phosphate, and a part of hydrogen of these compounds substituted with fluorine. Compounds.
- aromatic fluorine-containing solvent examples include fluorobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, pentafluorobenzene, hexafluorobenzene, and benzotrifluoride.
- a high dielectric constant solvent such as cyclic carbonates and cyclic carboxylic acid esters in combination with a low viscosity solvent such as chain carbonates and chain carboxylic acid esters.
- One preferred combination of non-aqueous solvents is a combination mainly composed of alkylene carbonate and dialkyl carbonate.
- the balance between the cycle characteristics and high-temperature storage characteristics (particularly, the remaining capacity and high-load discharge capacity after high-temperature storage) of a battery produced using the non-aqueous solvent may be improved.
- the total of alkylene carbonate and dialkyl carbonate in the nonaqueous solvent is preferably 70% by volume or more, more preferably 80% by volume or more, and further preferably 90% by volume or more.
- the proportion of alkylene carbonate to the total of alkylene carbonate and dialkyl carbonate is preferably 5% by volume or more, more preferably 10% by volume or more, and further preferably 15% by volume or more. Moreover, 50 volume% or less is preferable, 35 volume% or less is more preferable, 30 volume% or less is further more preferable, and 25 volume% or less is especially preferable.
- alkylene carbonate ethylene carbonate, propylene carbonate and fluoroethylene carbonate are preferable from the viewpoint of improving the cycle characteristics and high-temperature storage characteristics of the battery.
- ethylene carbonate and dialkyl carbonate examples include ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and ethyl methyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and ethyl methyl.
- examples thereof include carbonate, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.
- a combination in which propylene carbonate is further added to the combination of these ethylene carbonates and dialkyl carbonates is also a preferable combination.
- the volume ratio of ethylene carbonate to propylene carbonate is preferably 99: 1 to 40:60, particularly preferably 95: 5 to 50:50.
- the proportion of propylene carbonate in the entire non-aqueous solvent is preferably 0.1% by volume or more, more preferably 1% by volume or more, still more preferably 2% by volume or more, and preferably 20% by volume or less, and 8% by volume. % Or less is more preferable, and 5% by volume or less is still more preferable. It is preferable to contain propylene carbonate in this concentration range because the low temperature characteristics may be further improved while maintaining the combination characteristics of ethylene carbonate and dialkyl carbonate.
- ethylene carbonate such as ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, and symmetrical chain alkyl carbonates and asymmetric chain alkyl carbonates.
- the asymmetric chain alkyl carbonate is preferably ethyl methyl carbonate.
- the alkyl group of the alkyl carbonate preferably has 1 to 2 carbon atoms.
- fluoroethylene carbonate and dialkyl carbonate include fluoroethylene carbonate and dimethyl carbonate, fluoroethylene carbonate and diethyl carbonate, fluoroethylene carbonate and ethyl methyl carbonate, fluoroethylene carbonate and dimethyl carbonate and diethyl carbonate, and fluoroethylene carbonate. And dimethyl carbonate and ethyl methyl carbonate, fluoroethylene carbonate, diethyl carbonate and ethyl methyl carbonate, and fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
- a combination obtained by further adding ethylene carbonate and / or propylene carbonate to the combination of these fluoroethylene carbonate and dialkyl carbonate is also mentioned as a preferable combination.
- the proportion of diethyl carbonate in the total non-aqueous solvent is preferably 10% by volume or more, more preferably 20% by volume or more, and further preferably 25% by volume or more. 30% by volume or more is particularly preferable. Moreover, 90 volume% or less is preferable, 80 volume% or less is more preferable, 75 volume% or less is further more preferable, and 70 volume% or less is especially preferable.
- the non-aqueous solvent in this range, gas generation during high-temperature storage may be suppressed.
- the proportion of dimethyl carbonate in the total non-aqueous solvent is preferably 10% by volume or more, more preferably 20% by volume or more, and further preferably 25% by volume or more, 30% by volume or more is particularly preferable.
- 90 volume% or less is preferable, 80 volume% or less is more preferable, 75 volume% or less is further more preferable, and 70 volume% or less is especially preferable.
- the load characteristics of the battery may be improved.
- the battery characteristics after high-temperature storage are improved while ensuring the electrical conductivity of the electrolyte. This is preferable.
- the capacity ratio of dimethyl carbonate to ethyl methyl carbonate in all non-aqueous solvents is 1.1 or more in terms of improving the electrical conductivity of the electrolyte and improving the battery characteristics after storage. Is preferably 1.5 or more, more preferably 2.5 or more.
- the capacity ratio (dimethyl carbonate / ethyl methyl carbonate) is preferably 40 or less, more preferably 20 or less, still more preferably 10 or less, and particularly preferably 8 or less from the viewpoint of improving battery characteristics at low temperatures.
- cyclic carbonates other than the alkylene carbonates and dialkyl carbonates chain carbonates, cyclic carboxylic acid esters, chain carboxylic acid esters, Other solvents such as cyclic ethers, chain ethers, sulfur-containing organic solvents, phosphorus-containing organic solvents, and aromatic fluorine-containing solvents may be mixed.
- one organic solvent selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate, or a mixed solvent consisting of two or more organic solvents selected from the group is used as a whole. It occupies more than volume%.
- the non-aqueous electrolyte solution using the above mixed solvent may reduce solvent evaporation and liquid leakage even when used at a high temperature.
- the total of ethylene carbonate and propylene carbonate in the non-aqueous solvent is preferably 70% by volume or more, more preferably 80% by volume or more, still more preferably 90% by volume or more, and the capacity of ethylene carbonate and propylene carbonate. If the ratio is preferably 30:70 to 60:40, the balance between cycle characteristics and high temperature storage characteristics may be improved.
- the capacity of the non-aqueous solvent is a measured value at 25 ° C., but the measured value at the melting point is used for a solid at 25 ° C. such as ethylene carbonate.
- the non-aqueous electrolytic solution of the present invention includes a cyclic carbonate compound having a carbon-carbon unsaturated bond, a cyclic carbonate compound having a fluorine atom, a monofluorophosphate, and a difluorophosphate as long as the effects of the present invention are not impaired.
- Various other compounds such as at least one compound selected from the group consisting of the above and a conventionally known overcharge inhibitor may be contained as an auxiliary agent.
- a negative electrode when containing at least one compound selected from the group consisting of a cyclic carbonate compound having a carbon-carbon unsaturated bond, a cyclic carbonate compound having a fluorine atom, a monofluorophosphate and a difluorophosphate, a negative electrode In order to form a highly stable film, cycle characteristics and battery characteristics after high-temperature storage may be improved, which is preferable.
- Cyclic carbonate compound having carbon-carbon unsaturated bond examples include vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, 1,2-dimethyl vinylene carbonate, 1,2-diethyl vinylene carbonate, fluorovinylene carbonate, and trifluoromethyl.
- Vinylene carbonate compounds such as vinylene carbonate; vinyl ethylene carbonate, 1-methyl-2-vinylethylene carbonate, 1-ethyl-2-vinylethylene carbonate, 1-n-propyl-2-vinylethylene carbonate, 1-methyl-2- Vinyl ethylene carbonate compounds such as vinyl ethylene carbonate, 1,1-divinyl ethylene carbonate and 1,2-divinyl ethylene carbonate; 1,1-dimethyl Methylene ethylene carbonate compounds such as 2-methylene-ethylene carbonate and 1,1-diethyl-2-methylene-ethylene carbonate.
- vinylene carbonate, vinyl ethylene carbonate, and 1,2-divinyl ethylene carbonate are preferable from the viewpoint of improving cycle characteristics and capacity maintenance characteristics after high-temperature storage, among which vinylene carbonate and vinyl ethylene carbonate are more preferable, and vinylene carbonate is particularly preferable. preferable. These may be used alone or in combination of two or more.
- the proportion in the non-aqueous electrolyte is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, 0.1 mass% or more is still more preferable, and 0.3 mass% or more is especially preferable. Moreover, 8 mass% or less is preferable, 4 mass% or less is more preferable, and 3 mass% or less is still more preferable.
- the ratio of the cyclic carbonate compound having a carbon-carbon unsaturated bond By setting the ratio of the cyclic carbonate compound having a carbon-carbon unsaturated bond to the lower limit or more, the effect of improving the cycle characteristics of the battery and the capacity maintenance characteristics after high temperature storage can be sufficiently exhibited. Further, by setting the ratio of the cyclic carbonate compound having a carbon-carbon unsaturated bond to the upper limit or less, the amount of gas generated during high temperature storage can be suppressed, and the discharge characteristics at low temperature can be improved.
- Cyclic carbonate compound having fluorine atom examples include fluoroethylene carbonate, 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate, tetrafluoroethylene carbonate, 1- Fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-difluoro-1-methylethylene carbonate, 1,1,2-trifluoro-2-methylethylene carbonate and trifluoromethylethylene carbonate Etc.
- fluoroethylene carbonate 1,2-difluoroethylene carbonate and 1-fluoro-2-methylethylene carbonate are preferred from the viewpoint of improving cycle characteristics and high-temperature storage characteristics. These may be used alone or in combination of two or more.
- cyclic carbonate compound having a carbon-carbon unsaturated bond and the monofluorophosphate and difluorophosphate described below, and it is used in combination for improving cycle characteristics and high-temperature storage characteristics. Is preferred.
- the proportion in the non-aqueous electrolyte is preferably 0.001% by mass or more, more preferably 0.1% by mass or more, and 0 More preferably 3% by mass or more, and particularly preferably 0.5% by mass or more. Moreover, 10 mass% or less is preferable, 5 mass% or less is more preferable, 4 mass% or less is still more preferable, and 3 mass% or less is especially preferable.
- the ratio of the cyclic carbonate compound having a fluorine atom By setting the ratio of the cyclic carbonate compound having a fluorine atom to the lower limit or more, the effect of improving the cycle characteristics and high-temperature storage characteristics of the battery can be sufficiently exhibited. Moreover, the gas generation amount at the time of high temperature storage can be suppressed, and the discharge characteristic at low temperature can be improved by making the ratio of the cyclic carbonate compound which has a fluorine atom below the said upper limit.
- the counter cation of monofluorophosphate and difluorophosphate is not particularly limited.
- the organic group having 1 to 12 carbon atoms represented by R 1 to R 4 of ammonium is not particularly limited, and examples thereof include an alkyl group which may be substituted with a halogen atom, a halogen atom or an alkyl group. And an optionally substituted cycloalkyl group, an aryl group optionally substituted with a halogen atom or an alkyl group, and a nitrogen atom-containing heterocyclic group optionally having a substituent.
- R 1 to R 4 a hydrogen atom, an alkyl group, a cycloalkyl group, and a nitrogen atom-containing heterocyclic group are preferable.
- monofluorophosphate and difluorophosphate include lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, tetramethylammonium monofluorophosphate, tetraethylammonium monofluorophosphate, difluoro Examples thereof include lithium phosphate, sodium difluorophosphate, potassium difluorophosphate, tetramethylammonium difluorophosphate, and tetraethylammonium difluorophosphate. Among these, lithium monofluorophosphate and lithium difluorophosphate are preferable, and lithium difluorophosphate is more preferable.
- the proportion in the non-aqueous electrolyte is preferably 0.001% by mass or more, more preferably 0.01% by mass or more. 0.1% by mass or more is more preferable, and 0.2% by mass or more is particularly preferable. Moreover, 5 mass% or less is preferable, 3 mass% or less is more preferable, and 2 mass% or less is still more preferable.
- the ratio of monofluorophosphate and / or difluorophosphate By setting the ratio of monofluorophosphate and / or difluorophosphate to the lower limit or more, the effect of improving the cycle characteristics and high-temperature storage characteristics of the battery can be sufficiently exhibited. Moreover, it becomes easy to melt
- overcharge inhibitor examples include alkylbiphenyl such as biphenyl, 2-methylbiphenyl and 2-ethylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclopentylbenzene, cyclohexylbenzene, cis-1-propyl-4- Phenylcyclohexane, trans-1-propyl-4-phenylcyclohexane, cis-1-butyl-4-phenylcyclohexane, trans-1-butyl-4-phenylcyclohexane, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran, Methylphenyl carbonate, ethylphenyl carbonate, diphenyl carbonate, triphenyl phosphate, tris (2-tert-butylphenyl) phosphate, tris (3-tert-but
- alkylbiphenyls such as biphenyl and 2-methylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclopentylbenzene, cyclohexylbenzene, cis-1-propyl-4-phenylcyclohexane, trans-1-propyl-4 -Phenylcyclohexane, cis-1-butyl-4-phenylcyclohexane, trans-1-butyl-4-phenylcyclohexane, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran, methylphenyl carbonate, diphenyl carbonate, triphenyl phosphate Aromatic compounds such as tris (4-tert-butylphenyl) phosphate and tris (4-cyclohexylphenyl) phosphate; 2-fluorobiphenyl, 3-fluorobiphenyl Parti
- the content ratio of these overcharge inhibitors in the non-aqueous electrolyte is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and 0.5% by mass. % Or more is particularly preferable. Moreover, 5 mass% or less is preferable, 3 mass% or less is more preferable, and 2 mass% or less is still more preferable.
- the concentration of the overcharge inhibitor By setting the concentration of the overcharge inhibitor to the above lower limit or more, the desired effect of the overcharge inhibitor can be sufficiently exhibited. Conversely, by setting the concentration of the overcharge inhibitor to be equal to or lower than the above upper limit, it is possible to prevent deterioration of battery characteristics such as high-temperature storage characteristics.
- auxiliaries include carbonate compounds such as erythritan carbonate, spiro-bis-dimethylene carbonate, methoxyethyl-methyl carbonate, methoxyethyl-ethyl carbonate, ethoxyethyl-methyl carbonate, and ethoxyethyl-ethyl carbonate;
- carbonate compounds such as erythritan carbonate, spiro-bis-dimethylene carbonate, methoxyethyl-methyl carbonate, methoxyethyl-ethyl carbonate, ethoxyethyl-methyl carbonate, and ethoxyethyl-ethyl carbonate
- succinic acid glutaric anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaconic anhydride, diglycolic anhydride, cyclohexanedicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride,
- auxiliaries in terms of improving capacity maintenance characteristics and cycle characteristics after high-temperature storage.
- concentration of the auxiliary agent By setting the concentration of the auxiliary agent to the above lower limit or more, the effect of the auxiliary agent can be sufficiently exhibited. Moreover, it can prevent that the characteristic of batteries, such as a high load discharge characteristic, falls by making the density
- the nonaqueous electrolytic solution of the present invention can be prepared by dissolving an electrolyte, a compound represented by the general formula (3), and if necessary, other compounds in a nonaqueous solvent.
- each raw material is preferably dehydrated in advance in order to reduce the water content when the electrolyte solution is used.
- the dehydration is preferably performed to 50 ppm or less, more preferably 30 ppm or less, and still more preferably 10 ppm or less.
- the compound represented by the general formula (3) has a specific sulfur-containing functional group in the molecule and, when n is 0, a phenyl group substituted with an alkyl group having 2 or more carbon atoms, and n is 1. In some cases, it has a phenyl group substituted with an alkyl group having 5 or more carbon atoms.
- the electron donating property of an alkyl group increases as the carbon number of the alkyl group increases.
- the secondary alkyl group and the tertiary alkyl group have higher electron donating properties than the primary alkyl group. Therefore, compared to a compound having a phenyl group not substituted with an alkyl group, a compound having a phenyl group substituted with an alkyl group having 2 or more carbon atoms has a lower oxidation potential and reacts at an earlier stage during overcharge. Safety during overcharge can be improved.
- a compound with a low oxidation potential reacts at a site where the electrode activity is high even during high-temperature continuous charging, and deteriorates battery characteristics after high-temperature continuous charging, but certain sulfur-containing functional groups are present on the surface of the positive electrode.
- adsorbing it is considered that side reaction with a highly active positive electrode can be suppressed, and deterioration of battery characteristics after high-temperature continuous charging can be suppressed while enhancing safety during overcharging.
- the non-aqueous electrolyte solution of the present invention is suitable for use as a non-aqueous electrolyte solution for a secondary battery, that is, a non-aqueous electrolyte secondary battery, for example, a lithium secondary battery, among non-aqueous electrolyte batteries.
- a non-aqueous electrolyte secondary battery using the non-aqueous electrolyte of the present invention will be described.
- the lithium secondary battery of the present invention includes the above-described nonaqueous electrolytic solution of the present invention, and a positive electrode and a negative electrode capable of inserting and extracting lithium ions.
- the lithium secondary battery of the present invention may have other configurations.
- a lithium secondary battery usually includes a spacer.
- Positive electrode Any positive electrode can be used as long as it can occlude and release lithium as long as the effects of the present invention are not significantly impaired.
- a positive electrode having a positive electrode active material layer provided on a current collector is used.
- the positive electrode may include other layers as appropriate.
- the positive electrode active material layer includes a positive electrode active material.
- the positive electrode active material is not particularly limited as long as it can occlude and release lithium ions. Examples include oxides of transition metals such as Fe, Co, Ni, and Mn, composite oxides of transition metals and lithium, and sulfides of transition metals.
- transition metal oxides include MnO, V 2 O 5 , V 6 O 13 and TiO 2 .
- specific examples of the composite oxide of transition metal and lithium include a lithium nickel composite oxide whose basic composition is LiNiO 2 ; a lithium cobalt composite oxide whose basic composition is LiCoO 2 ; a basic composition of LiMnO 2 and LiMnO. 4 or the like.
- specific examples of transition metal sulfides include TiS 2 and FeS.
- lithium nickel-containing transition metal oxides are particularly preferable, and examples thereof include LiNiO 2 , LiNi x M y O 2 (M is Al, B, Ti, Zr, V, Cr, Mn, Fe, Co, Cu, And at least one selected from Zn, Mg, Ca and Ga, and x and y represent arbitrary numbers.
- M Co, Mn, Fe, Al, Mg, and Ti are particularly preferable.
- Mn alone and a combination of Co—Mn, Co—Al, and Co—Al—Mg are effective for improving thermal stability. .
- LiNi 1-ab Mn a Co b O 2 (a, b represents a number from 0 to less than 1) and LiNi 1-cd Co a Al d Mg e O 2 (c, d, e represents a number from 0 to less than 1, and LiNi 1-ab Mn a Co b O 2 (0 ⁇ a ⁇ 0.4, 0 ⁇ b ⁇ 0.4) and LiNi 1-cd Co a Al d Mg e O 2 (0 ⁇ c ⁇ 0.3, 0 ⁇ d ⁇ 0.1, 0 ⁇ e ⁇ 0.05) is more preferable, and LiNi 1/3 Mn 1/3 Co 1/3 O 2 , LiNi 0.5 Mn 0.3 Co 0.2 O 2 , LiNi 0.5 Mn 0.5 O 2 and LiNi 0.85 Co 0.10 Al 0.05 O 2 , LiNi 0.85 Co 0. 10 Al 0.03 Mg 0.02 O 2 is particularly preferred.
- the surface of the above-mentioned composite oxide of transition metal and lithium is oxidized on metals such as Al, B, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mg, Ca and Ga. Covering with an object is preferable because the oxidation reaction of the solvent at a high voltage is suppressed.
- metals such as Al, B, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mg, Ca and Ga.
- Covering with an object is preferable because the oxidation reaction of the solvent at a high voltage is suppressed.
- Al 2 O 3 , TiO 2 , ZrO 2 and MgO are particularly preferable because they have high strength and exhibit a stable coating effect.
- any one of these positive electrode active materials may be used alone, or two or more of them may be used in any combination and ratio.
- 0.1 m ⁇ 2 > / g or more is preferable normally and 0.2 m ⁇ 2 > / g or more is more preferable.
- 10 m ⁇ 2 > / g or less is preferable normally, 5.0 m ⁇ 2 > / g or less is more preferable, and 3.0 m ⁇ 2 > / g or less is more preferable.
- the rate characteristic and capacity can be improved by setting the specific surface area of the positive electrode active material to the lower limit or more. Moreover, by setting the specific surface area of the positive electrode active material to the upper limit or less, it is possible to prevent the positive electrode active material from causing an undesirable reaction with a nonaqueous electrolytic solution or the like, and to improve cycle characteristics.
- the average secondary particle size of the positive electrode active material is also arbitrary as long as the effect of the present invention is not significantly impaired, but is usually preferably 0.2 ⁇ m or more, and more preferably 0.3 ⁇ m or more. Further, it is usually preferably 20 ⁇ m or less, and more preferably 10 ⁇ m or less.
- the average secondary particle size of the positive electrode active material By making the average secondary particle size of the positive electrode active material equal to or more than the lower limit, it is possible to prevent the cycle deterioration of the lithium secondary battery from being increased and to be handled easily. In addition, by setting the average secondary particle size of the positive electrode active material to be equal to or less than the above upper limit, an increase in the internal resistance of the battery may be prevented and output may be difficult to output.
- the thickness of the positive electrode active material layer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, further preferably 20 ⁇ m or more, and most preferably 40 ⁇ m or more. Moreover, 200 micrometers or less are preferable normally, 150 micrometers or less are more preferable, and 100 micrometers or less are further more preferable.
- the thickness of the positive electrode active material layer By setting the thickness of the positive electrode active material layer to be equal to or more than the lower limit, it is easy to apply and ensure uniformity, and a sufficient capacity of the lithium secondary battery can be obtained. Moreover, the fall of a rate characteristic can be prevented by making thickness of a positive electrode active material layer below the said upper limit.
- the positive electrode active material layer is formed by, for example, slurrying the above-described positive electrode active material, a binder (binder), and various auxiliary agents as necessary with a solvent to form a coating liquid, and collecting the coating liquid. It can be manufactured by applying to the body and drying.
- the above-described positive electrode active material may be roll-formed to form a sheet electrode, or may be formed into a pellet electrode by compression molding.
- the binder is not particularly limited as long as it is a material that is stable with respect to the non-aqueous solvent used in the non-aqueous electrolyte solution and the solvent used during electrode production, but weather resistance, chemical resistance, heat resistance, and difficulty are limited. It is preferable to select in consideration of flammability and the like.
- inorganic compounds such as silicate and water glass
- alkane polymers such as polyethylene, polypropylene and poly-1,1-dimethylethylene
- unsaturated polymers such as polybutadiene and polyisoprene
- polystyrene polymethylstyrene
- polyvinyl Polymers having rings such as pyridine and poly-N-vinylpyrrolidone
- Acrylic derivative polymers such as polyvinyl fluoride, polyvinylidene fluoride and polytetrafluoroethylene, etc .
- CN group-containing poly such as polyacrylonitrile and polyvinylidene cyanide Chromatography
- mixtures, modified products, derivatives, random copolymers, alternating copolymers, graft copolymers, block copolymers, and the like of the above polymers can be used.
- preferred binders are fluororesins and CN group-containing polymers.
- a binder may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
- the weight average molecular weight of the resin is arbitrary as long as the effects of the present invention are not significantly impaired, but usually 10,000 or more is preferable and 100,000 or more is preferable. Moreover, usually 3 million or less is preferable and 1 million or less is more preferable.
- the strength of the electrode can be sufficiently obtained by setting the weight average molecular weight of the resin to the lower limit or more. On the other hand, when the weight average molecular weight of the resin is not more than the above upper limit, the viscosity can be suppressed and the formation of the electrode can be facilitated.
- the amount of the binder used is arbitrary as long as the effects of the present invention are not significantly impaired, but the positive electrode active material (when used for the negative electrode, the negative electrode active material (hereinafter, the positive electrode active material and the negative electrode active material are distinguished).
- the amount is usually 0.1 parts by weight or more, more preferably 1 part by weight or more, and usually 30 parts by weight or less, preferably 20 parts by weight per 100 parts by weight). Part or less is more preferable.
- the amount of the binder By setting the amount of the binder to the above lower limit or more, the strength of the electrode can be sufficiently obtained. Moreover, ion conductivity can be improved by making the quantity of a binder below the said upper limit.
- the electrode may contain various auxiliaries as described above.
- the auxiliary agent include a conductive material that increases the conductivity of the electrode, and a reinforcing material that improves the mechanical strength of the electrode.
- the conductive material are not particularly limited as long as an appropriate amount can be mixed with the active material to impart conductivity, but usually carbon powders such as acetylene black, carbon black and graphite, and various kinds of metals. Examples include fibers and foils.
- various inorganic and organic spherical and fibrous fillers can be used.
- these adjuvants etc. may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
- the solvent for forming the slurry is not particularly limited in type as long as it is a solvent that can dissolve or disperse the active material, the binder, and auxiliary agents used as necessary. Either an aqueous solvent or an organic solvent may be used.
- aqueous solvent examples include water and alcohol.
- organic solvent examples include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, NN-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran (THF). ), Toluene, acetone, dimethyl ether, dimethylacetamide, hexamethylphosphalamide, dimethyl sulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene and hexane.
- NMP N-methylpyrrolidone
- dimethylformamide dimethylacetamide
- methyl ethyl ketone cyclohexanone
- methyl acetate methyl acrylate
- diethyltriamine NN-dimethylaminopropylamine
- THF tetrahydrofur
- these solvents may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
- the active material layer obtained by coating and drying is preferably consolidated by a roller press or the like in order to increase the packing density of the positive electrode active material.
- the current collector As a material for the current collector, a known material can be arbitrarily used, but usually a metal or an alloy is used. Specifically, examples of the positive electrode current collector include aluminum, nickel, and SUS (stainless steel). Among these, aluminum is preferable as the current collector for the positive electrode. In addition, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and ratios.
- the surface of these current collectors is roughened in advance.
- Surface roughening methods include blasting or rolling with a rough surface roll, abrasive cloth paper with abrasive particles fixed, wire brush with grindstone, emery buff, steel wire, etc. Examples thereof include a mechanical polishing method, an electrolytic polishing method and a chemical polishing method.
- the shape of the current collector is arbitrary.
- perforated current collectors such as expanded metal and punched metal can be used to reduce the weight of the battery, i.e., to increase the energy density per weight.
- the weight can be freely changed by changing the aperture ratio.
- the coating layer when the coating layer is formed on both surfaces of the punching type current collector, the coating layer tends to be more difficult to peel due to the rivet effect of the coating layer through the hole, but the aperture ratio is too high. In this case, since the contact area between the coating layer and the current collector is small, the adhesive strength is rather low.
- a thin film When a thin film is used as the positive electrode current collector, its thickness is arbitrary as long as the effects of the present invention are not significantly impaired, but it is usually preferably 1 ⁇ m or more, and more preferably 5 ⁇ m or more. Moreover, 100 micrometers or less are preferable normally and 50 micrometers or less are more preferable.
- the thickness of the thin film By setting the thickness of the thin film below the upper limit, the capacity of the entire battery can be sufficiently obtained. Moreover, handling becomes easy by making thickness of a thin film more than the said minimum.
- Negative electrode Any negative electrode can be used as long as the effect of the present invention is not significantly impaired as long as it can occlude and release lithium.
- a negative electrode having a negative electrode active material layer provided on a current collector is used.
- the negative electrode may include other layers as appropriate.
- the negative electrode active material is not particularly limited as long as it is a material capable of occluding and releasing lithium ions, and a known negative electrode active material can be arbitrarily used.
- carbonaceous materials such as coke, acetylene black, mesophase microbeads and graphite; lithium metal; lithium alloys such as lithium-silicon and lithium-tin.
- a lithium alloy is particularly preferable from the viewpoint of high capacity per unit weight and good safety, and a carbonaceous material is particularly preferable from the viewpoint of good cycle characteristics and safety.
- a negative electrode active material may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
- the particle size of the negative electrode active material is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually preferably 1 ⁇ m or more and 15 ⁇ m in terms of excellent battery characteristics such as initial efficiency, rate characteristics and cycle characteristics. The above is more preferable. Moreover, usually 50 micrometers or less are preferable and 30 micrometers or less are more preferable.
- organic substances used for coating include coal tar pitch from soft pitch to hard pitch; coal heavy oil such as dry distillation liquefied oil; straight heavy oil such as atmospheric residue and vacuum residue; crude oil And heavy petroleum oils such as cracked heavy oil (eg, ethylene heavy end) produced as a by-product during thermal decomposition of naphtha and the like.
- a solid residue obtained by distilling these heavy oils at 200 to 400 ° C. and pulverized to 1 to 100 ⁇ m can also be used.
- a vinyl chloride resin, a phenol resin, an imide resin, etc. can also be used.
- the negative electrode active material layer can be formed into a sheet electrode by roll molding the negative electrode active material described above, or a pellet electrode by compression molding.
- the negative electrode active material, the binder, and, if necessary, various auxiliary agents and the like can be produced by applying a coating solution obtained by slurrying with a solvent onto a current collector and drying it. it can.
- the solvent, binder, and auxiliary agent that form the slurry the same materials as those described above for the positive electrode active material can be used.
- known materials can be arbitrarily used.
- metal materials such as copper, nickel and SUS are used.
- copper is particularly preferable from the viewpoint of ease of processing and cost.
- the negative electrode current collector is preferably subjected to a roughening treatment in advance, similarly to the positive electrode current collector.
- the shape of the current collector is also arbitrary, and a perforated current collector such as an expanded metal or a punching metal can be used.
- the preferable thickness when using a thin film as a current collector is the same as that of the positive electrode.
- a spacer is usually interposed between the positive electrode and the negative electrode.
- the material and shape of the spacer are not particularly limited, but those that are stable with respect to the non-aqueous electrolyte described above, have excellent liquid retention properties, and can reliably prevent short-circuiting between electrodes are preferable.
- polyolefin such as polyethylene and polypropylene, polytetrafluoroethylene, polyethersulfone, and the like can be used. Among these, polyolefin is preferable.
- the spacer is preferably porous.
- the non-aqueous electrolyte is used by impregnating a porous spacer.
- the thickness of the spacer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and further preferably 10 ⁇ m or more. Moreover, 50 micrometers or less are preferable normally, 40 micrometers or less are more preferable, and 30 micrometers or less are further more preferable.
- the thickness of the spacer By setting the thickness of the spacer to be equal to or more than the above lower limit, it is possible to sufficiently ensure insulation and mechanical strength. Further, by setting the thickness of the spacer to the upper limit or less, battery performance such as rate characteristics can be sufficiently ensured, and a decrease in energy density as the whole battery can be prevented.
- the porosity of the spacer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually preferably 20% or more, more preferably 35% or more, and 45% or more. Is more preferable. Moreover, 90% or less is preferable normally, 85% or less is more preferable, and 75% or less is further more preferable.
- the spacer porosity By setting the spacer porosity to the lower limit or more, the film resistance can be suppressed and the rate characteristics can be improved. Further, by setting the spacer porosity to be equal to or less than the above upper limit, the mechanical strength of the film can be ensured and the insulation can be improved.
- the average pore diameter of the spacer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually preferably 0.5 ⁇ m or less, more preferably 0.2 ⁇ m or less. Moreover, 0.05 micrometer or more is preferable normally.
- the lithium secondary battery of the present invention is manufactured by assembling the non-aqueous electrolyte solution according to the present invention, the positive electrode, the negative electrode, and the spacer used as necessary into an appropriate shape. Furthermore, other components such as an outer case can be used as necessary.
- the shape of the lithium secondary battery of the present invention is not particularly limited, and can be appropriately selected from various commonly employed shapes according to the application.
- a coin-type battery, a cylindrical battery, a square battery, etc. are mentioned.
- the method for assembling the battery is not particularly limited, and can be appropriately selected from various commonly used methods according to the intended shape of the battery.
- the present invention will be described more specifically with reference to examples and comparative examples.
- the present invention is not limited to these examples and comparative examples, and may be arbitrarily selected without departing from the gist of the present invention. It can be implemented with deformation.
- a negative electrode was obtained by mixing 94 parts by weight of graphite powder as a negative electrode active material and 6 parts by weight of PVdF, adding N-methylpyrrolidone into a slurry, and coating and drying on one side of a current collector made of copper. .
- the positive electrode, the negative electrode, and the polyethylene separator were laminated in the order of the negative electrode, the separator, the positive electrode, the separator, and the negative electrode.
- the battery element thus obtained was wrapped in a cylindrical aluminum laminate film, injected with an electrolyte solution described later, and then vacuum sealed to produce a sheet-like non-aqueous electrolyte secondary battery. Furthermore, in order to improve the adhesion between the electrodes, the sheet-like battery was sandwiched between glass plates and pressurized.
- 1C represents a current value for discharging the reference capacity of the battery in one hour, and for example, 0.2C represents a current value of 1/5 thereof.
- Capacity recovery rate (%) discharge capacity after storage (mAh / g) / initial discharge capacity (mAh / g)
- LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 2: 7: 1) with ethylene carbonate (EC) as a saturated cyclic carbonate and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) as chain carbonates.
- EC ethylene carbonate
- DMC dimethyl carbonate
- EMC ethyl methyl carbonate
- VC 4-fluorophenylacetate and vinylene carbonate
- VC 4-fluorophenylacetate and vinylene carbonate
- LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 2: 1: 7) with ethylene carbonate (EC) and propylene carbonate (PC), which are saturated cyclic carbonates, and dimethyl carbonate (DMC), which is a chain carbonate.
- the solution was dissolved at a rate of 1 mol / L, and 4-fluorophenyl acetate and vinylene carbonate (VC) were further added so as to be 2% by weight with respect to the total weight of the electrolyte solution to obtain a non-aqueous electrolyte solution.
- a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table 1.
- Example 3 Saturated cyclic carbonate in which ethylene carbonate (EC), and chain carbonate is a dimethyl carbonate (DMC) and a mixed solvent of ethyl methyl carbonate (EMC) (volume mixing ratio 2: 7: 1) to, an electrolyte LiPF 6 Is dissolved at a rate of 1 mol / L, and 4-fluorophenyl acetate and vinylene carbonate (VC) are further added so as to be 4% by weight and 2% by weight, respectively, with respect to the total weight of the electrolytic solution. It was. Using the obtained nonaqueous electrolytic solution, a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table 1.
- Example 4 A mixed solvent of ethylene carbonate (EC) and fluoroethylene carbonate (FEC), which are saturated cyclic carbonates, and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC), which are chain carbonates (mixing volume ratio 1: 1: 7: In 1), LiPF 6 as an electrolyte was dissolved at a rate of 1 mol / L, and 4-fluorophenyl acetate, vinylene carbonate (VC), and vinyl ethylene carbonate (VEC) were each 4 wt. %, 1% by weight and 0.5% by weight were added to obtain a non-aqueous electrolyte solution. Using the obtained nonaqueous electrolytic solution, a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table 1.
- Example 5 A mixed solvent of ethylene carbonate (EC) and fluoroethylene carbonate (FEC), which are saturated cyclic carbonates, and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC), which are chain carbonates (mixing volume ratio 1: 1: 7: In 1), LiPF 6 as an electrolyte was dissolved at a rate of 1 mol / L, and 4-fluorophenylacetate was further added so as to be 2% by weight with respect to the total weight of the electrolytic solution to obtain a non-aqueous electrolytic solution. . Using the obtained nonaqueous electrolytic solution, a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table 1.
- LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 3: 5: 2) with ethylene carbonate (EC) as a saturated cyclic carbonate and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) as chain carbonates. Is dissolved at a rate of 1 mol / L, and 2-fluorophenyl acetate and vinylene carbonate (VC) are further added so as to be 2% by weight and 1% by weight, respectively, with respect to the total weight of the electrolytic solution. It was. Using the obtained nonaqueous electrolytic solution, a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table 1.
- LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 3: 5: 2) with ethylene carbonate (EC) as a saturated cyclic carbonate and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) as chain carbonates. Is dissolved at a rate of 1 mol / L, and further, 3-fluorophenyl acetate and vinylene carbonate (VC) are added so as to be 2% by weight and 1% by weight, respectively, with respect to the total weight of the electrolytic solution. It was. Using the obtained nonaqueous electrolytic solution, a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table 1.
- LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 3: 5: 2) with ethylene carbonate (EC) as a saturated cyclic carbonate and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) as chain carbonates.
- EC ethylene carbonate
- DMC dimethyl carbonate
- EMC ethyl methyl carbonate
- VC 2,4-difluorophenylacetate and vinylene carbonate
- An electrolyte was used.
- a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table 1.
- Example 9 LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 3: 5: 2) with ethylene carbonate (EC) as a saturated cyclic carbonate and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) as chain carbonates.
- EC ethylene carbonate
- DMC dimethyl carbonate
- EMC ethyl methyl carbonate
- VC 2,3,4-trifluorophenylacetate and vinylene carbonate
- VC 2,3,4-trifluorophenylacetate and vinylene carbonate
- LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 2: 5: 3) with ethylene carbonate (EC) as a saturated cyclic carbonate and ethyl methyl carbonate (EMC) and diethyl carbonate (DMC) as chain carbonates.
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- DMC diethyl carbonate
- VC 4-trifluoromethylphenylacetate and vinylene carbonate
- VC 4-trifluoromethylphenylacetate and vinylene carbonate
- LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 2: 5: 3) with ethylene carbonate (EC) as a saturated cyclic carbonate and ethyl methyl carbonate (EMC) and diethyl carbonate (DMC) as chain carbonates.
- EC ethylene carbonate
- EMC ethyl methyl carbonate
- DMC diethyl carbonate
- VC 3,4-difluorophenylacetate and vinylene carbonate
- VC 3,4-difluorophenylacetate and vinylene carbonate
- Example 12 Mixed solvent (mixture) with saturated cyclic carbonates ethylene carbonate (EC) and fluoroethylene carbonate (FEC), chain carbonate dimethyl carbonate (DMC), and aliphatic carboxylic acid ester ethyl propionate (EP)
- EC ethylene carbonate
- FEC fluoroethylene carbonate
- DMC chain carbonate dimethyl carbonate
- EP aliphatic carboxylic acid ester ethyl propionate
- LiPF 6 as an electrolyte was dissolved at a rate of 1 mol / L
- 4-fluorophenyl acetate and vinylene carbonate (VC) were added to the electrolyte solution in a weight ratio of 2 respectively. It added so that it might become weight%, and it was set as the nonaqueous electrolyte solution.
- a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table
- Example 13 Mixed solvent (mixing volume ratio) with ethylene carbonate (EC) and fluoroethylene carbonate (FEC) which are saturated cyclic carbonates, dimethyl carbonate (DMC) which is a chain carbonate, and fluorobenzene (PhF) which is another organic solvent 10: 10: 75: 5), LiPF 6 as an electrolyte was dissolved at a rate of 1 mol / L, and 4-fluorophenyl acetate and lithium difluorophosphate (LiPO 2 F 2 ) were added to the total weight of the electrolyte. Were added to 2 wt% and 0.5 wt%, respectively, to obtain a non-aqueous electrolyte solution. Using the obtained nonaqueous electrolytic solution, a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table 1.
- LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 2: 7: 1) with ethylene carbonate (EC) as a saturated cyclic carbonate and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) as chain carbonates.
- EC ethylene carbonate
- DMC dimethyl carbonate
- EMC ethyl methyl carbonate
- PS 4-fluorophenyl acetate and 1,3-propane sultone
- PS 4-fluorophenyl acetate and 1,3-propane sultone
- a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table 1.
- Example 15 LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 2: 7: 1) with ethylene carbonate (EC) as a saturated cyclic carbonate and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) as chain carbonates. Is dissolved at a rate of 1 mol / L, and further, 4-fluorophenyl acetate and ethylene sulfite (ES) are added so as to be 2% by weight and 1% by weight, respectively, with respect to the total weight of the electrolytic solution, thereby providing nonaqueous electrolysis. Liquid. Using the obtained nonaqueous electrolytic solution, a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table 1.
- LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 2: 7: 1) with ethylene carbonate (EC) as a saturated cyclic carbonate and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) as chain carbonates.
- EC ethylene carbonate
- DMC dimethyl carbonate
- EMC ethyl methyl carbonate
- PRES 4-fluorophenyl acetate and 1,3-propene sultone
- a non-aqueous electrolyte was used.
- a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table 1.
- LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 2: 7: 1) with ethylene carbonate (EC) as a saturated cyclic carbonate and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) as chain carbonates.
- EC ethylene carbonate
- DMC dimethyl carbonate
- EMC ethyl methyl carbonate
- VC vinylene carbonate
- LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 2: 7: 1) with ethylene carbonate (EC) as a saturated cyclic carbonate and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) as chain carbonates.
- EC ethylene carbonate
- DMC dimethyl carbonate
- EMC ethyl methyl carbonate
- VC pentafluorophenylacetate and vinylene carbonate
- VC pentafluorophenylacetate and vinylene carbonate
- LiPF 6 as an electrolyte was added to a mixed solvent (mixing volume ratio 2: 7: 1) with ethylene carbonate (EC) as a saturated cyclic carbonate and dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) as chain carbonates. Is dissolved at a rate of 1 mol / L, and 4-fluorophenyl acetate and vinylene carbonate (VC) are further added to 12 wt% and 2 wt% with respect to the total weight of the electrolytic solution, respectively, and a non-aqueous electrolytic solution It was. Using the obtained nonaqueous electrolytic solution, a lithium secondary battery was produced according to the above-described method, and a capacity evaluation test, an overcharge characteristic evaluation test, and a storage characteristic evaluation test were performed. The results are shown in Table 1.
- the current supply can be stopped at a safer stage in a battery equipped with a device that detects the internal pressure and cuts off the current. Does not lead to smoke or fire.
- the storage characteristics have been greatly improved in capacity retention.
- 1C represents a current value for discharging the reference capacity of the battery in one hour, and for example, 0.2C represents a current value of 1/5 thereof.
- the volume was measured by immersing in an ethanol bath, and the amount of gas generated from the volume change before and after overcharging was determined.
- the larger the amount of gas generated after overcharging the more preferable the battery that senses this when the internal pressure rises abnormally due to an abnormality such as overcharging and activates the safety valve because the safety valve can be activated earlier. .
- the greater the difference between the amount of gas generated after overcharging and the amount of gas generated during high-temperature continuous charging, etc., will cause the safety valve to malfunction during high-temperature continuous charging while reliably operating the safety valve during overcharging. Since it can prevent, it is preferable.
- the battery was cooled to 25 ° C. and then immersed in an ethanol bath to measure the volume, and the amount of gas generated from the volume change before and after the continuous charge was determined.
- Example 17 [Manufacture of negative electrode]
- the d-value of the lattice plane (002 plane) in X-ray diffraction is 0.336 nm
- the crystallite size (Lc) is 652 nm
- the ash content is 0.07 parts by mass
- the median diameter by laser diffraction / scattering method is 12 ⁇ m
- the positive electrode, the negative electrode, and the polyethylene separator were laminated in the order of the negative electrode, the separator, the positive electrode, the separator, and the negative electrode to produce 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 electrolyte was poured into the bag and vacuum sealed.
- the sheet-like battery was manufactured and the overcharge characteristics and the high temperature continuous charge characteristics were evaluated. The evaluation results are shown in Table 3.
- Example 18 A sheet-like battery was prepared in the same manner as in Example 17 except that methanesulfonic acid (4-t-amylphenyl) was used in place of methanesulfonic acid (4-cyclohexylphenyl) in the electrolytic solution of Example 1. The overcharge characteristics and the high temperature continuous charge characteristics were evaluated. The evaluation results are shown in Table 3.
- Example 19 A mixture of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (capacity ratio 2: 3: 3) with a non-aqueous electrolyte content of 2% by weight of vinylene carbonate, 0.5% by weight of lithium difluorophosphate and methanesulfonic acid 1% by mass of (4-cyclohexylphenyl) was mixed.
- a sheet-like battery was prepared in the same manner as in Example 17 except that an electrolyte prepared by dissolving LiPF 6 sufficiently dried at a ratio of 1.0 mol / liter was used. The high temperature continuous charge characteristics were evaluated. The evaluation results are shown in Table 3.
- Example 20 A sheet-like battery was prepared in the same manner as in Example 19 except that methanesulfonic acid (4-t-amylphenyl) was used in place of methanesulfonic acid (4-cyclohexylphenyl) in the electrolytic solution of Example 3. The overcharge characteristics and the high temperature continuous charge characteristics were evaluated. The evaluation results are shown in Table 3.
- Example 21 A mixture of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (volume ratio 2: 3: 3) was added to the non-aqueous electrolyte as vinylene carbonate 1% by mass, fluoroethylene carbonate 1% by mass and methanesulfonic acid (4- 1% by mass of (cyclohexylphenyl) was mixed.
- a sheet-like battery was prepared in the same manner as in Example 17 except that an electrolyte prepared by dissolving LiPF 6 sufficiently dried at a ratio of 1.0 mol / liter was used. The high temperature continuous charge characteristics were evaluated. The evaluation results are shown in Table 3.
- Example 22 A sheet-like battery was produced in the same manner as in Example 17 except that ethanesulfonic acid (4-cyclohexylphenyl) was used in place of methanesulfonic acid (4-cyclohexylphenyl) in the electrolytic solution of Example 17. Charging characteristics and high temperature continuous charging characteristics were evaluated. The evaluation results are shown in Table 3.
- Example 6 A sheet-like battery was produced in the same manner as in Example 17 except that phenylcyclohexane was used in place of methanesulfonic acid (4-cyclohexylphenyl) in the electrolytic solution of Example 17, and the overcharge characteristics and high temperature continuous The charging characteristics were evaluated. The evaluation results are shown in Table 3.
- Example 7 A sheet-like battery was produced in the same manner as in Example 17 except that phenyl methanesulfonate was used in place of methanesulfonic acid (4-cyclohexylphenyl) in the electrolytic solution of Example 17, and the overcharge characteristics and high temperature continuous The charging characteristics were evaluated. The evaluation results are shown in Table 3.
- Example 8 A sheet-like battery was prepared in the same manner as in Example 17 except that methanesulfonic acid (4-methylphenyl) was used instead of methanesulfonic acid (4-cyclohexylphenyl) in the electrolytic solution of Example 17, Charging characteristics and high temperature continuous charging characteristics were evaluated. The evaluation results are shown in Table 3.
- the batteries of Comparative Examples 5, 7, and 8 are excellent in the amount of generated gas after high-temperature continuous charging, the remaining capacity, and the 1C discharge capacity, but the amount of generated gas after overcharging is small and excessive. Safety when charging was low.
- the battery of Comparative Example 6 had a large amount of generated gas after overcharging and high safety during overcharging, but was inferior in the amount of generated gas, remaining capacity and 1C discharge capacity after high-temperature continuous charging.
- the batteries of Examples 17 to 22 have a large amount of gas generation after overcharging, high safety during overcharging, and excellent gas generation amount, residual capacity and 1C discharge capacity after high-temperature continuous charging. . Therefore, it can be seen that the battery using the non-aqueous electrolyte according to the present invention has high safety during overcharge and is excellent in high-temperature continuous charge characteristics.
- the application of the non-aqueous electrolyte battery of the present invention is not particularly limited, and can be used for various known applications. Specific examples include notebook computers, pen input computers, mobile computers, electronic book players, mobile phones, mobile faxes, mobile copy, mobile printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CD players, and mini disc players. , Transceivers, electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, lighting equipment, toys, game machines, watches, strobes and cameras.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
Description
1.リチウム塩および非水系有機溶媒を含む非水系電解液であって、該非水系有機溶媒は、飽和環状カーボネート、鎖状カーボネートおよび脂肪族カルボン酸エステルからなる群から選ばれる少なくとも1種を合計割合で90容量%を超えて含有し、さらに下記一般式(1)で表されるフッ素置換芳香族エステル化合物を、該非水系電解液全体の重量に対して0.01~10重量%含有することを特徴とする非水系電解液。
2.飽和環状カーボネートが、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、モノフルオロエチレンカーボネートおよびジフルオロエチレンカーボネートからなる群から選ばれる少なくとも1種であることを特徴とする前項1に記載の非水系電解液。
3.鎖状カーボネートが、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、メチルプロピルカーボネートおよびエチルプロピルカーボネートからなる群から選ばれる少なくとも1種であることを特徴とする前項1又は2に記載の非水系電解液。
4.脂肪族カルボン酸エステルが、下記一般式(2)で表される化合物群から選ばれる少なくとも1種であることを特徴とする前項1~3のいずれか1項に記載の非水系電解液。
5.さらに不飽和環状カーボネート、モノフルオロリン酸塩、ジフルオロリン酸塩、スルトンおよびサルファイトからなる群から選ばれる少なくとも1種を非水系電解液全体の重量に対して0.01~10重量%含有することを特徴とする前項1~4のいずれか1項に記載の非水系電解液。
6.リチウムイオンを吸蔵・放出可能な負極および正極、並びに非水系電解液を含む非水系電解液電池であって、該非水系電解液が前項1~5のいずれか1項に記載の非水系電解液であることを特徴とする非水系電解液電池。
7.電解質および非水溶媒を含む非水系電解液であって、一般式(3)で表される化合物を含有することを特徴とする非水系電解液。
8.一般式(3)中、R1はメチル基、エチル基、ビニル基、フェニル基およびトリフルオロメチル基からなる群より選ばれる基を表し、R2~R6は、それぞれ独立して、水素原子又はフッ素原子で置換されていてもよい炭素数2~6のアルキル基を表すことを特徴とする前項7に記載の非水系電解液。
9.一般式(3)中、R2~R6の少なくとも一つはフッ素原子で置換されていてもよい炭素数5以上のアルキル基を表すことを特徴とする前項7又は8に記載の非水系電解液。
10.一般式(3)で表される化合物を、非水系電解液全体の重量に対して0.001~10質量%含有することを特徴とする前項7~9のいずれか1項に記載の非水系電解液。
11.さらに炭素-炭素不飽和結合を有する環状カーボネート化合物、フッ素原子を有する環状カーボネート化合物、モノフルオロリン酸塩およびジフルオロリン酸塩からなる群から選ばれる少なくとも一種の化合物を含有することを特徴とする前項7~10のいずれか1項に記載の非水系電解液。
12.リチウムイオンを吸蔵・放出可能な負極および正極、並びに非水系電解液を含む非水系電解液電池であって、該非水系電解液が前項7~11のいずれか1項に記載の非水系電解液であることを特徴とする非水系電解液電池。
[I.非水系電解液]
本発明の非水系電解液(以下適宜、「本発明における非水系電解液」ともいう)は、リチウム塩および非水系有機溶媒を含む非水系電解液であって、該非水系有機溶媒は飽和環状カーボネート、鎖状カーボネートおよび脂肪族カルボン酸エステルからなる群から選ばれる少なくとも1種を合計割合で90容量%を超えて含有し、さらに下記一般式(1)で表されるフッ素置換芳香族エステル化合物(以下適宜、「本発明におけるフッ素置換芳香族エステル化合物」ともいう)を、該非水系電解液の重量に対して0.01~10重量%含有する非水系電解液である。
[1-1.種類]
上記一般式(1)において、R1は炭化水素基であり、フッ素置換されていてもよい。R1として好ましい炭化水素基の例としては、アルキル基、アリール基、アルケニル基およびアラルキル基などが挙げられる。なかでも、アルキル基およびアリール基が好ましく、アルキル基がより好ましい。
フッ素置換芳香族エステル化合物の添加量は、非水系電解液の全体の重量に対して、通常0.01重量%以上が好ましく、0.1重量%以上がより好ましく、0.3重量%以上がさらに好ましく、1重量%以上が特に好ましく、2重量%以上が最も好ましい。また、通常10重量%以下が好ましく、7重量%以下がより好ましく、5重量%以下がさらに好ましく、4重量%以下が特に好ましい。
[2-1.飽和環状カーボネート]
本発明に用いる飽和環状カーボネートとしては、炭素-炭素不飽和結合を有しない環状カーボネートであって、本発明の効果を著しく損なわない限り、任意に選択できる。
本発明に用いる鎖状カーボネートとしては、本発明の効果を著しく損なわない限り任意に選択できる。例えば、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、プロピルメチルカーボネート、ジプロピルカーボネート、メチルフェニルカーボネート、エチルフェニルカーボネート、ジフェニルカーボネートなどのカーボネート類;ビス(トリフルオロメチル)カーボネート、メチルトリフルオロメチルカーボネート、ビス(モノフルオロエチル)カーボネート、メチルモノフルオロエチルカーボネート、ビス(トリフルオロエチル)カーボネートおよびメチルトリフルオロエチルカーボネートなどのハロゲン置換カーボネート類が挙げられる。
本発明に用いる脂肪族カルボン酸エステルとしては、本発明の効果を著しく損なわない限り任意に選択できるが、中でも下記一般式(2)で表される化合物群から選ばれる少なくとも1種を含有することが好ましい。
本発明の非水系電解液は、飽和環状カーボネート、鎖状カーボネートおよび脂肪族カルボン酸エステルからなる群から選ばれる少なくとも1種を合計割合で90容量%を超えて含有した非水系有機溶媒を含む。なお、上記フッ素置換芳香族エステル化合物、および後述する被膜形成剤、助剤は当該非水系有機溶媒の合計には含めないこととする。
本発明の非水系電解液は、前述の炭素-炭素不飽和結合を有しない環状カーボネートおよび鎖状カーボネート以外の溶媒を10容量%未満の範囲内で含有してもよい。当該溶媒としては、例えば、γ-ブチロラクトン、α-メチル-γ-ブチロラクトン、δ-バレロラクトン、1,2-ジメトキシエタン、1,2-ジエトキシエタン、ジエチルエーテル、テトラヒドロフラン、2-メチルテトラヒドロフラン、1,3-ジオキソラン、4-メチル-1,3-ジオキソラン、N-メチルピロリドン、N-エチルピロリドン、N-ビニルピロリドン、スルホラン、ジメチルスルホキシド、アセトニトリル、リン酸トリメチル、リン酸トリエチル、フルオロベンゼン、2,4-ジフルオロベンゼンおよびトリフルオロメチルベンゼンから選ばれる少なくとも1種を挙げることができる。
リチウム塩は電解質として用いられ、種類は特に制限はなく、無機リチウム塩および有機リチウム塩のいずれを用いてもよい。
本発明の非水系電解液は、負極上に被膜を形成させ、電池特性を改善させる目的で、さらに不飽和環状カーボネート、モノフルオロリン酸塩、ジフルオロリン酸塩、スルトンおよびサルファイトから選ばれる1種を含有することが好ましい。
本発明の非水系電解液は、本発明の効果を著しく損なわない範囲において、非水系電解液の濡れ性、過充電特性等を改善する目的で他の助剤を含有させてもよい。
本発明の非水系電解液は、本発明のリチウム二次電池に用いる際、通常は液体状態で存在するが、例えば、これを高分子によってゲル化して、半固体状電解質にしてもよい。
本発明の非水系電解液の製造方法は特に限定されない。例えば、炭素-炭素不飽和結合を有しない環状カーボネートおよび/または鎖状カーボネートを合計の割合が95容量%以上となるようにした非水系有機溶媒にリチウム塩を加え、さらに本発明におけるフッ素置換芳香族エステル化合物を該非水系電解液の重量に対して0.01~10重量%添加することにより調製することができる。
本発明の非水系電解液により効果が得られるメカニズムは定かではないが、以下のように考えられる。
[II.非水系電解液]
本発明の非水系電解液は、一般的な非水系電解液と同様に、通常はその主成分として、電解質およびこれを溶解する非水溶媒を含有し、更に一般式(3)で表される化合物を含有している。
[1-1.種類]
上記一般式(3)中、R1で表されるフッ素原子で置換されていてもよい炭素数1~12の炭化水素基としては、例えば、炭素数1~12のアルキル基、炭素数2~12のアルケニル基、炭素数6~12のアリール基および炭素数7~12のアラルキル基等が挙げられる。
(n=1の化合物)
n=1の化合物としては、例えば、炭素数1~12のアルキル基である化合物、炭素数2~12のアルケニル基である化合物、炭素数6~12のアリール基である化合物、R1が炭素数7~12のアラルキル基である化合物およびR1がフッ素置換されている炭素数1~12のアルキル基である化合物が挙げられる。
n=0の化合物としては、例えば、R1が炭素数1~12のアルキル基である化合物、R1が炭素数2~12のアルケニル基である化合物、R1が炭素数6~12のアリール基である化合物、R1が炭素数7~12のアラルキル基である化合物およびR1がフッ素置換されている炭素数1~12のアルキル基である化合物が挙げられる。
非水系電解液に占める一般式(3)で表される化合物の割合は、0.001質量%以上が好ましく、0.01質量%以上がより好ましく、0.05質量%以上がさらに好ましく、0.1質量%以上が特に好ましい。また、10質量%以下が好ましく、5質量%以下がより好ましく、3質量%以下がさらに好ましく、2質量%以下が特に好ましく、1.5質量%以下が最も好ましい。
本発明の非水系電解液に用いる電解質に制限は無く、目的とする非水系電解液二次電池に電解質として用いられるものであれば公知のものを任意に用いることができる。本発明の非水系電解液をリチウム二次電池に用いる場合には、通常は、電解質としてリチウム塩を用いる。
非水溶媒も、従来から非水系電解液の溶媒として公知のものの中から適宜選択して用いることができる。例えば、環状カーボネート類、鎖状カーボネート類、環状カルボン酸エステル類、鎖状カルボン酸エステル類、環状エーテル類、鎖状エーテル類、含硫黄有機溶媒、含燐有機溶媒および芳香族含フッ素溶媒等が挙げられる。
本発明の非水系電解液は、本発明の効果を損ねない範囲で、炭素-炭素不飽和結合を有する環状カーボネート化合物、フッ素原子を有する環状カーボネート化合物、モノフルオロリン酸塩およびジフルオロリン酸塩からなる群から選ばれる少なくとも一種の化合物や従来公知の過充電防止剤などの種々の他の化合物を助剤として含有していてもよい。
炭素-炭素不飽和結合を有する環状カーボネート化合物としては、例えば、ビニレンカーボネート、メチルビニレンカーボネート、エチルビニレンカーボネート、1,2-ジメチルビニレンカーボネート、1,2-ジエチルビニレンカーボネート、フルオロビニレンカーボネートおよびトリフルオロメチルビニレンカーボネート等のビニレンカーボネート化合物;ビニルエチレンカーボネート、1-メチル-2-ビニルエチレンカーボネート、1-エチル-2-ビニルエチレンカーボネート、1-n-プロピル-2-ビニルエチレンカーボネート、1-メチル-2-ビニルエチレンカーボネート、1,1-ジビニルエチレンカーボネートおよび1,2-ジビニルエチレンカーボネート等のビニルエチレンカーボネート化合物;1,1-ジメチル-2-メチレンエチレンカーボネートおよび1,1-ジエチル-2-メチレンエチレンカーボネート等のメチレンエチレンカーボネート化合物等が挙げられる。
フッ素原子を有する環状カーボネート化合物としては、例えば、フルオロエチレンカーボネート、1,2-ジフルオロエチレンカーボネート、1,1-ジフルオロエチレンカーボネート、1,1,2-トリフルオロエチレンカーボネート、テトラフルオロエチレンカーボネート、1-フルオロ-2-メチルエチレンカーボネート、1-フルオロ-1-メチルエチレンカーボネート、1,2-ジフルオロ-1-メチルエチレンカーボネート、1,1,2-トリフルオロ-2-メチルエチレンカーボネートおよびトリフルオロメチルエチレンカーボネート等が挙げられる。
モノフルオロリン酸塩およびジフルオロリン酸塩のカウンターカチオンとしては特に限定はないが、例えば、リチウム、ナトリウム、カリウム、マグネシウム、カルシウムおよびNR1R2R3R4(式中、R1~R4は、各々独立に、水素原子又は炭素数1~12の有機基を表す。)で表されるアンモニウム等が挙げられる。
過充電防止剤としては、例えば、ビフェニル、2-メチルビフェニルおよび2-エチルビフェニル等のアルキルビフェニル、ターフェニル、ターフェニルの部分水素化体、シクロペンチルベンゼン、シクロヘキシルベンゼン、シス-1-プロピル-4-フェニルシクロヘキサン、トランス-1-プロピル-4-フェニルシクロヘキサン、シス-1-ブチル-4-フェニルシクロヘキサン、トランス-1-ブチル-4-フェニルシクロヘキサン、t-ブチルベンゼン、t-アミルベンゼン、ジフェニルエーテル、ジベンゾフラン、メチルフェニルカーボネート、エチルフェニルカーボネート、ジフェニルカーボネート、トリフェニルホスフェート、トリス(2-t-ブチルフェニル)ホスフェート、トリス(3-t-ブチルフェニル)ホスフェート、トリス(4-t-ブチルフェニル)ホスフェート、トリス(2-t-アミルフェニル)ホスフェート、トリス(3-t-アミルフェニル)ホスフェート、トリス(4-t-アミルフェニル)ホスフェート、トリス(2-シクロヘキシルフェニル)ホスフェート、トリス(3-シクロヘキシルフェニル)ホスフェートおよびトリス(4-シクロヘキシルフェニル)ホスフェート等の芳香族化合物;2-フルオロビフェニル、3-フルオロビフェニル、4-フルオロビフェニル、4,4’-ジフルオロビフェニル、2,4-ジフルオロビフェニル、o-シクロヘキシルフルオロベンゼンおよびp-シクロヘキシルフルオロベンゼン等の前記芳香族化合物の部分フッ素化物;2,4-ジフルオロアニソール、2,5-ジフルオロアニソール、2,6-ジフルオロアニソールおよび3,5-ジフルオロアニソール等の含フッ素アニソール化合物等が挙げられる。
本発明の非水系電解液は、非水溶媒に、電解質、一般式(3)で表される化合物、必要に応じて他の化合物を溶解することにより調製することができる。非水系電解液の調製に際しては、各原料は、電解液とした場合の水分を低減させるため予め脱水しておくのが好ましい。好ましくは50ppm以下、より好ましくは30ppm以下、更に好ましくは10ppm以下までそれぞれ脱水するのがよい。また、電解液調製後に、脱水、脱酸処理等を実施してもよい。
本発明に係る非水系電解液が、過充電時の安全性に優れ、高温連続充電特性にも優れる理由は明らかではなく、また、本発明は下記作用原理に限定されるものではないが、次のように推察される。
本発明のリチウム二次電池は、上述した本発明の非水系電解液と、リチウムイオンを吸蔵・放出可能な正極および負極とを備えて構成される。また、本発明のリチウム二次電池はその他の構成を備えていてもよい。例えば、リチウム二次電池は、通常、スペーサを備えている。
正極は、リチウムの吸蔵および放出が可能なものであれば、本発明の効果を著しく損なわない限り任意のものを用いることができる。
正極活物質層は、正極活物質を含んで構成される。正極活物質としては、リチウムイオンを吸蔵・放出可能なものであれば、その種類に制限はない。例としては、Fe、Co、NiおよびMnなどの遷移金属の酸化物、遷移金属とリチウムとの複合酸化物並びに遷移金属の硫化物などが挙げられる。
なお、これらの助剤等は、1種を単独で用いてもよく、2種以上を任意の組み合わせおよび比率で併用してもよい。
集電体の素材としては、公知のものを任意に使用することができるが、通常は金属や合金が用いられる。具体的には、正極の集電体としては、アルミニウム、ニッケルおよびSUS(ステンレス)等が挙げられる。中でも、正極の集電体としてはアルミニウムが好ましい。なお、これらは1種を単独で用いてもよく、2種以上を任意の組み合わせおよび比率で併用してもよい。
負極は、リチウムの吸蔵および放出が可能なものであれば、本発明の効果を著しく損なわない限り任意のものを用いることができる。
負極活物質としては、リチウムイオンの吸蔵放出が可能な材料であれば他に制限は無く、公知の負極活物質を任意に用いることができる。例えば、コークス、アセチレンブラック、メゾフェーズマイクロビーズおよびグラファイト等の炭素質材料;リチウム金属;リチウム-シリコンおよびリチウム-スズ等のリチウム合金などを使用することが好ましい。
負極の集電体の材質としては、公知のものを任意に用いることができるが、例えば、銅、ニッケルおよびSUS等の金属材料が用いられる。中でも加工し易さとコストの点から特に銅が好ましい。
正極と負極との間には、短絡を防止するために、通常はスペーサを介在させる。スペーサの材質や形状は特に制限されないが、上述の非水系電解液に対して安定で、保液性に優れ、且つ、電極同士の短絡を確実に防止できるものが好ましい。
本発明のリチウム二次電池は、上述した本発明における非水系電解液と、正極と、負極と、必要に応じて用いられるスペーサとを、適切な形状に組み立てることにより製造される。更に、必要に応じて外装ケース等の他の構成要素を用いることも可能である。
[実施例1]
<試験操作の説明>
[正極の製造]
正極活物質であるリチウムニッケルコバルトマンガン複合酸化物(LiNi1/3Co1/3Mn1/3O2)94重量部とポリフッ化ビニリ デン(以下適宜、「PVdF」という)3重量部とアセチレンブラック3重量部とを混合し、N-メチルピロリドンを加えてスラリー状にしたものを、アルミニウムからなる集電体の両面に塗布・乾燥して正極を得た。
負極活物質であるグラファイト粉末94重量部とPVdF6重量部とを混合し、N-メチルピロリドンを加えスラリー状にしたものを、銅からなる集電体の片面に塗布・乾燥して負極を得た。
上記の正極、負極、およびポリエチレン製セパレータを、負極、セパレータ、正極、セパレータ、負極の順に積層した。こうして得られた電池要素を筒状のアルミニウムラミネートフィルムで包み込み、後述する電解液を注入した後で真空封止し、シート状の非水系電解液二次電池を作製した。更に、電極間の密着性を高めるために、ガラス板でシート状電池を挟んで加圧した。
25℃の恒温槽中、0.2Cに相当する電流で4.2Vまで定電流-定電圧充電(以下適宜、「CCCV充電」という)した後、0.2Cで3Vまで放電した。これを3回繰り返し初期のフォーメーションを行なった。次いで、0.2Cで4.2VまでCCCV充電した後、0.5Cで3Vまで再度放電し、初期放電容量を求めた。なお充電時のカット電流は0.05Cとした。
容量評価の終了した電池を25℃の恒温槽中、0.2Cで4.2VまでCCCV充電した。ついで電池を45℃の恒温槽に移し、1Cの電流値で過充電を開始し5Vに到達したところで通電を停止した。そして電池を25℃まで冷却後、直ちにエタノール浴に漬けて浮力を測定(アルキメデスの原理)することにより発生したガス量を求めた。
容量評価の終了した電池を25℃の恒温槽中、0.2Cで4.2Vまで充電した後に、85℃の高温槽に3日間保存した。その後、電池を取り出し0.2Cで4.2VまでCCCV充電した後0.5Cで3Vまで放電し、保存後の容量を求めた。また保存前後の放電容量から下記計算式により容量回復率を求めた。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比2:7:1)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに4-フルオロフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ2重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)およびプロピレンカーボネート(PC)、および鎖状カーボネートであるジメチルカーボネート(DMC)との混合溶媒(混合体積比2:1:7)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに4-フルオロフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ2重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比2:7:1)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに4-フルオロフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ4重量%および2重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)およびフルオロエチレンカーボネート(FEC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比1:1:7:1)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに4-フルオロフェニルアセテート、ビニレンカーボネート(VC)およびビニルエチレンカーボネート(VEC)を電解液全体の重量に対してそれぞれ4重量%、1重量%および0.5重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)およびフルオロエチレンカーボネート(FEC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比1:1:7:1)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに4-フルオロフェニルアセテートを電解液全体の重量に対して2重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比3:5:2)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに2-フルオロフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ2重量%および1重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比3:5:2)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに3-フルオロフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ2重量%および1重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比3:5:2)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに2,4-ジフルオロフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ2重量%および1重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比3:5:2)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに2,3,4-トリフルオロフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ2重量%および1重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるエチルメチルカーボネート(EMC)およびジエチルカーボネート(DMC)との混合溶媒(混合体積比2:5:3)に、電解質であるLiPF6を1.2mol/Lの割合で溶解させ、さらに4-トリフルオロメチルフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ2重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるエチルメチルカーボネート(EMC)およびジエチルカーボネート(DMC)との混合溶媒(混合体積比2:5:3)に、電解質であるLiPF6を1.2mol/Lの割合で溶解させ、さらに3、4-ジフルオロフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ2重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)およびフルオロエチレンカーボネート(FEC)、および鎖状カーボネートであるジメチルカーボネート(DMC)、および脂肪族カルボン酸エステルであるプロピオン酸エチル(EP)との混合溶媒(混合体積比1:1:2:5)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに4-フルオロフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ2重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)およびフルオロエチレンカーボネート(FEC)、および鎖状カーボネートであるジメチルカーボネート(DMC)、およびその他の有機溶媒であるフルオロベンゼン(PhF)との混合溶媒(混合体積比10:10:75:5)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに4-フルオロフェニルアセテートおよびジフルオロリン酸リチウム(LiPO2F2)を電解液全体の重量に対してそれぞれ2重量%および0.5重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比2:7:1)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに4-フルオロフェニルアセテートおよび1,3-プロパンスルトン(PS)を電解液全体の重量に対してそれぞれ2重量%および1重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比2:7:1)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに4-フルオロフェニルアセテートおよびエチレンサルファイト(ES)を電解液全体の重量に対してそれぞれ2重量%および1重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比2:7:1)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに4-フルオロフェニルアセテートおよび1,3-プロペンスルトン(PRES)を電解液全体の重量に対してそれぞれ2重量%および1重量%となるように添加して非水系電解液とした。 得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)、およびその他の有機溶媒であるリン酸トリメチル(TMP)との混合溶媒(混合体積比2:7:1)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに4-フルオロフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ2重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比2:7:1)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらにビニレンカーボネート(VC)を電解液全体の重量に対して2重量%となるように添加して非水系電解液とした。 得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比2:7:1)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらにペンタフルオロフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ2重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
飽和環状カーボネートであるエチレンカーボネート(EC)、および鎖状カーボネートであるジメチルカーボネート(DMC)およびエチルメチルカーボネート(EMC)との混合溶媒(混合体積比2:7:1)に、電解質であるLiPF6を1mol/Lの割合で溶解させ、さらに4-フルオロフェニルアセテートおよびビニレンカーボネート(VC)を電解液全体の重量に対してそれぞれ12重量%および2重量%となるように添加して非水系電解液とした。得られた非水系電解液を用いて、上述した方法にしたがってリチウム二次電池を作製し、容量評価試験、過充電特性評価試験および保存特性評価試験を行った。結果を表1に示す。
<試験操作の説明>
[容量評価]
シート状非水系電解液二次電池を、電極間の密着性を高めるためにガラス板で挟んだ状態で、25℃において、0.2Cに相当する定電流で4.2Vまで充電した後、0.2Cの定電流で3Vまで放電した。これを3サイクル行って電池を安定させ、4サイクル目は、0.5Cの定電流で4.2Vまで充電後、4.2Vの定電圧で電流値が0.05Cになるまで充電を実施し、0.2Cの定電流で3Vまで放電して、初期放電容量を求めた。
容量評価試験の終了した電池を、エタノール浴中に浸して体積を測定した後、45℃において、0.2Cの定電流で4.9Vまで定電流充電を行い、4.9Vに達した時点で電流をカットして、過充電試験後の電池の開回路電圧(OCV)を測定した。
容量評価試験の終了した電池を、エタノール浴中に浸して体積を測定した後、60℃において、0.5Cの定電流で定電流充電を行い、4.25Vに到達した後、定電圧充電に切り替え、1週間連続充電を行った。
[負極の製造]
X線回折における格子面(002面)のd値が0.336nm、結晶子サイズ(Lc)が652nm、灰分が0.07質量部、レーザー回折・散乱法によるメジアン径が12μm、BET法による比表面積が7.5m2/g、アルゴンイオンレーザー光を用いたラマンスペクトル分析から求めたR値(=IB/IA)が0.12、1570~1620cm-1の範囲にあるピークの半値幅が19.9cm-1である天然黒鉛粉末94質量部とポリフッ化ビニリデン(呉羽化学社製、商品名「KF-1000」)6質量部とを混合し、N-メチル-2-ピロリドンを加えスラリー状にした。このスラリーを厚さ12μmの銅箔の片面に均一に塗布、乾燥した後、負極活物質層の密度が1.67g/cm3になるようにプレスして負極とした。
LiCoO290質量部、カーボンブラック4質量部およびポリフッ化ビニリデン(呉羽化学社製、商品名「KF-1000」)6質量部を混合し、N-メチル-2-ピロリドンを加えスラリー状にし、これを厚さ15μmのアルミニウム箔の両面に均一に塗布、乾燥した後、正極活物質層の密度が3.2g/cm3になるようにプレスして正極とした。
乾燥アルゴン雰囲気下、エチレンカーボネートとエチルメチルカーボネートとジメチルカーボネートの混合物(容量比2:3:3)に、非水系電解液中の含有量としてビニレンカーボネート2質量%とメタンスルホン酸(4-シクロヘキシルフェニル)1質量%を混合し、次いで十分に乾燥したLiPF6を1.0モル/リットルの割合となるように溶解して電解液とした。
上記の正極、負極、およびポリエチレン製のセパレータを、負極、セパレータ、正極、セパレータ、負極の順に積層して電池要素を作製した。この電池要素をアルミニウム(厚さ40μm)の両面を樹脂層で被覆したラミネートフィルムからなる袋内に正極負極の端子を突設させながら挿入した後、上記電解液を袋内に注入し、真空封止を行い、シート状電池を作製し、過充電特性および高温連続充電特性の評価を行った。評価結果を表3に示す。
実施例1の電解液において、メタンスルホン酸(4-シクロヘキシルフェニル)に代えて、メタンスルホン酸(4-t-アミルフェニル)を使用した以外、実施例17と同様にしてシート状電池を作製し、過充電特性および高温連続充電特性の評価を行った。評価結果を表3に示す。
エチレンカーボネートとエチルメチルカーボネートとジメチルカーボネートの混合物(容量比2:3:3)に、非水系電解液中の含有量としてビニレンカーボネート2質量%、ジフルオロリン酸リチウム0.5質量%およびメタンスルホン酸(4-シクロヘキシルフェニル)1質量%を混合した。次いで十分に乾燥したLiPF6を1.0モル/リットルの割合となるように溶解して調製した電解液を使用した以外、実施例17と同様にしてシート状電池を作製し、過充電特性および高温連続充電特性の評価を行った。評価結果を表3に示す。
実施例3の電解液において、メタンスルホン酸(4-シクロヘキシルフェニル)に代えて、メタンスルホン酸(4-t-アミルフェニル)を使用した以外、実施例19と同様にしてシート状電池を作製し、過充電特性および高温連続充電特性の評価を行った。評価結果を表3に示す。
エチレンカーボネートとエチルメチルカーボネートとジメチルカーボネートの混合物(容量比2:3:3)に、非水系電解液中の含有量としてビニレンカーボネート1質量%、フルオロエチレンカーボネート1質量%およびメタンスルホン酸(4-シクロヘキシルフェニル)1質量%を混合した。次いで十分に乾燥したLiPF6を1.0モル/リットルの割合となるように溶解して調製した電解液を使用した以外、実施例17と同様にしてシート状電池を作製し、過充電特性および高温連続充電特性の評価を行った。評価結果を表3に示す。
実施例17の電解液において、メタンスルホン酸(4-シクロヘキシルフェニル)に代えて、エタンスルホン酸(4-シクロヘキシルフェニル)を使用した以外、実施例17と同様にしてシート状電池を作製し、過充電特性および高温連続充電特性の評価を行った。評価結果を表3に示す。
エチレンカーボネートとエチルメチルカーボネートとジメチルカーボネートの混合物(容量比2:3:3)に、非水系電解液中の含有量としてビニレンカーボネート2質量%を混合した。次いで十分に乾燥したLiPF6を1.0モル/リットルの割合となるように溶解して調製した電解液を使用した以外、実施例17と同様にしてシート状電池を作製し、過充電特性および高温連続充電特性の評価を行った。評価結果を表3に示す。
実施例17の電解液において、メタンスルホン酸(4-シクロヘキシルフェニル)に代えて、フェニルシクロへキサンを使用した以外、実施例17と同様にしてシート状電池を作製し、過充電特性および高温連続充電特性の評価を行った。評価結果を表3に示す。
実施例17の電解液において、メタンスルホン酸(4-シクロヘキシルフェニル)に代えて、メタンスルホン酸フェニルを使用した以外、実施例17と同様にしてシート状電池を作製し、過充電特性および高温連続充電特性の評価を行った。評価結果を表3に示す。
実施例17の電解液において、メタンスルホン酸(4-シクロヘキシルフェニル)に代えて、メタンスルホン酸(4-メチルフェニル)を使用した以外、実施例17と同様にしてシート状電池を作製し、過充電特性および高温連続充電特性の評価を行った。評価結果を表3に示す。
Claims (12)
- 飽和環状カーボネートが、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、モノフルオロエチレンカーボネートおよびジフルオロエチレンカーボネートからなる群から選ばれる少なくとも1種であることを特徴とする請求項1に記載の非水系電解液。
- 鎖状カーボネートが、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、メチルプロピルカーボネートおよびエチルプロピルカーボネートからなる群から選ばれる少なくとも1種であることを特徴とする請求項1又は2に記載の非水系電解液。
- さらに不飽和環状カーボネート、モノフルオロリン酸塩、ジフルオロリン酸塩、スルトンおよびサルファイトからなる群から選ばれる少なくとも1種を非水系電解液全体の重量に対して0.01~10重量%含有することを特徴とする請求項1~4のいずれか1項に記載の非水系電解液。
- リチウムイオンを吸蔵・放出可能な負極および正極、並びに非水系電解液を含む非水系電解液電池であって、該非水系電解液が請求項1~5のいずれか1項に記載の非水系電解液であることを特徴とする非水系電解液電池。
- 一般式(3)中、R1はメチル基、エチル基、ビニル基、フェニル基およびトリフルオロメチル基からなる群より選ばれる基を表し、R2~R6は、それぞれ独立して、水素原子又はフッ素原子で置換されていてもよい炭素数2~6のアルキル基を表すことを特徴とする請求項7に記載の非水系電解液。
- 一般式(3)中、R2~R6の少なくとも一つはフッ素原子で置換されていてもよい炭素数5以上のアルキル基を表すことを特徴とする請求項7又は8に記載の非水系電解液。
- 一般式(3)で表される化合物を、非水系電解液全体の重量に対して0.001~10質量%含有することを特徴とする請求項7~9のいずれか1項に記載の非水系電解液。
- さらに炭素-炭素不飽和結合を有する環状カーボネート化合物、フッ素原子を有する環状カーボネート化合物、モノフルオロリン酸塩およびジフルオロリン酸塩からなる群から選ばれる少なくとも一種の化合物を含有することを特徴とする請求項7~10のいずれか1項に記載の非水系電解液。
- リチウムイオンを吸蔵・放出可能な負極および正極、並びに非水系電解液を含む非水系電解液電池であって、該非水系電解液が請求項7~11のいずれか1項に記載の非水系電解液であることを特徴とする非水系電解液電池。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010800372413A CN102484281A (zh) | 2009-08-31 | 2010-08-30 | 非水电解液及使用该非水电解液的非水电解质电池 |
EP10812062.7A EP2475041A4 (en) | 2009-08-31 | 2010-08-30 | NONAQUEOUS ELECTROLYTIC SOLUTION, AND NONAQUEOUS ELECTROLYTE BATTERY COMPRISING SAME |
US13/408,436 US20120219866A1 (en) | 2009-08-31 | 2012-02-29 | Nonaqueous electrolytic solution and nonaqueous-electrolyte battery employing the same |
US13/871,550 US20130244122A1 (en) | 2009-08-31 | 2013-04-26 | Nonaqueous electrolytic solution and nonaqueous-electrolyte battery employing the same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009200621 | 2009-08-31 | ||
JP2009-200621 | 2009-08-31 | ||
JP2010019215 | 2010-01-29 | ||
JP2010-019215 | 2010-01-29 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/408,436 Continuation US20120219866A1 (en) | 2009-08-31 | 2012-02-29 | Nonaqueous electrolytic solution and nonaqueous-electrolyte battery employing the same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011025016A1 true WO2011025016A1 (ja) | 2011-03-03 |
Family
ID=43628105
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/064752 WO2011025016A1 (ja) | 2009-08-31 | 2010-08-30 | 非水系電解液及びそれを用いた非水系電解液電池 |
Country Status (5)
Country | Link |
---|---|
US (2) | US20120219866A1 (ja) |
EP (1) | EP2475041A4 (ja) |
KR (1) | KR20120083290A (ja) |
CN (2) | CN104112870A (ja) |
WO (1) | WO2011025016A1 (ja) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012144306A1 (ja) * | 2011-04-22 | 2012-10-26 | 宇部興産株式会社 | 非水電解液、それを用いた蓄電デバイス、及びトリフルオロメチルベンゼン化合物 |
CN103326062A (zh) * | 2012-03-20 | 2013-09-25 | 珠海银通新能源有限公司 | 锂离子电池电解液及锂离子电池 |
WO2013184881A1 (en) * | 2012-06-06 | 2013-12-12 | Johnson Controls Technology Corporation | Electrolyte formulation for high voltage and wide temperature lithium-ion cells |
WO2014115690A1 (ja) * | 2013-01-23 | 2014-07-31 | 宇部興産株式会社 | 非水電解液及びそれを用いた蓄電デバイス |
JP2014192145A (ja) * | 2013-03-28 | 2014-10-06 | Fujifilm Corp | 非水二次電池及び二次電池用電解液 |
US10923764B2 (en) | 2016-12-26 | 2021-02-16 | Daikin Industries, Ltd. | Electrolyte solution, electrochemical device, lithium ion secondary battery, and module |
US10950896B2 (en) | 2016-12-26 | 2021-03-16 | Toyota Jidosha Kabushiki Kaisha | Nonaqueous electrolyte solution, nonaqueous electrolyte secondary battery, and method of producing nonaqueous electrolyte secondary battery |
CN113571771A (zh) * | 2021-02-08 | 2021-10-29 | 深圳市研一新材料有限责任公司 | 锂离子电池用电解液及其制备方法和锂离子电池 |
CN113851637A (zh) * | 2021-08-23 | 2021-12-28 | 合肥国轩高科动力能源有限公司 | 一种多官能团电解液添加剂、含该添加剂的电解液和锂离子电池 |
Families Citing this family (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9979050B2 (en) | 2011-09-02 | 2018-05-22 | Solvay Sa | Fluorinated electrolyte compositions |
KR101938921B1 (ko) | 2011-09-02 | 2019-01-15 | 솔베이(소시에떼아노님) | 리튬 이온 배터리 |
US9130246B2 (en) * | 2012-01-11 | 2015-09-08 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery having lithium difluorophosphate and a sultone-based compound |
EP2856540A1 (en) | 2012-06-01 | 2015-04-08 | E. I. Du Pont de Nemours and Company | Lithium- ion battery |
WO2013180783A1 (en) | 2012-06-01 | 2013-12-05 | E. I. Du Pont De Nemours And Company | Fluorinated electrolyte compositions |
JP5678936B2 (ja) * | 2012-09-07 | 2015-03-04 | トヨタ自動車株式会社 | リチウムイオン二次電池の製造方法 |
CN104685693B (zh) * | 2012-09-28 | 2018-08-31 | 大金工业株式会社 | 电解液、电化学器件、锂电池以及模块 |
JP6177339B2 (ja) * | 2012-11-12 | 2017-08-09 | ビーエーエスエフ コーポレーション | 非水電解液及びそれを含む電気化学電池(セル) |
KR20140068413A (ko) | 2012-11-28 | 2014-06-09 | 한양대학교 산학협력단 | 전해질 염 용해용 용매로 알킬메탄설포네이트를 사용하는 비수계 전해액을 포함하는 이차전지 |
US20140186723A1 (en) * | 2012-12-28 | 2014-07-03 | Johnson Controls Technology Company | Systems and methods for wide temperature operation for lithium-ion battery cells |
JP5932150B2 (ja) | 2013-02-20 | 2016-06-08 | エルジー・ケム・リミテッド | 非水性電解液及びこれを含むリチウム二次電池 |
WO2014129823A1 (ko) * | 2013-02-20 | 2014-08-28 | 주식회사 엘지화학 | 리튬 이차 전지용 전해액 첨가제, 상기 전해액 첨가제를 포함하는 비수성 전해액 및 리튬 이차 전지 |
EP3588657A1 (en) | 2013-04-04 | 2020-01-01 | Solvay SA | Nonaqueous electrolyte compositions |
CN105580193B (zh) | 2013-09-24 | 2018-01-09 | 旭硝子株式会社 | 二次电池用非水电解液及锂离子二次电池 |
WO2015046171A1 (ja) * | 2013-09-24 | 2015-04-02 | 旭硝子株式会社 | 二次電池用非水電解液およびリチウムイオン二次電池 |
WO2015088053A1 (ko) * | 2013-12-09 | 2015-06-18 | 에스케이이노베이션 주식회사 | 리튬 이차전지용 전해액 및 이를 포함하는 리튬 이차전지 |
CN103779599B (zh) * | 2013-12-19 | 2015-12-02 | 宁波维科电池股份有限公司 | 一种循环富锂锰固溶体电池 |
WO2015158578A1 (en) * | 2014-04-17 | 2015-10-22 | Basf Se | Alkylbenzoate derivatives as electrolyte additive for lithium based batteries |
CN105161753B (zh) * | 2014-05-26 | 2017-12-26 | 宁德时代新能源科技股份有限公司 | 锂离子电池及其电解液 |
KR102355697B1 (ko) | 2014-06-30 | 2022-01-27 | 솔브레인 주식회사 | 전해질 및 이를 포함하는 리튬 이차 전지 |
FR3024292B3 (fr) * | 2014-07-25 | 2017-03-17 | Renault | Procede de preparation d'un electrolyte a base d'un solvant ester d'alkyle specifique |
WO2016060038A1 (ja) * | 2014-10-16 | 2016-04-21 | 株式会社Adeka | 非水電解液及び非水電解液二次電池 |
US11211637B2 (en) | 2016-01-25 | 2021-12-28 | Panasonic Intellectual Property Management Co., Ltd. | Lithium battery |
KR102233778B1 (ko) | 2016-01-28 | 2021-03-30 | 삼성에스디아이 주식회사 | 전해질 및 이를 포함하는 이차 전지 |
US11205796B2 (en) | 2016-04-07 | 2021-12-21 | StoreDot Ltd. | Electrolyte additives in lithium-ion batteries |
CN110383565B (zh) * | 2017-03-07 | 2022-08-23 | 住友精化株式会社 | 非水电解液用添加剂、非水电解液及蓄电装置 |
CN109133023B (zh) * | 2017-06-27 | 2021-12-31 | 天津金牛电源材料有限责任公司 | 一种二氟磷酸锂制备过程中非水溶剂的循环利用方法 |
CN109326825B (zh) * | 2017-07-31 | 2024-01-19 | 住友化学株式会社 | 非水电解液二次电池 |
CN107369849B (zh) * | 2017-08-04 | 2021-04-13 | 广州天赐高新材料股份有限公司 | 一种锂二次电池电解液和锂二次电池 |
KR102472907B1 (ko) | 2017-08-16 | 2022-12-02 | 삼성에스디아이 주식회사 | 술폰계 첨가제를 포함하는 리튬이차전지 |
CN107799821A (zh) * | 2017-10-24 | 2018-03-13 | 广州天赐高新材料股份有限公司 | 锂二次电池电解液及其锂二次电池 |
CN107732303A (zh) * | 2017-10-31 | 2018-02-23 | 桂林市漓江机电制造有限公司 | 锂离子电池电解液添加剂 |
CN107932199A (zh) * | 2017-12-11 | 2018-04-20 | 浙江三瑞铜业有限公司 | 一种金属工件的抛光方法 |
CN110350244B (zh) * | 2018-04-05 | 2022-10-11 | 三星Sdi株式会社 | 用于可再充电的锂电池的电解质和包括其的可再充电的锂电池 |
JP7133776B2 (ja) * | 2018-04-16 | 2022-09-09 | パナソニックIpマネジメント株式会社 | 非水電解質二次電池 |
JP7264890B2 (ja) * | 2018-05-31 | 2023-04-25 | Мuアイオニックソリューションズ株式会社 | 蓄電デバイス用非水電解液、及び蓄電デバイス |
CN110635167B (zh) * | 2018-06-22 | 2021-04-20 | 比亚迪股份有限公司 | 非水电解液、含有该非水电解液的电池及电动车辆 |
CN110797566B (zh) * | 2018-08-03 | 2021-12-10 | 惠州市豪鹏科技有限公司 | 一种锂离子电池电解液及锂离子电池 |
KR20200044539A (ko) * | 2018-10-19 | 2020-04-29 | 에스케이이노베이션 주식회사 | 리튬 이차전지 전해액 및 이를 포함하는 리튬 이차전지 |
CN111349029A (zh) * | 2018-12-21 | 2020-06-30 | 石家庄圣泰化工有限公司 | 双(甲基磺酰基)甲烷的合成方法 |
US20200220220A1 (en) * | 2019-01-08 | 2020-07-09 | Tesla Motors Canada ULC | Electrolytes with lithium difluoro(oxalato)borate and lithium tetrafluoroborate salts for lithium metal and anode-free cells |
CN109786824B (zh) * | 2019-01-25 | 2021-09-24 | 宁德新能源科技有限公司 | 电解液和使用其的电化学装置 |
KR20200095860A (ko) * | 2019-02-01 | 2020-08-11 | 삼성전자주식회사 | 리튬전지 |
CN109818063A (zh) * | 2019-03-12 | 2019-05-28 | 杉杉新材料(衢州)有限公司 | 一种三元锂离子电池非水电解液及三元锂离子电池 |
JP7216805B2 (ja) * | 2019-03-29 | 2023-02-01 | 三井化学株式会社 | 電池用非水電解液及びリチウム二次電池 |
CN110212235B (zh) * | 2019-06-12 | 2022-04-08 | 广州天赐高新材料股份有限公司 | 一种降低电池阻抗的锂二次电池电解液及其锂二次电池 |
CN112290087B (zh) * | 2019-07-22 | 2022-05-20 | 杉杉新材料(衢州)有限公司 | 一种宽温型锂离子电池电解液及含该电解液的锂离子电池 |
CN112290091B (zh) * | 2019-07-25 | 2022-03-15 | 杉杉新材料(衢州)有限公司 | 一种兼顾高低温性能的锂离子电池电解液及锂离子电池 |
CN112397783B (zh) * | 2019-08-12 | 2022-03-15 | 杉杉新材料(衢州)有限公司 | 用于硅碳负极的电池电解液及含该电解液的锂离子电池 |
CN113394443A (zh) * | 2020-03-12 | 2021-09-14 | 通用汽车环球科技运作有限责任公司 | 用于电容器辅助蓄电池的浓缩电解质 |
CN111342134B (zh) * | 2020-03-13 | 2022-09-13 | 河南电池研究院有限公司 | 一种宽温域锂离子电池非水电解液及其制备方法 |
CN113851711B (zh) * | 2020-06-28 | 2023-06-30 | 深圳市研一新材料有限责任公司 | 电池电解液及其中苯磺酸酯化合物的制备方法 |
CN114122513B (zh) * | 2020-08-28 | 2024-06-18 | 天津中电新能源研究院有限公司 | 一种功能电解液添加剂、电池电解液和钠离子电池 |
CN112216890B (zh) * | 2020-11-19 | 2021-11-02 | 江西海量动力新能源有限公司 | 一种锰酸锂电池的化成方法 |
CN114597489A (zh) * | 2022-03-22 | 2022-06-07 | 香河昆仑新能源材料股份有限公司 | 一种含氟代苯碳酸酯的电解液及由该电解液组成的电池 |
CN114914543A (zh) * | 2022-05-09 | 2022-08-16 | 四川大学 | 一种高效抑制枝晶的电解液添加剂及其应用和锂金属二次电池 |
CN115911570B (zh) * | 2022-11-28 | 2023-09-26 | 九江天赐高新材料有限公司 | 甲基三氟乙基碳酸酯的用途、电解液、抑制锰溶出的方法和电池 |
CN117913358A (zh) * | 2022-11-28 | 2024-04-19 | 九江天赐高新材料有限公司 | 一种锂离子电池电解液和锂离子电池 |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08306387A (ja) * | 1995-05-08 | 1996-11-22 | Mitsubishi Chem Corp | リチウムイオン電池 |
JPH09106835A (ja) | 1995-08-23 | 1997-04-22 | Moli Energy 1990 Ltd | 非水系の再充電可能電池における過充電保護のための重合性の芳香族添加剤 |
JPH09171840A (ja) | 1995-11-17 | 1997-06-30 | Moli Energy 1990 Ltd | 非水系リチウム電池における過充電保護用芳香族モノマー系気体発生剤 |
WO1999016144A1 (fr) * | 1997-09-19 | 1999-04-01 | Mitsubishi Chemical Corporation | Pile a electrolyte non aqueux |
JP2002015728A (ja) * | 2000-06-30 | 2002-01-18 | Nec Corp | リチウム二次電池およびその製造方法 |
JP2002050398A (ja) | 1999-06-30 | 2002-02-15 | Matsushita Electric Ind Co Ltd | 非水電解液二次電池と充電制御システムとを含む非水電解液二次電池システムおよびこれを搭載した機器 |
JP2002056891A (ja) * | 2000-08-09 | 2002-02-22 | Mitsui Chemicals Inc | 非水電解液およびそれを用いた二次電池 |
JP2003282055A (ja) | 2002-03-25 | 2003-10-03 | Sanyo Electric Co Ltd | 非水電解液二次電池 |
WO2005091422A1 (ja) * | 2004-03-22 | 2005-09-29 | Ube Industries, Ltd. | 非水電解液及びそれを用いたリチウム二次電池 |
JP2007317654A (ja) | 2006-04-27 | 2007-12-06 | Mitsubishi Chemicals Corp | 非水系電解液及びそれを用いた非水系電解液二次電池 |
JP2008091823A (ja) * | 2006-10-05 | 2008-04-17 | Japan Carlit Co Ltd:The | 電気二重層キャパシタ用電解液及び電気二重層キャパシタ |
WO2008123014A1 (ja) * | 2007-03-06 | 2008-10-16 | Ube Industries, Ltd. | スルホン酸tert-ブチルフェニル化合物及びそれを用いたリチウム二次電池用非水電解液、並びにそれを用いたリチウム二次電池 |
JP2009512418A (ja) | 2005-10-19 | 2009-03-19 | ゼップ・ローレンス・ピー. | 磁石に誘因されたトルク損失を排除するために軸ロータデカプリングを備えたブラシレス永久磁石モーター/発電機 |
WO2009057515A1 (ja) * | 2007-11-01 | 2009-05-07 | Ube Industries, Ltd. | スルホン酸フェニル化合物、それを用いた非水電解液及びリチウム電池 |
WO2009107786A1 (ja) * | 2008-02-29 | 2009-09-03 | 三菱化学株式会社 | 非水系電解液および非水系電解液電池 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3579280B2 (ja) * | 1999-01-29 | 2004-10-20 | 三洋電機株式会社 | 非水電解液二次電池用負極およびこの負極を備えた非水電解液二次電池 |
CN1934743A (zh) * | 2004-03-22 | 2007-03-21 | 宇部兴产株式会社 | 非水电解液及使用该非水电解液的锂二次电池 |
WO2005117197A1 (ja) * | 2004-05-28 | 2005-12-08 | Ube Industries, Ltd. | 非水電解液およびリチウム二次電池 |
JP4527605B2 (ja) * | 2004-06-21 | 2010-08-18 | 三星エスディアイ株式会社 | リチウムイオン二次電池用電解液及びこれを含むリチウムイオン二次電池 |
DE102005048802A1 (de) * | 2005-10-10 | 2007-04-12 | Solvay Fluor Gmbh | Fluorierte Additive für Lithiumionenbatterien |
KR101017875B1 (ko) * | 2006-04-27 | 2011-03-04 | 미쓰비시 가가꾸 가부시키가이샤 | 비수계 전해액 및 비수계 전해액 이차 전지 |
KR101531483B1 (ko) * | 2007-03-19 | 2015-06-25 | 미쓰비시 가가꾸 가부시키가이샤 | 비수계 전해액 및 비수계 전해액 전지 |
-
2010
- 2010-08-30 CN CN201410305224.3A patent/CN104112870A/zh active Pending
- 2010-08-30 EP EP10812062.7A patent/EP2475041A4/en not_active Withdrawn
- 2010-08-30 CN CN2010800372413A patent/CN102484281A/zh active Pending
- 2010-08-30 KR KR1020127004515A patent/KR20120083290A/ko not_active Application Discontinuation
- 2010-08-30 WO PCT/JP2010/064752 patent/WO2011025016A1/ja active Application Filing
-
2012
- 2012-02-29 US US13/408,436 patent/US20120219866A1/en not_active Abandoned
-
2013
- 2013-04-26 US US13/871,550 patent/US20130244122A1/en not_active Abandoned
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08306387A (ja) * | 1995-05-08 | 1996-11-22 | Mitsubishi Chem Corp | リチウムイオン電池 |
JPH09106835A (ja) | 1995-08-23 | 1997-04-22 | Moli Energy 1990 Ltd | 非水系の再充電可能電池における過充電保護のための重合性の芳香族添加剤 |
JPH09171840A (ja) | 1995-11-17 | 1997-06-30 | Moli Energy 1990 Ltd | 非水系リチウム電池における過充電保護用芳香族モノマー系気体発生剤 |
WO1999016144A1 (fr) * | 1997-09-19 | 1999-04-01 | Mitsubishi Chemical Corporation | Pile a electrolyte non aqueux |
JP2002050398A (ja) | 1999-06-30 | 2002-02-15 | Matsushita Electric Ind Co Ltd | 非水電解液二次電池と充電制御システムとを含む非水電解液二次電池システムおよびこれを搭載した機器 |
JP2002015728A (ja) * | 2000-06-30 | 2002-01-18 | Nec Corp | リチウム二次電池およびその製造方法 |
JP2002056891A (ja) * | 2000-08-09 | 2002-02-22 | Mitsui Chemicals Inc | 非水電解液およびそれを用いた二次電池 |
JP2003282055A (ja) | 2002-03-25 | 2003-10-03 | Sanyo Electric Co Ltd | 非水電解液二次電池 |
WO2005091422A1 (ja) * | 2004-03-22 | 2005-09-29 | Ube Industries, Ltd. | 非水電解液及びそれを用いたリチウム二次電池 |
JP2009512418A (ja) | 2005-10-19 | 2009-03-19 | ゼップ・ローレンス・ピー. | 磁石に誘因されたトルク損失を排除するために軸ロータデカプリングを備えたブラシレス永久磁石モーター/発電機 |
JP2007317654A (ja) | 2006-04-27 | 2007-12-06 | Mitsubishi Chemicals Corp | 非水系電解液及びそれを用いた非水系電解液二次電池 |
JP2008091823A (ja) * | 2006-10-05 | 2008-04-17 | Japan Carlit Co Ltd:The | 電気二重層キャパシタ用電解液及び電気二重層キャパシタ |
WO2008123014A1 (ja) * | 2007-03-06 | 2008-10-16 | Ube Industries, Ltd. | スルホン酸tert-ブチルフェニル化合物及びそれを用いたリチウム二次電池用非水電解液、並びにそれを用いたリチウム二次電池 |
WO2009057515A1 (ja) * | 2007-11-01 | 2009-05-07 | Ube Industries, Ltd. | スルホン酸フェニル化合物、それを用いた非水電解液及びリチウム電池 |
WO2009107786A1 (ja) * | 2008-02-29 | 2009-09-03 | 三菱化学株式会社 | 非水系電解液および非水系電解液電池 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2475041A4 |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9472828B2 (en) | 2011-04-22 | 2016-10-18 | Ube Industries, Ltd. | Nonaqueous electrolyte solution, electricity storage device using same, and trifluoromethylbenzene compound |
JP6070543B2 (ja) * | 2011-04-22 | 2017-02-01 | 宇部興産株式会社 | 非水電解液、それを用いた蓄電デバイス、及びトリフルオロメチルベンゼン化合物 |
WO2012144306A1 (ja) * | 2011-04-22 | 2012-10-26 | 宇部興産株式会社 | 非水電解液、それを用いた蓄電デバイス、及びトリフルオロメチルベンゼン化合物 |
CN103493277A (zh) * | 2011-04-22 | 2014-01-01 | 宇部兴产株式会社 | 非水电解液、使用了该非水电解液的蓄电设备及三氟甲基苯化合物 |
CN103326062A (zh) * | 2012-03-20 | 2013-09-25 | 珠海银通新能源有限公司 | 锂离子电池电解液及锂离子电池 |
WO2013184881A1 (en) * | 2012-06-06 | 2013-12-12 | Johnson Controls Technology Corporation | Electrolyte formulation for high voltage and wide temperature lithium-ion cells |
WO2014115690A1 (ja) * | 2013-01-23 | 2014-07-31 | 宇部興産株式会社 | 非水電解液及びそれを用いた蓄電デバイス |
JPWO2014115690A1 (ja) * | 2013-01-23 | 2017-01-26 | 宇部興産株式会社 | 非水電解液及びそれを用いた蓄電デバイス |
JP2014192145A (ja) * | 2013-03-28 | 2014-10-06 | Fujifilm Corp | 非水二次電池及び二次電池用電解液 |
US10950896B2 (en) | 2016-12-26 | 2021-03-16 | Toyota Jidosha Kabushiki Kaisha | Nonaqueous electrolyte solution, nonaqueous electrolyte secondary battery, and method of producing nonaqueous electrolyte secondary battery |
US10923764B2 (en) | 2016-12-26 | 2021-02-16 | Daikin Industries, Ltd. | Electrolyte solution, electrochemical device, lithium ion secondary battery, and module |
CN113571771A (zh) * | 2021-02-08 | 2021-10-29 | 深圳市研一新材料有限责任公司 | 锂离子电池用电解液及其制备方法和锂离子电池 |
CN113571771B (zh) * | 2021-02-08 | 2023-03-28 | 深圳市研一新材料有限责任公司 | 锂离子电池用电解液及其制备方法和锂离子电池 |
CN113851637A (zh) * | 2021-08-23 | 2021-12-28 | 合肥国轩高科动力能源有限公司 | 一种多官能团电解液添加剂、含该添加剂的电解液和锂离子电池 |
Also Published As
Publication number | Publication date |
---|---|
CN102484281A (zh) | 2012-05-30 |
US20130244122A1 (en) | 2013-09-19 |
KR20120083290A (ko) | 2012-07-25 |
EP2475041A4 (en) | 2014-03-12 |
CN104112870A (zh) | 2014-10-22 |
US20120219866A1 (en) | 2012-08-30 |
EP2475041A1 (en) | 2012-07-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2011025016A1 (ja) | 非水系電解液及びそれを用いた非水系電解液電池 | |
JP6017697B2 (ja) | 電池用非水電解液、及びリチウム二次電池 | |
KR101508788B1 (ko) | 비수계 전해액 및 비수계 전해액 전지 | |
KR101658678B1 (ko) | 비수계 전해액 및 비수계 전해액 전지 | |
JP5699465B2 (ja) | 非水系電解液及びそれを用いたリチウム二次電池 | |
JP5817797B2 (ja) | 非水系電解液及び非水系電解液電池 | |
JP5471616B2 (ja) | 非水系電解液及びそれを用いた非水系電解液二次電池 | |
JP5565212B2 (ja) | 非水系電解液及びそれを用いた非水系電解液電池 | |
JPWO2016121935A1 (ja) | 非水系電解液、及びそれを用いた非水系電解液二次電池 | |
JP2012064472A (ja) | 非水系電解液及びそれを用いたリチウム二次電池 | |
JP5790135B2 (ja) | 非水系電解液及びそれを用いたリチウム二次電池 | |
US10056646B2 (en) | Nonaqueous electrolyte solution and nonaqueous electrolyte battery | |
JP5978796B2 (ja) | 非水系電解液及びそれを用いた非水系電解液電池 | |
JP2011023160A (ja) | 非水系電解液及び非水系電解液電池 | |
JP6064357B2 (ja) | 非水系電解液及びそれを用いた非水系電解液電池 | |
JP5654191B2 (ja) | 非水系電解液及びそれを用いた非水系電解液二次電池 | |
JP4894157B2 (ja) | 非水系電解液及びリチウム二次電池 | |
JP6024387B2 (ja) | 非水系電解液及びそれを用いた非水系電解液電池 | |
JP2017091687A (ja) | 電池用非水電解液、及びリチウム二次電池 | |
JP5900569B2 (ja) | 非水系電解液二次電池 | |
JP2012038716A (ja) | 非水系電解液及び非水系電解液電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080037241.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10812062 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20127004515 Country of ref document: KR Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2010812062 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010812062 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |