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
  • H01M10/052—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
  • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• • 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
• • 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 secondary battery.
• Non-aqueous electrolytes are no exception, and it has been proposed to suppress deterioration due to decomposition of the electrolyte on the surface of the active positive electrode or negative electrode by electrolysis coatings with various durability improvers.
• Patent Document 1 discloses non-aqueous oxalate salts such as difluoro (bis (oxalato)) lithium phosphate, tetrafluoro (oxalato) lithium phosphate, difluoro (oxalato) lithium borate, and bis (oxalato) lithium borate.
• difluoro (bis (oxalato)) lithium phosphate tetrafluoro (oxalato) lithium phosphate
• difluoro (oxalato) lithium borate difluoro (oxalato) lithium borate
• bis (oxalato) lithium borate bis (oxalato) lithium borate
• Patent Document 2 in a lithium ion secondary battery, in order to form a passivating layer on an electrode, it contains at least one unsaturated bond in a proportion of 0.01 to 10% by mass of the nonaqueous electrolytic solution, and An electrolyte solution for a secondary battery is disclosed in which a soluble compound that can be reduced at the anode at a potential 1 V higher than lithium is added to form a passivation layer.
• a soluble compound containing the unsaturated bond for example, adding a carbonate compound having an unsaturated bond typified by vinylene carbonate (hereinafter sometimes referred to as “VC”) is disclosed.
• VC vinylene carbonate
• Patent Document 3 in a lithium ion secondary battery, for the purpose of improving the capacity retention rate after repeating the charge / discharge cycle at a high temperature, VC and Li [M (C 2 O 4 ) x R y ] (wherein M is one selected from the group consisting of P, Al, Si and C, R is selected from the group consisting of a halogen group, an alkyl group and a halogenated alkyl group) And a total amount of oxalate salt represented by 1 type of group, x is a positive integer, and y is 0 or a positive integer).
• An electrolytic solution for a secondary battery is disclosed.
• Patent Document 4 for the purpose of providing a non-aqueous electrolyte for a secondary battery that suppresses a decrease in the repeated charge / discharge characteristics (cycle characteristics) of the battery and is excellent in low-temperature discharge characteristics, at least a non-aqueous solvent,
• a non-aqueous electrolyte solution for a secondary battery which contains phosphate at 10 ppm or more with respect to the total mass of the electrolyte solution.
• Patent Document 5 proposes that an ionic complex represented by any one of the following formulas (1) to (3) having high-temperature durability is contained in a non-aqueous electrolyte and used in a non-aqueous electrolyte battery.
• the following compound No. It is disclosed that a VC represented by 21-1 may further be contained.
• [A is a metal ion, proton or onium ion; M is a group 13-15 element; R 1 is a C 1-10 ring, a hydrocarbon group that may have a hetero atom or a halogen atom, or —N (R 2 )-; R 2 is H, an alkali metal, a C1-10 ring, a hydrocarbon group which may have a hetero atom or a halogen atom; when the number of carbon atoms is 3 or more, R 2 has a branched chain or cyclic structure Y is C or S; when Y is carbon, r is 1; when Y is sulfur, r is 1 or 2; a is 1 or 2; o is 2 or 4; n is 1 or 2; p is 0 or 1; q is 1 or 2; r is 0, 1 or 2; when p is 0, a direct bond is formed between SY. ]
• Patent Document 6 a non-aqueous electrolyte solution containing an imide salt having a phosphoryl group represented by the following general formula (I) as a component for improving cycle characteristics and internal resistance characteristics is used in a non-aqueous electrolyte battery.
• an imide salt having a phosphoryl group represented by the following general formula (I) as a component for improving cycle characteristics and internal resistance characteristics is used in a non-aqueous electrolyte battery.
• VC may be further contained as a commonly used additive.
• R 1 to R 4 are each independently a fluorine atom or an organic group represented by —OR 5 ;
• R 5 is a linear or branched alkyl group, alkenyl group having 1 to 10 carbon atoms, or And at least one organic group selected from an alkynyl group, a cycloalkyl group or a cycloalkenyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and a fluorine atom or an oxygen atom in the organic group
• Unsaturated bonds can also be present.
• M represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer equal to the valence of the corresponding cation. However, at least one of R 1 to R 4 represents a fluorine atom. ]
• Patent Document 7 a non-aqueous electrolyte secondary battery excellent in cycle characteristics and low-temperature characteristics is formed by containing a salt having a divalent imide anion represented by the following general formulas (1) to (4).
• Non-aqueous electrolyte battery electrolytes have been proposed and disclosed that they may further contain VC.
• R 1 to R 3 are each independently a fluorine atom, a linear or branched alkoxy group having 1 to 10 carbon atoms, or an alkenyl having 2 to 10 carbon atoms.
• An organic group selected from an oxy group, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group, and an aryloxy group having 6 to 10 carbon atoms.
• a fluorine atom, an oxygen atom, or an unsaturated bond may be present.
• X represents a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms.
• a fluorine atom, an oxygen atom, or an unsaturated bond may be present.
• M 1 and M 2 are each independently a proton, a metal cation or an onium cation. ]
• Patent Document 8 proposes an electrolyte for a non-aqueous electrolyte battery having improved storage stability by containing at least one siloxane compound represented by the following general formula (1) or general formula (2). , VC may be further contained.
• R 1 , R 2 , and R 7 are independently selected from alkyl groups, alkenyl groups, alkynyl groups, and aryl groups containing at least one fluorine atom. These groups may have an oxygen atom.
• R 3 to R 6 and R 8 each independently represent a group selected from an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an aryl group, and an aryloxy group; These groups may have a fluorine atom and an oxygen atom.
• N represents an integer of 1 to 10.
• Patent Document 9 by including a predetermined oxalato compound and a silicon compound represented by the following general formula (2), excellent high-temperature cycle characteristics and high-temperature storage characteristics assuming use at a high temperature of 60 ° C. or higher can be exhibited.
• a non-aqueous electrolyte battery electrolyte has been proposed, and it is disclosed that VC may be further contained.
• each R 3 independently represents a group having a carbon-carbon unsaturated bond.
• R 4 each independently represents a fluorine atom, an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an aryl group, or an aryloxy group, The group may have a fluorine atom and / or an oxygen atom.
• x is 2-4.
• Patent Document 10 by incorporating a predetermined oxalato compound and at least one siloxane compound represented by the following general formula (1) or general formula (2), the effect of improving cycle characteristics and suppressing an increase in internal resistance, An electrolyte for a non-aqueous electrolyte battery having an increased initial electric capacity without impairing improvement in low temperature characteristics or the like has been proposed, and it is disclosed that VC may further be contained.
• R 1 to R 8 are each independently an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an aryl group, and The group selected from the aryloxy group is shown, These groups may have a fluorine atom and an oxygen atom.
• N represents an integer of 1 to 10.
• n is 2 or more, the plurality of R 4 , R 6 , R 7 or R 8 may be the same as or different from each other.
• Patent Document 11 proposes an electrolyte for a secondary battery that includes an aprotic solvent and a cyclic sulfonic acid ester having at least two sulfonyl groups, thereby suppressing decomposition of the solvent of the electrolyte of the secondary battery. It is disclosed that VC may be further contained.
• Patent Document 12 discloses a non-aqueous electrolytic solution having improved self-extinguishing properties by containing trimethyl phosphate and vinylene carbonate in a predetermined ratio.
• Patent Document 13 discloses a nonflammable non-aqueous electrolyte containing vinylene carbonate and vinyl ethylene carbonate as essential components.
• Patent Document 14 discloses a nonaqueous electrolytic solution that contains a compound having at least two isocyanate groups in the molecule as an essential component and may further contain VC.
• Patent Document 15 discloses a non-aqueous electrolytic solution that contains 1,3-dioxane as an essential component and may further contain VC.
• Patent Document 16 discloses a nonaqueous electrolytic solution containing vinylene carbonate and a compound having a higher reduction potential than vinylene carbonate such as succinic anhydride and maleic anhydride as essential components.
• Patent Document 17 proposes a non-aqueous electrolyte that improves the safety and battery characteristics of a non-aqueous electrolyte secondary battery by containing a cyclic phosphazene compound having a predetermined structure as an essential component, and further contains VC. It is disclosed that it may be.
• Patent Document 18 discloses a non-aqueous electrolyte that contains cyclohexylbenzene and biphenyl as essential components and may further contain VC.
• the durability improving additive containing an unsaturated bond as described above is generally added as a monomer body.
• a polymerization inhibitor is also added so that the battery does not swell due to a reaction at a portion other than that where VC should function.
• patent document 20 when forming the polymer gel layer containing the electrolyte solution containing VC, it is made to gelatinize by cationic polymerization, a free radical seed
• the durability improving additive containing an unsaturated bond has been conventionally added as a monomer body.
• a non-aqueous electrolyte solution containing a compound, a cyclic phosphazene compound, an aromatic compound, and a carbonate compound containing an unsaturated bond which has been added as a conventional monomer body, is used in a non-aqueous electrolyte secondary battery, Although excellent cycle characteristics are exhibited, the rate characteristics tend to be low, and improvement is desired.
• the present invention provides an oxalato salt, a difluorophosphate, an ionic complex having a cyclic structure, a salt having an imide anion, a Si-containing compound, a sulfate ester compound, a phosphate ester compound, a cyclic carbonate compound, an isocyanate compound, and a cyclic acetal compound.
• a non-aqueous electrolyte solution containing at least one selected from the group consisting of cyclic acid anhydrides, cyclic phosphazene compounds, and aromatic compounds and a carbonate compound containing an unsaturated bond.
• the present invention (I) Oxalato salt, difluorophosphate, ionic complex having cyclic structure, salt having imide anion, Si-containing compound, sulfate ester compound, phosphate ester compound, cyclic carbonate compound, isocyanate compound, cyclic acetal compound, cyclic At least one selected from the group consisting of acid anhydrides, cyclic phosphazene compounds, aromatic compounds, (II) a monomer represented by the following general formula [1], (III) a non-aqueous organic solvent, (IV) solute, and (V) an oligomer having a repeating unit represented by the following general formula [2], including a non-aqueous electrolyte additive having a polystyrene-equivalent number average molecular weight of 170 to 5,000, A non-aqueous electrolyte in which the content of (V) is 0.03 to 14.0% by mass with respect to 100% by mass of the total amount of (I), (II), (
• R represents a hydrogen atom, a halogen, or a lower alkyl group. R may be all the same or different, and may be linked to each other to have a cyclic structure.
• the inside of the parenthesis means that each is a repeating unit.
• R represents a hydrogen atom, a halogen or a lower alkyl group. R may be all the same or different, and may be linked to each other to have a cyclic structure.
• the number average molecular weight of the non-aqueous electrolyte additive is preferably 340 to 4000, and more preferably 800 to 3000.
• the oxalato salt comprises bis (oxalato) borate, difluoro (oxalato) borate, tris (oxalato) phosphate, difluorobis (oxalato) phosphate, and tetrafluoro (oxalato) phosphate. It is preferably at least one selected from the group.
• the electrolytic solution contains at least lithium difluorobis (oxalato) phosphate and lithium difluorophosphate as (I).
• the ionic complex having a cyclic structure is preferably at least one selected from the group consisting of compounds represented by the following general formulas [3] to [5].
• A is at least one selected from the group consisting of metal ions, protons and onium ions
• F is fluorine
• M is a group 13 element (Al, B)
• group 14 element ( Si) and at least one selected from the group consisting of Group 15 elements (P, As, Sb)
• O oxygen
• S sulfur.
• R 1 is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can be used) Or -N (R 2 )-.
• R 2 represents hydrogen, an alkali metal, a hydrocarbon group having 1 to 10 carbon atoms, a hetero atom or a halogen atom which may have a halogen atom.
• R 2 can also take a branched chain or a cyclic structure.
• Y is carbon or sulfur.
• R is 1 when Y is carbon.
• Y sulfur, r is 1 or 2.
• a is 1 or 2, o is 2 or 4, n is 1 or 2, p is 0 or 1, q is 1 or 2, and r is 0, 1 or 2.
• A is at least one selected from the group consisting of metal ions, protons and onium ions, F is fluorine, M is a group 13 element (Al, B), group 14 element ( Si) and at least one selected from the group consisting of Group 15 elements (P, As, Sb), O is oxygen, and N is nitrogen.
• Y is carbon or sulfur. When Y is carbon, q is 1. When Y is sulfur, q is 1 or 2.
• R 1 is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can be used) Or -N (R 2 )-.
• R 2 represents hydrogen, an alkali metal, a hydrocarbon group having 1 to 10 carbon atoms, a hetero atom or a halogen atom which may have a halogen atom.
• R 2 can also take a branched chain or a cyclic structure.
• R 3 is hydrogen, a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure is also used. Or -N (R 2 )-.
• R 2 represents hydrogen, an alkali metal, a hydrocarbon group having 1 to 10 carbon atoms, a hetero atom or a halogen atom which may have a halogen atom.
• R 2 can also take a branched chain or a cyclic structure.
• a is 1 or 2
• o is 2 or 4
• n is 1 or 2
• p is 0 or 1
• q is 1 or 2
• r is 0 or 1.
• D represents a halogen ion, hexafluorophosphate anion, tetrafluoroborate anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (fluorosulfonyl) (trifluoromethanesulfonyl) )
• Anion anion, bis (difluorophosphonyl) imide anion F is fluorine
• M is a group 13 element (Al, B)
• O oxygen
• N nitrogen.
• Y is carbon or sulfur.
• R 1 is a hydrocarbon group which may have a ring having 1 to 10 carbon atoms, a hetero atom or a halogen atom (in the case of 3 or more carbon atoms, a branched chain or cyclic structure can be used) Or -N (R 2 )-.
• R 2 represents hydrogen, an alkali metal, a hydrocarbon group having 1 to 10 carbon atoms, a hetero atom or a halogen atom which may have a halogen atom.
• R 2 can also take a branched chain or a cyclic structure.
• R 4 and R 5 are each independently a hydrocarbon group optionally having a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom.
• a branched chain or An annular structure can also be used.
• o 2 or 4
• n 1 or 2
• p is 0 or 1
• q is 1 or 2
• r is 1 or 2
• s is 0 or 1.
• p a direct bond is formed between YX.
• N (R 4 ) (R 5 ) and R 1 are directly bonded, and in this case, the following structures [7] to [10] can be taken.
• R 5 does not exist. Moreover, it can also take the structure where the double bond went out of the ring like [9].
• R 6 and R 7 are each independently hydrogen or a hydrocarbon group optionally having a ring having 1 to 10 carbon atoms, a hetero atom, or a halogen atom.
• a branched chain or cyclic structure can be used.
• the salt having the imide anion is a compound represented by the following general formulas [11] to [17], a salt of (CF 2 ) 2 (SO 2 ) 2 N ⁇ , and (CF 2 ) 3 (SO 2 ) 2.
• N - is preferably at least one selected from the group consisting of a salt.
• R 8 to R 11 are each independently a fluorine atom or a linear or branched alkoxy group having 1 to 10 carbon atoms.
• An alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryl having 6 to 10 carbon atoms It is an organic group selected from oxy groups, and fluorine atoms, oxygen atoms, and unsaturated bonds may be present in the organic groups.
• X 2 and X 3 are each independently a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, An alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkenyl group, an aryl group having 6 to 10 carbon atoms, and a carbon number of 1
• the Si-containing compound is at least one compound represented by the following general formula [18]: hexamethylsiloxane, 1,3-divinyltetramethyldisiloxane, (bishexafluoroisopropoxy) (dimethyl) (divinyl) disiloxane , Tetramethylsilane, trimethylvinylsilane, vinyldimethylfluorosilane, and at least one selected from the group consisting of divinylmethylfluorosilane.
• R 12 each independently represents a group having a carbon-carbon unsaturated bond.
• R 13 each independently represents a fluorine atom, an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkynyl group, an alkynyloxy group, an aryl group, or an aryloxy group, The group may have a fluorine atom and / or an oxygen atom.
• x is 2-4.
• the sulfate compound is a cyclic sulfonic acid compound represented by the following general formulas [19], [20] and [21], 2,2-dioxide-1,2-oxathiolan-4-yl, 1,3-propane It is preferably at least one selected from the group consisting of sultone, 1,3-butane sultone, and 1,4-butane sultone.
• O is an oxygen atom
• S is a sulfur atom
• n 2 is an integer of 1 to 3.
• R 14 , R 15 , R 16 and R 17 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted carbon group having 1 to 4 carbon atoms.
• a substituted alkyl group having 1 to 5 carbon atoms, and R 20 and R 21 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted group.
• n 4 is an integer of 0 or more and 4 or less.
• O is an oxygen atom
• S is a sulfur atom
• n 5 is an integer of 0 to 3
• R 22 and R 23 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted atom.
• the phosphoric acid ester compound is composed of trimethyl phosphate, tributyl phosphate, trioctyl phosphate, tris (2,2,2-trifluoroethyl) phosphate, and monofluoropropargyloxyphosphate-lithium pentafluorophosphate. It is preferably at least one selected from the group consisting of
• the cyclic carbonate compound is preferably at least one selected from the group consisting of the cyclic carbonate compound represented by the following general formula [22] and dimethyl vinylene carbonate.
• O is an oxygen atom
• A is a hydrocarbon having 10 or less carbon atoms and may have an unsaturated bond, a cyclic structure or a halogen
• B is an unsaturated bond having 10 or less carbon atoms.
• a double bond may be present between AB.
• the isocyanate compound is preferably at least one selected from the group consisting of hexamethylene diisocyanate, octamethylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate.
• the cyclic acetal compound is preferably at least one selected from the group consisting of 1,3-dioxolane, 1,3-dioxane, and 1,3,5-trioxane.
• the cyclic acid anhydride is preferably at least one selected from the group consisting of succinic anhydride, maleic anhydride, and 3-allyl succinic anhydride.
• the cyclic phosphazene compound is at least one selected from the group consisting of methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, diethoxypentafluorocyclotriphosphazene, and ethoxyheptafluorocyclotetraphosphazene.
• it is a seed.
• the aromatic compound is at least selected from the group consisting of cyclohexylbenzene, biphenyl, tert-butylbenzene, 4-fluorobiphenyl, fluorobenzene, 2,4-difluorobenzene, 1-cyclohexyl-4-fluorobenzene, and difluoroanisole.
• One type is preferable.
• the electrolyte solution is an ionic complex having a cyclic structure, a salt having an imide anion, a Si-containing compound, a sulfate ester compound, a phosphate ester compound, a cyclic carbonate compound, an isocyanate, together with an oxalate salt and / or a difluorophosphate. It is also one of preferable modes to contain at least one compound selected from the group consisting of a compound, a cyclic acetal compound, a cyclic acid anhydride, a cyclic phosphazene compound, and an aromatic compound.
• the solute is lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), bis (trifluoromethanesulfonyl) imidolithium (LiN (CF 3 SO 2 ) 2 ), bis (pentafluoroethanesulfonyl) It consists of imidolithium (LiN (C 2 F 5 SO 2 ) 2 ), bis (fluorosulfonyl) imide lithium (LiN (FSO 2 ) 2 ), and bis (difluorophosphonyl) imide lithium (LiN (POF 2 ) 2 ). It is preferably at least one selected from the group.
• the non-aqueous solvent is preferably at least one selected from the group consisting of cyclic carbonates, chain carbonates, cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids. .
• the present invention is a non-aqueous electrolyte secondary battery comprising at least a positive electrode, a negative electrode, and the non-aqueous electrolyte solution described above.
• a non-aqueous electrolyte solution containing at least one selected from the group consisting of cyclic acid anhydrides, cyclic phosphazene compounds and aromatic compounds and a carbonate compound (monomer body) containing an unsaturated bond To provide a non-aqueous electrolyte and a non-aqueous electrolyte secondary battery that can improve rate characteristics and exhibit cycle characteristics and rate characteristics in a well-balanced manner when used in an electrolyte secondary battery. it can.
• Non-aqueous electrolyte The non-aqueous electrolyte of the present invention is (I) Oxalato salt, difluorophosphate, ionic complex having cyclic structure, salt having imide anion, Si-containing compound, sulfate ester compound, phosphate ester compound, cyclic carbonate compound, isocyanate compound, cyclic acetal compound, cyclic At least one selected from the group consisting of acid anhydrides, cyclic phosphazene compounds, aromatic compounds, (II) a monomer represented by the above general formula [1], (III) a non-aqueous organic solvent, (IV) solute, and (V) an oligomer having a repeating unit represented by the general formula [2], having a polystyrene-equivalent number average molecular weight of 170 to 5000, and a non-aqueous electrolyte additive, A non-aqueous electrolyte in which the content of (V) is 0.03 to 14.0%
• bis (oxalato) borate, difluoro (oxalato) borate, difluorobis (oxalato) phosphate and from the viewpoint of exhibiting excellent cycle characteristics while preventing excessive generation of gas , At least one selected from the group consisting of tetrafluoro (oxalato) phosphates is preferred.
• Bis (oxalato) borate and difluoro (oxalato) borate may be used in combination, bis (oxalato) borate and tris (oxalato) phosphate may be used in combination, or bis ( Oxalato) borate and difluorobis (oxalato) phosphate may be used in combination, bis (oxalato) borate and tetrafluoro (oxalato) phosphate may be used in combination, or difluoro (oxalato) Borate and tris (oxalato) phosphate may be used in combination, difluoro (oxalato) borate and difluorobis (oxalato) phosphate may be used in combination, or difluoro (oxalato) borate And tetrafluoro (oxalato) phosphate may be used in combination, or tris (oxalato) phosphate and difluorobis (oxal
• (Oxalato) phosphate, difluorobis (oxalato) phosphate and tetrafluoro (oxalato) phosphate may be used in combination, or bis (oxalato) borate, difluoro (oxalato) borate and tris ( Oxalato) phosphate, difluorobis (oxalato) phosphate and tetrafluoro (oxalato) phosphate in combination May be.
• the content of (I) is 100% by mass with respect to the total amount of (I), (II), (III), (IV), and (V).
• a content of 0.01 to 10.0% by mass is preferable because when used in a non-aqueous electrolyte secondary battery, the cycle characteristics and rate characteristics are easily exhibited in a well-balanced manner.
• the content of (I) is more preferably 0.05 to 5.0% by mass.
• lithium salt is preferable, and as the oxalate salt, bis (oxalato) lithium borate, difluoro (oxalato) lithium borate, difluorobis (oxalato).
• Lithium phosphate and lithium tetrafluoro (oxalato) phosphate are preferred. Accordingly, lithium difluorophosphate and lithium bis (oxalato) borate may be used in combination, lithium difluorophosphate and lithium difluoro (oxalate) borate may be used in combination, or lithium difluorophosphate and difluorobis (oxalato).
• Lithium phosphate may be used in combination, lithium difluorophosphate and lithium tetrafluoro (oxalato) phosphate may be used in combination, lithium difluorophosphate, lithium bis (oxalato) borate, and difluoro (oxalato) Lithium borate may be used in combination, lithium difluorophosphate, lithium bis (oxalato) borate, and lithium difluorobis (oxalato) phosphate may be used in combination, or lithium difluorophosphate and bis (oxalato) borohydride.
• Lithium oxide and tetrafluoro (oxa G) Lithium phosphate may be used in combination, lithium difluorophosphate, lithium difluoro (oxalato) borate, and lithium difluorobis (oxalato) phosphate may be used in combination, or lithium difluorophosphate and difluoro (oxalato).
• Lithium borate and tetrafluoro (oxalato) lithium phosphate may be used in combination, or difluorolithium phosphate, difluorobis (oxalato) lithium phosphate and tetrafluoro (oxalato) lithium phosphate may be used in combination.
• Lithium difluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate and lithium difluorobis (oxalato) phosphate, or lithium difluorophosphate and lithium bis (oxalato) borate And difluoro (Oki Lato) lithium borate and tetrafluoro (oxalato) lithium phosphate may be used in combination, lithium difluorophosphate, lithium difluoro (oxalato) borate, lithium difluorobis (oxalato) phosphate and tetrafluoro (oxalato) phosphorus
• Lithium phosphate may be used in combination, or lithium difluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium difluorobis (oxalato) phosphate, and lithium tetrafluoro (oxalato)
• the electrolytic solution contains at least lithium difluorobis (oxalato) phosphate and lithium difluorophosphate as (I).
• the content of lithium difluorobis (oxalato) phosphate is 0.15 to 2.50% by mass with respect to the total amount of 100% by mass of the above (I) to (V), and the content of lithium difluorophosphate Is particularly preferably 0.3 to 3.0% by mass.
• Specific examples of the ionic complex represented by the general formula [3] include the following compounds.
• A is any one cation selected from the group consisting of Li ions, Na ions, K ions, or quaternary alkyl ammonium ions.
• the ionic complex is selected from the group consisting of [3Bb] and [3Bd] in that the cycle characteristics of the nonaqueous electrolyte battery are enhanced by using it as a component of the electrolyte for a nonaqueous electrolyte battery. At least one is preferred.
• the compound represented by the general formula [4] include the following compounds.
• A is any one cation selected from the group consisting of Li ions, Na ions, K ions, or quaternary alkyl ammonium ions.
• the ionic complex is used in the above [4Pa], [4Pc], [4Ba], and [4Ba] in that the cycle characteristics of the nonaqueous electrolyte battery are enhanced by using it as a component of the electrolyte for a nonaqueous electrolyte battery. It is preferably at least one selected from the group consisting of the above [4Bc].
• D ⁇ represents hexafluorophosphate anion, tetrafluoroborate anion, bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (fluorosulfonyl) (trifluoromethanesulfonyl) imide anion, bis ( It is any one anion selected from the group consisting of (difluorophosphonyl) imide anions.
• the ionic complex is used in the above [5Pa], [5Pb], [5Pd], and [5Pd] in that the cycle characteristics of the nonaqueous electrolyte battery are enhanced by using it as a component of the electrolyte for the nonaqueous electrolyte battery. It is preferably any one selected from the group consisting of [5Pg], [5Ba], [5Bb], [5Bf], [5Bg] and [5Bi].
• the relationship between the type of ionic complex and the strength of the effect of improving the cycle characteristics when the ionic complex is used as a component of the electrolyte for a non-aqueous electrolyte battery is 5Pa> 3Bd-Li >> 5Ba> 5Bi. 5Bf >> 5Pd. Therefore, the ionic complex is particularly preferably 5 Pa or 3Bd—Li.
• the “3Bd—Li” means an ionic complex in which A of 3Bd is Li.
• the cycle characteristics of the non-aqueous electrolyte battery can be improved by using the ionic complex (IB-1) having a cyclic structure as a component of the electrolyte for the non-aqueous electrolyte battery.
• the ionic complex (IB-1) having a cyclic structure as a component of the electrolyte for the non-aqueous electrolyte battery.
• the content of the ionic complex (IB-1) having a cyclic structure with respect to the total amount of (I) to (V) of 100% by mass is preferably 0.001 to 20% by mass, and 0.01 to 10. It is more preferably in the range of 0% by mass, more preferably in the range of 0.1 to 5.0% by mass, and still more preferably in the range of 0.5 to 2.0% by mass. If the concentration of the ionic complex is too low, the effect of improving durability at high temperatures such as the cycle characteristics of the non-aqueous electrolyte battery may not be sufficiently obtained. If it is too high, the viscosity of the electrolyte will increase.
• ionic complexes having a cyclic structure may be used alone, or two or more kinds may be mixed in any combination and ratio according to the application.
• the salt having an imide anion contains a site having a high electron-withdrawing property (for example, a fluorine atom or a fluorine-containing alkoxy group), the bias of charge becomes larger, and the film with lower resistance (better output characteristics) It is considered that a film is formed.
• a site having a high electron-withdrawing property for example, a fluorine atom or a fluorine-containing alkoxy group
• the anion of the salt having an imide anion represented by the above general formulas [11] to [17] include the following compounds.
• the salt having an imide anion used in the present invention is not limited by the following examples. Among these, from the viewpoint of forming a film with lower resistance (good output characteristics), [11a], [11c], [12a], [12b], [12c], [13a], and the above [13d] and [14a] above are preferable.
• the high-temperature cycle characteristics can be improved by using the salt having an imide anion (IB-2) as a component of the electrolyte for a non-aqueous electrolyte battery.
• Some salts having an imide anion further tend to improve high-temperature storage characteristics and low-temperature cycle characteristics.
• the imide anion is contained even in a system containing the salt having the imide anion and a monomer body of a carbonate compound containing an unsaturated bond. It is easy to improve the rate characteristics without impairing the effect of improving the cycle characteristics of the salt.
• the preferred content of the salt (IB-2) having an imide anion with respect to 100% by mass of the total amount of (I) to (V) is 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably Is 0.1% by mass or more, and the upper limit is 13.0% by mass or less, more preferably 10.0% by mass or less, and still more preferably 7.0% by mass or less. If it is less than 0.001% by mass, the effect of improving the output characteristics of the nonaqueous electrolyte battery at low temperature may not be sufficiently obtained.
• the salt which has this imide anion may be used individually by 1 type, and may mix 2 or more types by arbitrary combinations and a ratio according to a use.
• Si-containing compound [(IB-3) Si-containing compound] There exists a tendency which can improve cycling characteristics because a non-aqueous electrolyte contains a Si containing compound. Further, some Si-containing compounds can further reduce the amount of gas generated. As the Si-containing compound, a compound represented by the above general formula [18] is preferable.
• Si-containing compound represented by the general formula [18] include the following [18a] to [18y].
• the Si-containing compound used in the present invention is not limited by the following examples. Among these, [18c] and [181] are preferable from the viewpoint of forming a stronger film (good durability).
• the cycle characteristics of the non-aqueous electrolyte battery can be improved by using the Si-containing compound (IB-3) as a component of the electrolyte for the non-aqueous electrolyte battery.
• the Si-containing compound (IB-3) as a component of the electrolyte for the non-aqueous electrolyte battery.
• a suitable content of the Si-containing compound (IB-3) with respect to 100% by mass of the total amount of (I) to (V) is 0.005% by mass or more, more preferably 0.03% by mass or more, and further preferably Moreover, it is 0.05 mass% or more, and an upper limit is 7.0 mass% or less, More preferably, it is 5.0 mass% or less, More preferably, it is 2.5 mass% or less. If the concentration is less than 0.005% by mass, it is difficult to sufficiently obtain the effect of improving the high-temperature cycle characteristics of a non-aqueous electrolyte battery using the non-aqueous electrolyte.
• One of these Si-containing compounds may be used alone, or two or more of these Si-containing compounds may be mixed in any combination and ratio according to the application.
• Examples of the cyclic sulfonate ester having an unsaturated bond represented by the general formula [19] include 1,3-propene sultone, 1,4-butene sultone, 2,4-pentene sultone, 3,5-pentene sultone, 1- Fluoro-1,3-propene sultone, 1-trifluoromethyl-1,3-propene sultone, 1,1,1-trifluoro-2,4-butene sultone, 1,4-butene sultone, 1,5-pentene sultone, etc. Is mentioned. In particular, considering the reactivity in the battery system, it is more preferable to use 1,3-propene sultone or 1,4-butene sultone.
• Examples of the cyclic disulfonic acid ester represented by the general formula [20] include compounds represented by [20a] to [20ac]. Of these, the compounds shown in [20a], [20b], [20j], [20o] or [20p] are more preferable.
• the cyclic disulfonic acid ester represented by the general formula [20] is not limited to the compounds represented by [20a] to [20ac], and may be other compounds.
• Examples of the cyclic disulfonic acid ester represented by the general formula [21] include compounds represented by [21a] to [21e]. Of these, the compounds shown in [21a], [21b] or [21e] are more preferred.
• the cyclic disulfonic acid ester represented by the general formula [21] is not limited to the compounds shown in [21a] to [21e], and may be other compounds.
• the cycle characteristics of the non-aqueous electrolyte battery tend to be improved.
• the cycle of the sulfate ester compound It is easy to improve the rate characteristics without impairing the effect of improving the characteristics.
• the preferred content of the sulfate ester compound (IB-4) with respect to 100% by mass of the total amount of (I) to (V) is 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably Moreover, it is 0.1 mass% or more, and an upper limit is 10.0 mass% or less, More preferably, it is 5.0 mass% or less, More preferably, it is the range of 2.0 mass% or less. When the concentration is less than 0.001% by mass, it is not preferable because the effect of improving the cycle characteristics of a non-aqueous electrolyte battery using the non-aqueous electrolyte is not sufficiently obtained.
• the concentration exceeds 10.0% by mass, the effect of improving the cycle characteristics of a non-aqueous electrolyte battery using the non-aqueous electrolyte is not sufficiently obtained, which is not preferable.
• One of these sulfate ester compounds may be used alone, or two or more thereof may be mixed in any combination and ratio according to the application.
• phosphoric acid ester compound examples are not particularly limited to these.
• cycle characteristics can be improved by using a phosphoric acid ester compound (IB-5) as a component of an electrolyte for a non-aqueous electrolyte battery.
• a phosphoric acid ester compound IB-5
• the phosphate ester compound It is easy to improve the rate characteristics without impairing the effect of improving the cycle characteristics.
• the preferred content of the phosphate ester compound (IB-5) with respect to 100% by mass of the total amount of (I) to (V) is 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably Is 0.1% by mass or more, and the upper limit is 15.0% by mass or less, more preferably 12.0% by mass or less, and still more preferably 10.0% by mass or less.
• concentration is less than 0.001% by mass, it is not preferable because the effect of improving the cycle characteristics of a non-aqueous electrolyte battery using the non-aqueous electrolyte is not sufficiently obtained.
• phosphate ester compounds may be used individually by 1 type, and may mix 2 or more types by arbitrary combinations and a ratio according to a use.
• [(IB-6) cyclic carbonate compound] There exists a tendency which can improve cycling characteristics because a non-aqueous electrolyte solution contains a cyclic carbonate compound.
• Specific examples of the cyclic carbonate compound represented by the general formula [22] include, for example, cyclic carbonate compounds represented by [22a] to [22f]. Especially, the compound shown in [22a] is more preferable at the point with the durable improvement effect.
• the cyclic carbonate compound represented by the general formula [22] is not limited to the compounds represented by [22a] to [22f], and may be other compounds.
• the cyclic carbonate compound may correspond to a monomer corresponding to the repeating unit represented by the general formula [1], in which case, as described above,
• the cycle characteristics of the non-aqueous electrolyte battery tend to be improved. Even if the cyclic carbonate compound is a system containing the cyclic carbonate compound and a monomer compound of a carbonate compound containing an unsaturated bond by containing a predetermined amount of the additive for non-aqueous electrolyte solution of the present invention, the cycle of the cyclic carbonate compound It is easy to improve the rate characteristics without impairing the characteristics improvement effect.
• the cyclic carbonate compound (IB-6) with respect to 100% by mass of the total amount of (I) to (V)
• the preferred content of is 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.1% by mass or more, and the upper limit is 10.0% by mass or less, more preferably It is 5.0 mass% or less, More preferably, it is the range of 2.0 mass% or less. If the concentration is less than 0.001% by mass, it is not preferable because the effect of improving the cycle characteristics of a non-aqueous electrolyte battery using the non-aqueous electrolyte is not sufficiently obtained.
• cyclic carbonate compounds may be used alone, or two or more thereof may be mixed in any combination and ratio according to the application.
• isocyanate compound examples are not particularly limited, and examples thereof include hexamethylene diisocyanate, octamethylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate.
• the high-temperature cycle characteristics can be improved by using the isocyanate compound (IB-7) as a component of the electrolyte for a non-aqueous electrolyte battery.
• the isocyanate compound and a monomer compound of a carbonate compound containing an unsaturated bond can be used in the high-temperature cycle characteristics of the isocyanate compound. It is easy to improve rate characteristics without impairing the improvement effect.
• a suitable content of the isocyanate compound (IB-7) with respect to 100% by mass of the total amount of (I) to (V) is 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.
• the upper limit is 7.0% by mass or less, more preferably 5.0% by mass or less, and still more preferably 2.0% by mass or less. If the concentration is less than 0.001% by mass, it is not preferable because the effect of improving the cycle characteristics of a non-aqueous electrolyte battery using the non-aqueous electrolyte is not sufficiently obtained.
• isocyanate compounds may be used individually by 1 type, and may mix 2 or more types by arbitrary combinations and a ratio according to a use.
• cyclic acetal compound examples include 1,3-dioxolane, 1,3-dioxane, and 1,3,5-trioxane. Among them, 1,3-dioxane is preferable.
• the high-temperature cycle characteristics can be improved by using the cyclic acetal compound (IB-8) as a component of the electrolyte for a non-aqueous electrolyte battery. Even if the system contains the cyclic acetal compound and a monomer compound of a carbonate compound containing an unsaturated bond by containing a predetermined amount of the additive for non-aqueous electrolyte solution of the present invention, the cyclic acetal compound has a high temperature. It is easy to improve the rate characteristics without impairing the cycle characteristics improvement effect.
• the preferred content of the cyclic acetal compound (IB-8) with respect to 100% by mass of the total amount of (I) to (V) is 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably Moreover, it is 0.1 mass% or more, and an upper limit is 7.0 mass% or less, More preferably, it is 5.0 mass% or less, More preferably, it is the range of 2.0 mass% or less. If the concentration is less than 0.001% by mass, it is not preferable because the effect of improving the cycle characteristics of a non-aqueous electrolyte battery using the non-aqueous electrolyte is not sufficiently obtained.
• cyclic acetal compounds may be used individually by 1 type, and may mix 2 or more types by arbitrary combinations and a ratio according to a use.
• cyclic acid anhydride examples include succinic anhydride, maleic anhydride, 3-allyl succinic anhydride, etc. Among them, succinic anhydride and 3-allyl succinic anhydride are preferable.
• cyclic acid anhydride (IB-9) as a component of the electrolyte for non-aqueous electrolyte batteries. Even if it is a system containing the cyclic acid anhydride and a monomer body of a carbonate compound containing an unsaturated bond by containing a predetermined amount of the additive for non-aqueous electrolyte solution of the present invention, the cyclic acid anhydride It is easy to improve the rate characteristics without impairing the high temperature cycle characteristics improvement effect.
• the preferred content of the cyclic acid anhydride (IB-9) with respect to 100% by mass of the total amount of (I) to (V) is 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably Is 0.1% by mass or more, and the upper limit is 7.0% by mass or less, more preferably 5.0% by mass or less, and still more preferably 2.0% by mass or less. If the concentration is less than 0.001% by mass, it is not preferable because the effect of improving the cycle characteristics of a non-aqueous electrolyte battery using the non-aqueous electrolyte is not sufficiently obtained.
• cyclic acid anhydrides may be used individually by 1 type, and may mix 2 or more types by arbitrary combinations and a ratio according to a use.
• cyclic phosphazene compound examples include methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, diethoxypentafluorocyclotriphosphazene, and ethoxyheptafluorocyclotetraphosphazene. Ethoxypentafluorocyclotriphosphazene is preferred.
• the high-temperature cycle characteristics can be improved by using the cyclic phosphazene compound (IB-10) as a component of the electrolyte for a non-aqueous electrolyte battery.
• the cyclic phosphazene compound is a system containing the cyclic phosphazene compound and a monomeric compound of a carbonate compound containing an unsaturated bond by containing a predetermined amount of the additive for non-aqueous electrolyte solution of the present invention, the cyclic phosphazene compound has a high temperature. It is easy to improve the rate characteristics without impairing the cycle characteristics improvement effect.
• a suitable content of the cyclic phosphazene compound (IB-10) with respect to 100% by mass of the total amount of (I) to (V) is 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably Moreover, it is 0.1 mass% or more, and an upper limit is 7.0 mass% or less, More preferably, it is 5.0 mass% or less, More preferably, it is the range of 3.0 mass% or less. If the concentration is less than 0.001% by mass, it is not preferable because the effect of improving the cycle characteristics of a non-aqueous electrolyte battery using the non-aqueous electrolyte is not sufficiently obtained.
• cyclic phosphazene compounds may be used individually by 1 type, and may mix 2 or more types by arbitrary combinations and a ratio according to a use.
• Aromatic Compound There exists a tendency which can improve a high temperature cycling characteristic because a non-aqueous electrolyte solution contains an aromatic compound. Some aromatic compounds further tend to suppress overcharge under high voltage conditions.
• aromatic compound examples include cyclohexylbenzene, biphenyl, tert-butylbenzene, 4-fluorobiphenyl, fluorobenzene, 2,4-difluorobenzene, 1-cyclohexyl-4-fluorobenzene, and difluoroanisole, Of these, 1-cyclohexyl-4-fluorobenzene is preferable.
• the high-temperature cycle characteristics can be improved by using the aromatic compound (IB-11) as a component of the electrolyte for a non-aqueous electrolyte battery.
• the aromatic compound (IB-11) as a component of the electrolyte for a non-aqueous electrolyte battery.
• a suitable content of the aromatic compound (IB-11) with respect to 100% by mass of the total amount of (I) to (V) is 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably Moreover, it is 0.1 mass% or more, and an upper limit is 20.0 mass% or less, More preferably, it is 10.0 mass% or less, More preferably, it is the range of 5.0 mass% or less. If the concentration is less than 0.001% by mass, it is not preferable because the effect of improving the cycle characteristics of a non-aqueous electrolyte battery using the non-aqueous electrolyte is not sufficiently obtained.
• aromatic compounds may be used individually by 1 type, and may mix 2 or more types by arbitrary combinations and a ratio according to a use.
• the electrolytic solution of the present invention includes, as (I), an ionic complex having a cyclic structure, a salt having an imide anion, a Si-containing compound, a sulfate ester compound, a phosphate ester compound, a cyclic carbonate compound, and an isocyanate compound.
• a cyclic acetal compound, a cyclic acid anhydride, a cyclic phosphazene compound, and an aromatic compound may contain only one kind of substance, or may contain a plurality of substances in any combination, but oxalato Salt and / or difluorophosphate, ionic complex having cyclic structure, salt having imide anion, Si-containing compound, sulfate ester compound, phosphate ester compound, cyclic carbonate compound, isocyanate compound, cyclic acetal compound, cyclic acid Is it a group consisting of anhydrides, cyclic phosphazene compounds, aromatic compounds? It is one of the preferred embodiments containing at least one compound selected.
• the non-aqueous electrolyte solution of the present invention contains a monomer represented by the following general formula [1].
• R represents a hydrogen atom, a halogen, or a lower alkyl group. R may be all the same or different, and may be linked to each other to have a cyclic structure.
• R in the general formula [1] is a hydrogen atom, a halogen or a lower alkyl group.
• the halogen include a fluorine atom, a chlorine atom, and a bromine atom
• examples of the lower alkyl group include a methyl group, an ethyl group, and a propyl group.
• R is preferably a hydrogen atom.
• the monomer represented by the general formula [1] is considered to constitute a part of a film formed on the electrode surface during charge and discharge and to improve cycle characteristics. From the viewpoint of improving cycle characteristics, the content of (II) with respect to 100% by mass of the total amount of (I), (II), (III), (IV), and (V) is 0.0001% by mass or more. preferable. On the other hand, if the content of the monomer represented by the general formula [1] is too large, the rate characteristics tend to be impaired, so the upper limit of the content of (II) is preferably 0.25% by mass. . A more preferred upper limit is 0.2% by mass.
• Non-aqueous organic solvent If a non-aqueous solvent is used, the non-aqueous electrolyte is generally called a non-aqueous electrolyte, and if a polymer is used, it becomes a polymer solid electrolyte.
• the polymer solid electrolyte includes those containing a non-aqueous solvent as a plasticizer.
• the non-aqueous organic solvent (III) is not particularly limited as long as it is an aprotic solvent that can dissolve (I), (II), (IV), and (V) of the present invention.
• Carbonates, esters, ethers, lactones, nitriles, imides, sulfones and the like can be used.
• not only a single solvent but 2 or more types of mixed solvents may be sufficient.
• ethyl methyl carbonate dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl butyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4, 5-difluoroethylene carbonate, 4,5-difluoro-4,5-dimethylethylene carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate, diethyl ether , Acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, furan, tetrahydropyran, 1, - dioxane, 1,4-dioxane, dibutyl ether, diisopropyl ether,
• the polymer used for obtaining the polymer solid electrolyte is not particularly limited as long as it is an aprotic polymer capable of dissolving (I), (II), (IV), and (V).
• aprotic polymer capable of dissolving (I), (II), (IV), and (V).
• examples thereof include a polymer having polyethylene oxide in the main chain or side chain, a homopolymer or copolymer of polyvinylidene fluoride, a methacrylic acid ester polymer, polyacrylonitrile and the like.
• a plasticizer is added to these polymers, the above-mentioned aprotic non-aqueous solvent can be used.
• the solute is not particularly limited, and a salt composed of an arbitrary cation and anion pair can be used.
• a salt composed of an arbitrary cation and anion pair can be used.
• Specific examples include alkali metal ions such as lithium ions and sodium ions, alkaline earth metal ions, quaternary ammonium, etc. as cations, and hexafluorophosphoric acid, tetrafluoroboric acid, perchloric acid as anions.
• the cation is preferably at least one selected from the group consisting of lithium, sodium, magnesium and quaternary ammonium, and the anion is hexafluorophosphate, tetra From the group consisting of fluoroboric acid, bis (trifluoromethanesulfonyl) imide, bis (pentafluoroethanesulfonyl) imide, bis (fluorosulfonyl) imide, bis (difluorophosphonyl) imide, (difluorophosphonyl) (fluorosulfonyl) imide At least one selected is preferred.
• lithium hexafluorophosphate LiPF 6
• lithium tetrafluoroborate LiBF 4
• bis (trifluoromethanesulfonyl) imide lithium LiN (CF 3 SO 2 ) 2
• bis (pentafluoroethanesulfonyl) imide lithium From the group consisting of (LiN (C 2 F 5 SO 2 ) 2 ), bis (fluorosulfonyl) imide lithium (LiN (FSO 2 ) 2 ), and bis (difluorophosphonyl) imide lithium (LiN (POF 2 ) 2 ) At least one selected is preferred.
• the total amount of (IV) (hereinafter referred to as “solute concentration”) with respect to 100% by mass of the total amount of (I), (II), (III), (IV), (V) is not particularly limited.
• the lower limit is 0.5 mol / L or more, preferably 0.7 mol / L or more, more preferably 0.9 mol / L or more, and the upper limit is 5.0 mol / L or less, preferably 4.0 mol / L or less. More preferably, it is the range of 2.0 mol / L or less.
• concentration is less than 0.5 mol / L, the ionic conductivity decreases, thereby reducing the cycle characteristics and output characteristics of the non-aqueous electrolyte secondary battery.
• the concentration exceeds 5.0 mol / L, the viscosity of the non-aqueous electrolyte is decreased. If it rises, the ionic conduction may be lowered, and the cycle characteristics and output characteristics of the non-aqueous electrolyte secondary battery may be lowered.
• the non-aqueous electrolyte of the present invention includes an additive for a non-aqueous electrolyte that is an oligomer having a repeating unit represented by the following general formula [2] and has a polystyrene-equivalent number average molecular weight of 170 to 5,000. It is.
• a non-aqueous electrolyte that is an oligomer having a repeating unit represented by the following general formula [2] and has a polystyrene-equivalent number average molecular weight of 170 to 5,000. It is.
• the inside of the parenthesis means that each is a repeating unit.
• R represents a hydrogen atom, a halogen or a lower alkyl group.
• R may be all the same or different, and may be linked to each other by a covalent bond to have a cyclic structure.
• the additive for non-aqueous electrolyte solution of the present invention is an oligomer having a repeating unit represented by the general formula [2]. It is important that the non-aqueous electrolyte additive is an oligomer, that is, a multimer rather than a monomer. It is important that the non-aqueous electrolyte additive has a polystyrene-equivalent number average molecular weight of 170 to 5,000. When the polymer is a multimer of repeating units represented by the general formula [2] and has the number average molecular weight, when used in a non-aqueous electrolyte secondary battery, the cycle characteristics and rate characteristics are exhibited in a balanced manner. be able to. From the viewpoint of cycle characteristics and / or rate characteristics, the number average molecular weight is preferably 340 to 4000, more preferably 800 to 3000, and particularly preferably 1000 to 2500.
• R in the general formula [2] is a hydrogen atom, a halogen or a lower alkyl group.
• the halogen include a fluorine atom, a chlorine atom, and a bromine atom
• examples of the lower alkyl group include a methyl group, an ethyl group, and a propyl group.
• R is preferably a hydrogen atom.
• the non-aqueous electrolyte additive is obtained by previously polymerizing the corresponding monomer.
• the polymerization method is not particularly limited as long as it is a generally used method, but it can be polymerized by a radical polymerization method or a photopolymerization method. Of these, radical polymerization is particularly preferred.
• Radical polymerization is carried out in the presence of a radical polymerization initiator or a radical initiator by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, and is either batch-wise, semi-continuous or continuous. Can be implemented by operation.
• the radical initiator is not particularly limited, and examples thereof include azo compounds, peroxide compounds, and redox compounds.
• azo compounds peroxide compounds, and redox compounds.
• the reactor used in the polymerization reaction for obtaining the polymer represented by the general formula [2] is not particularly limited.
• a polymerization solvent may be used.
• the polymerization solvent those which do not inhibit radical polymerization are preferable, and ester solvents such as ethyl acetate, n-butyl acetate, ketone solvents such as acetone, methyl isobutyl ketone, hydrocarbon solvents such as toluene, cyclohexane, and aprotic solvents. Examples thereof include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and dimethyl sulfoxide, which are polar solvents.
• the reaction temperature is appropriately selected depending on the radical initiator or radical initiator, and is preferably in the range of 20 to 200 ° C, more preferably 30 to 140 ° C. Moreover, you may perform reprecipitation refinement
• the non-aqueous electrolyte solution of the present invention contains the above-mentioned additive for non-aqueous electrolyte solution.
• the content of (V) is 0.03 to 14.0% by mass with respect to 100% by mass of the total amount of (I), (II), (III), (IV), and (V)
• a non-aqueous electrolyte solution When used in a secondary battery, it is preferable because the cycle characteristics and rate characteristics are easily exhibited in a well-balanced manner. From the viewpoint of cycle characteristics and / or rate characteristics, the content of (V) is more preferably 0.07 to 12.0% by mass.
• the total amount (M) of the monomer and the total amount (P) of the non-aqueous electrolyte additive (in monomer conversion) in the non-aqueous electrolyte are calculated from the 1 H-NMR measurement results.
• an additive having an overcharge prevention effect, a negative electrode film formation effect, and a positive electrode protection effect generally used in the non-aqueous electrolyte solution of the present invention may be added at an arbitrary ratio. good.
• a non-aqueous electrolyte by quasi-solidifying it with a gelling agent or a cross-linked polymer as in the case of use in a non-aqueous electrolyte secondary battery called a polymer battery.
• Non-aqueous electrolyte secondary battery Non-aqueous electrolyte, negative electrode material capable of reversibly inserting and removing alkali metal ions such as lithium ions and sodium ions, or alkaline earth metal ions, lithium ions and sodium
• An electrochemical device using a positive electrode material into which alkali metal ions such as ions or alkaline earth metal ions can be reversibly inserted and removed is called a non-aqueous electrolyte secondary battery.
• the negative electrode is not particularly limited, but a material in which an alkali metal ion such as lithium ion or sodium ion or an alkaline earth metal ion can be reversibly inserted and removed is used, and the positive electrode is not particularly limited. However, materials in which alkali metal ions such as lithium ions and sodium ions or alkaline earth metal ions can be reversibly inserted and removed are used.
• the negative electrode material is lithium metal, alloys of lithium and other metals, intermetallic compounds, various carbon materials capable of inserting and extracting lithium, metal oxides, metal nitrides, activated carbon
• the carbon material include graphitizable carbon, non-graphitizable carbon (also referred to as hard carbon) having a (002) plane spacing of 0.37 nm or more, and a (002) plane spacing of 0.
• Examples include graphite having a thickness of 37 nm or less, and the latter is made of artificial graphite, natural graphite, or the like.
• lithium-containing transition metal composite oxides such as 4 as a positive electrode material
• a mixture of a plurality of transition metals for example, LiNi 0.5 Mn 1.5 O 4 ), a transition metal part of those lithium-containing transition metal composite oxides substituted with a metal other than the transition metal, called olivine LiFePO 4, LiCoPO 4, LiMnPO phosphate compound of a transition metal such as 4, an oxide such as TiO 2, V 2 O 5, MoO 3, TiS 2, sulfides such as FeS, or polyacetylene, polyparaphenylene, polyaniline, And conductive polymers such as polypyrrole, activated carbon, polymers generating radicals, carbon materials, etc. are used. olivine LiFePO 4, LiCoPO 4, LiMnPO phosphate compound of a transition metal such as 4, an oxide such as TiO 2, V 2 O 5, MoO 3, TiS 2, sulfides such as FeS, or polyacetylene, polyparaphenylene, polyaniline, And conductive polymers such as polypyrrole, activated carbon, polymers generating radicals, carbon materials
• acetylene black, ketjen black, carbon fiber, or graphite is added as a conductive material, and polytetrafluoroethylene, polyvinylidene fluoride, or SBR resin is added as a binder.
• the electrode sheet made can be used.
• a separator for preventing contact between the positive electrode and the negative electrode a nonwoven fabric or a porous sheet made of polypropylene, polyethylene, paper, glass fiber or the like is used.
• an electrochemical device having a coin shape, cylindrical shape, square shape, aluminum laminate sheet shape or the like is assembled.
• a non-aqueous electrolyte secondary battery includes a non-aqueous electrolyte comprising: (i) the non-aqueous electrolyte described above; (ii) a positive electrode; (iii) a negative electrode; and (iv) a separator.
• An electrolyte secondary battery may be used.
• the positive electrode preferably contains at least one oxide and / or polyanion compound as the positive electrode active material.
• the positive electrode active material constituting the positive electrode is not particularly limited as long as it is various materials that can be charged and discharged.
• the positive electrode active material constituting the positive electrode is not particularly limited as long as it is various materials that can be charged and discharged.
• mold phosphate and the lithium excess layered transition metal oxide which has (D) layered rock salt type structure is mentioned.
• lithium transition metal composite oxide Cathode active material
• lithium transition metal composite oxides containing at least one metal selected from nickel, manganese and cobalt and having a layered structure include lithium-cobalt composite oxides and lithium-nickel composite oxides. Lithium / nickel / cobalt composite oxide, lithium / nickel / cobalt / aluminum composite oxide, lithium / cobalt / manganese composite oxide, lithium / nickel / manganese composite oxide, lithium / nickel / manganese / cobalt composite oxide Etc.
• transition metal atoms that are the main components of these lithium transition metal composite oxides are Al, Ti, V, Cr, Fe, Cu, Zn, Mg, Ga, Zr, Si, B, Ba, Y, Sn. Those substituted with other elements such as may also be used.
• lithium-cobalt composite oxide and the lithium-nickel composite oxide include LiCoO 2 , LiNiO 2 and lithium cobaltate to which a different element such as Mg, Zr, Al, Ti is added (LiCo 0.98 Mg 0.01 Zr 0.01 O 2 , LiCo 0.98 Mg 0.01 Al 0.01 O 2 , LiCo 0.975 Mg 0.01 Zr 0.005 Al 0.01 O 2, etc.), lithium cobaltate with a rare earth compound fixed to the surface described in WO2014 / 034043, etc. may be used. . Further, as described in Japanese Patent Application Laid-Open No. 2002-151077, etc., a part of the particle surface of LiCoO 2 particle powder coated with aluminum oxide may be used.
• the lithium / nickel / cobalt composite oxide and the lithium / nickel / cobalt / aluminum composite oxide are represented by the general formula (1-1).
• M 1 is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, and B, a is 0.9 ⁇ a ⁇ 1.2, b , C satisfy the conditions of 0.1 ⁇ b ⁇ 0.3 and 0 ⁇ c ⁇ 0.1.
• the composite oxide examples include LiNi 0.5 Mn 0.5 O 2 and LiCo 0.5 Mn 0.5 O 2 .
• lithium / nickel / manganese / cobalt composite oxide examples include a lithium-containing composite oxide represented by the general formula (1-2).
• M 2 is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, B, and Sn, and d is 0.9 ⁇ d ⁇ 1.2.
• Lithium / nickel / manganese / cobalt composite oxides contain manganese in the range represented by the general formula (1-2) in order to improve structural stability and improve safety at high temperatures in lithium secondary batteries.
• cobalt in the range represented by the general formula (1-2).
• Li [Ni 1/3 Mn 1/3 Co 1/3 ] O 2 Li [Ni 0.45 Mn 0.35 Co 0.2 ] O 2 , Li [Ni having a charge / discharge region at 4.3 V or higher.
• lithium manganese composite oxide having spinel structure examples include a spinel type lithium manganese composite oxide represented by the general formula (1-3).
• M 3 is at least one metal element selected from the group consisting of Ni, Co, Fe, Mg, Cr, Cu, Al, and Ti, and j is 1.05 ⁇ j ⁇ 1. 15 and k is 0 ⁇ k ⁇ 0.20.
• LiMn 2 O 4 LiMn 1.95 Al 0.05 O 4 , LiMn 1.9 Al 0.1 O 4 , LiMn 1.9 Ni 0.1 O 4 , LiMn 1.5 Ni 0.5 O 4 and the like can be mentioned.
• Examples of the positive electrode active material (C) lithium-containing olivine-type phosphate include those represented by the general formula (1-4).
• M 4 is at least one selected from Co, Ni, Mn, Cu, Zn, Nb, Mg, Al, Ti, W, Zr, and Cd, and n is 0 ⁇ n ⁇ 1.
• LiFePO 4 , LiCoPO 4 , LiNiPO 4 , LiMnPO 4 and the like can be mentioned, among which LiFePO 4 and / or LiMnPO 4 are preferable.
• lithium-excess layered transition metal oxide examples include those represented by the general formula (1-5).
• x is a number satisfying 0 ⁇ x ⁇ 1
• M 5 is at least one metal element having an average oxidation number of 3 +
• M 6 is an average oxidation It is at least one metal element having a number of 4 + .
• M 5 is preferably one or more metal elements selected from trivalent Mn, Ni, Co, Fe, V, and Cr. The average oxidation number may be trivalent with an amount of metal.
• M 6 is preferably one or more metal elements selected from Mn, Zr, and Ti.
• the positive electrode active material (D) represented by the general formula (1-5) is known to exhibit a high capacity when charged at a high voltage of 4.4 V (Li standard) or higher (for example, US Pat. No. 7 , 135, 252).
• These positive electrode active materials can be prepared according to the production methods described in, for example, JP 2008-270201 A, WO 2013/118661, JP 2013-030284 A, and the like.
• the positive electrode active material may contain at least one selected from the above (A) to (D) as a main component, but other examples include FeS 2 , TiS 2 , V 2 O 5. , Transition element chalcogenides such as MoO 3 and MoS 2 , or conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, polymers that generate radicals, and carbon materials.
• the positive electrode has a positive electrode current collector.
• the positive electrode current collector for example, aluminum, stainless steel, nickel, titanium, or an alloy thereof can be used.
• a positive electrode active material layer is formed on at least one surface of the positive electrode current collector.
• a positive electrode active material layer is comprised by the above-mentioned positive electrode active material, a binder, and a electrically conductive agent as needed, for example.
• binder examples include polytetrafluoroethylene, polyvinylidene fluoride, or styrene butadiene rubber (SBR) resin.
• SBR styrene butadiene rubber
• a carbon material such as acetylene black, ketjen black, carbon fiber, or graphite (granular graphite or flake graphite) can be used.
• acetylene black or ketjen black having low crystallinity.
• the negative electrode preferably contains at least one negative electrode active material.
• the negative electrode active material constituting the negative electrode can be doped / dedoped with lithium ions.
• a material (G) an oxide of one or more metals selected from Si, Sn, Al, (H) one or more metals selected from Si, Sn, Al, alloys containing these metals, or these metals or alloys; Examples include an alloy with lithium and (I) at least one selected from lithium titanium oxide.
• These negative electrode active materials can be used individually by 1 type, and can also be used in combination of 2 or more type.
• Examples of the carbon material having a d value of 0.340 nm or less in the lattice plane (002 plane) in the negative electrode active material (E) X-ray diffraction include pyrolytic carbons and cokes (for example, pitch coke, needle coke, and petroleum coke).
• Graphites organic polymer compound fired bodies (for example, those obtained by firing and carbonizing a phenol resin, furan resin, etc.), carbon fibers, activated carbon, and the like. These may be graphitized.
• the carbon material has a (002) plane spacing (d002) of 0.340 nm or less measured by an X-ray diffraction method, among which graphite having a true density of 1.70 g / cm 3 or more, or A highly crystalline carbon material having close properties is preferred.
• amorphous carbon As the carbon material in which the d value of the lattice plane (002 plane) in the negative electrode active material (F) X-ray diffraction exceeds 0.340 nm, amorphous carbon can be cited, which is obtained by heat treatment at a high temperature of 2000 ° C. or higher. Is a carbon material whose stacking order hardly changes. Examples thereof include non-graphitizable carbon (hard carbon), mesocarbon microbeads (MCMB) baked at 1500 ° C. or less, and mesopage bitch carbon fiber (MCF). A typical example is Carbotron (registered trademark) P manufactured by Kureha Co., Ltd.
• Negative electrode active material (G) One or more metal oxides selected from Si, Sn, and Al)
• Negative electrode active material (G) One or more metal oxides selected from Si, Sn, and Al can be doped / dedoped with lithium ions, such as silicon oxide and tin oxide. .
• Examples include SiO x having a structure in which ultrafine particles of Si are dispersed in SiO 2 .
• SiO x particles having the above structure itself have a small surface area, so that the negative electrode active material layer
• the coating properties and the adhesion of the negative electrode mixture layer to the current collector when the composition (paste) is used to form the film are also good.
• SiO x has a large volume change due to charge / discharge
• high capacity and good charge / discharge cycle characteristics can be obtained by using SiO x and graphite of the negative electrode active material (E) in a specific ratio in combination with the negative electrode active material. And both.
• Negative electrode active material (H) one or more metals selected from Si, Sn, Al, alloys containing these metals, or alloys of these metals or alloys and lithium)
• Negative electrode active material (H) one or more metals selected from Si, Sn, Al, alloys containing these metals, or alloys of these metals or alloys and lithium include, for example, metals such as silicon, tin, and aluminum, and silicon alloys , Tin alloys, aluminum alloys, and the like, and materials in which these metals and alloys are alloyed with lithium during charge and discharge can also be used.
• a negative electrode active material formed of silicon micro pillars having a submicron diameter a negative electrode active material formed of fibers made of silicon, and the like described in WO 2004/042851 and WO 2007/083155 may be used. .
• Examples of the negative electrode active material (I) lithium titanium oxide include lithium titanate having a spinel structure and lithium titanate having a ramsdellite structure.
• lithium titanate having a spinel structure examples include Li 4 + ⁇ Ti 5 O 12 ( ⁇ varies within a range of 0 ⁇ ⁇ ⁇ 3 due to a charge / discharge reaction).
• lithium titanate having a ramsdellite structure examples include Li 2 + ⁇ Ti 3 O 7 ( ⁇ varies within a range of 0 ⁇ ⁇ ⁇ 3 due to charge / discharge reaction).
• These negative electrode active materials can be prepared according to the production methods described in, for example, Japanese Patent Application Laid-Open No. 2007-018883 and Japanese Patent Application Laid-Open No. 2009-176752.
• the cation in the non-aqueous electrolyte is mainly sodium
• hard carbon oxides such as TiO 2 , V 2 O 5 , and MoO 3 are used as the negative electrode active material.
• a sodium-containing transition metal composite oxide such as NaFeO 2 , NaCrO 2 , NaNiO 2 , NaMnO 2 , NaCoO 2 as the positive electrode active material
• transition metals such as Fe, Cr, Ni, Mn, Co, etc.
• transition metal phosphate compounds such as Na 2 FeP 2 O 7 , NaCo 3 (PO 4 ) 2 P 2 O 7
• sulfides such as TiS 2 and FeS 2
• polyacetylene polypara Conductive polymers such as phenylene, polyaniline, and polypyrrole, activated carbon, polymers that generate radicals, and carbon materials are used.
• the negative electrode has a negative electrode current collector.
• the negative electrode current collector for example, copper, stainless steel, nickel, titanium, or an alloy thereof can be used.
• a negative electrode active material layer is formed on at least one surface of the negative electrode current collector.
• a negative electrode active material layer is comprised by the above-mentioned negative electrode active material, a binder, and a electrically conductive agent as needed, for example.
• binder examples include polytetrafluoroethylene, polyvinylidene fluoride, or styrene butadiene rubber (SBR) resin.
• SBR styrene butadiene rubber
• a carbon material such as acetylene black, ketjen black, carbon fiber, or graphite (granular graphite or flake graphite) can be used.
• the electrode is obtained, for example, by dispersing and kneading an active material, a binder, and, if necessary, a conductive agent in a solvent such as N-methyl-2-pyrrolidone (NMP) or water in a predetermined blending amount.
• NMP N-methyl-2-pyrrolidone
• the paste can be applied to a current collector and dried to form an active material layer.
• the obtained electrode is preferably compressed by a method such as a roll press to adjust the electrode to an appropriate density.
• the non-aqueous electrolyte battery includes (iv) a separator.
• a separator for preventing contact between (ii) the positive electrode and (iii) the negative electrode, a nonwoven fabric or a porous sheet made of polyolefin such as polypropylene or polyethylene, cellulose, paper, glass fiber or the like is used. These films are preferably microporous so that the electrolyte can penetrate and ions can easily pass therethrough.
• the polyolefin separator examples include a membrane that electrically insulates the positive electrode and the negative electrode and is permeable to lithium ions, such as a microporous polymer film such as a porous polyolefin film.
• a porous polyolefin film for example, a porous polyethylene film alone or a porous polyethylene film and a porous polypropylene film may be overlapped and used as a multilayer film.
• the film etc. which compounded the porous polyethylene film and the polypropylene film are mentioned.
• a metal can such as a coin shape, a cylindrical shape, or a square shape, or a laminate exterior body can be used.
• the metal can material include a steel plate subjected to nickel plating, a stainless steel plate, a stainless steel plate subjected to nickel plating, aluminum or an alloy thereof, nickel, and titanium.
• the laminate outer package for example, an aluminum laminate film, a SUS laminate film, a laminate film made of silica, polypropylene, polyethylene, or the like can be used.
• the configuration of the non-aqueous electrolyte battery according to the present embodiment is not particularly limited.
• an electrode element in which a positive electrode and a negative electrode are opposed to each other and a non-aqueous electrolyte are included in an outer package. It can be set as a structure.
• the shape of the non-aqueous electrolyte battery is not particularly limited, but an electrochemical device having a shape such as a coin shape, a cylindrical shape, a square shape, or an aluminum laminate sheet type is assembled from the above elements.
• VC Vinylene carbonate
• NMP N-methylpyrrolidone
• V601 Wako Pure Chemical Industries, Ltd.
• Non-aqueous electrolyte additive No. 1 was subjected to 1 H-NMR measurement, and it was confirmed that all Rs in the above general formula [1] were H and a compound comprising an oligomer.
• non-aqueous electrolyte additive No. 1 GPC measurement was performed, and it was confirmed that the number average molecular weight in terms of polystyrene was 750. The results are shown in Table 1.
• Non-aqueous electrolyte additive No. 1 was subjected to 1 H-NMR measurement, and it was confirmed that all the Rs in the above general formula [1] were H and a compound comprising an oligomer.
• non-aqueous electrolyte additive No. GPC measurement of No. 2 was performed, and it was confirmed that the number average molecular weight in terms of polystyrene was 1000. The results are shown in Table 1.
• Non-aqueous electrolyte additive No. Subjected to 1 H-NMR measurement of 3, that R in the general formula [1] are all H, and was confirmed to be a compound consisting of an oligomer.
• non-aqueous electrolyte additive No. 3 GPC measurement was performed, and it was confirmed that the number average molecular weight in terms of polystyrene was 2000. The results are shown in Table 1.
• Non-aqueous electrolyte additive No. 1 was subjected to 1 H-NMR measurement, and it was confirmed that all Rs in the above general formula [1] were H and that the compound was composed of oligomers.
• non-aqueous electrolyte additive No. GPC measurement of No. 4 was performed, and it was confirmed that the number average molecular weight in terms of polystyrene was 2500. The results are shown in Table 1.
• Non-aqueous electrolyte additive No. 1 was subjected to 1 H-NMR measurement, and it was confirmed that all Rs in the above general formula [1] were H and a compound comprising an oligomer.
• non-aqueous electrolyte additive No. 5 GPC measurement was performed, and it was confirmed that the number average molecular weight in terms of polystyrene was 4500. The results are shown in Table 1.
• Non-aqueous electrolyte additive No. 1 was subjected to 1 H-NMR measurement, and it was confirmed that all Rs in the above general formula [1] were H and a compound comprising an oligomer.
• non-aqueous electrolyte additive No. GPC measurement of 6 was performed, and it was confirmed that the number average molecular weight in terms of polystyrene was 6500. The results are shown in Table 1.
• the non-aqueous organic solvent (III) was prepared such that ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were in a volume ratio of 3: 7.
• EC ethylene carbonate
• EMC ethyl methyl carbonate
• LiPF 6 lithium hexafluorophosphate
• IV lithium hexafluorophosphate
• II lithium difluorobis (oxalato) phosphate
• Table 2 concentration of lithium difluorobis (oxalato) phosphate as (I) is as shown in Table 2 in the solution.
• the monomer of the type shown in Table 2 as (II) is added so as to have the concentration shown in Table 2, and the additive for a non-aqueous electrolyte solution of the type shown in Table 2 is added as (V). By adding so that the concentration shown in FIG. 1A-1 to 1A-23 were obtained.
• LiFSI bis (fluorosulfonyl) imidolithium
• PS 1,3-propane sultone
• PRS 1,3-propene sultone
• MMDS methylenemethane disulfonate
• TFP-MDS 1,5,2,4-dioxadithian-6-trifluoro Ethyl-2,2,4,4-tetraoxide
• VEC vinyl ethylene carbonate
• VEC bis (difluorophosphoryl) imidolithium
• HISHICOLI bis (fluorosulfonyl) imidolithium
• HISHICOLI 1,3-propane sultone
• PRS 1,3-propene sultone
• MMDS methylenemethane disulfonate
• TFP-MDS vinyl ethylene carbonate
• VEC bis (difluorophosphoryl) imidolithium
• HISHICOLI bis (difluorophosphoryl) imidolithium
• FPI difluorophosphoryl (trifluoromethanesulfonyl) imide lithium
• LiDFP-TFMSI difluorophosphoryl (vinylsulfonyl) imide lithium
• LiDFP-VSI difluorophosphoryl (vinylsulfonyl) imide lithium
• FTVSi fluorotrivinylsilane
• TVSi tetravinylsilane
• L difluorophosphoryl (fluorosulfonyl) imide lithium
• The may be described as DFP-FSI "), respectively, by adding to give a concentration shown in Table 4, the electrolytic solution No. 1A-24 to 1A-38 were obtained.
• lithium difluorobis (oxalato) phosphate instead of lithium difluorobis (oxalato) phosphate, lithium difluorophosphate (hereinafter referred to as “LiPO 2 F 2 ” including the table) is used, and the concentration of (II) , (V) as shown in Table 6, the electrolytic solution No. 2A-1 to 2A-23 were obtained.
• lithium difluorobis (oxalato) phosphate instead of using lithium difluorobis (oxalato) phosphate, lithium difluorobis (oxalato) phosphate and LiPO 2 F 2 are used in the ratios shown in Table 10, and the type of (III), (V) Except that the type and content were changed as shown in Table 10, electrolyte No. In the same manner as in 1A-3, the electrolyte No. 3A-1 to 3A-10 were obtained.
• “EC / EMC / DMC3 / 4/3” is a non-aqueous organic solvent in which EC, EMC, and dimethyl carbonate (DMC) are mixed at a volume ratio of 3: 4: 3, and “EC / EMC / FEC3 / 6”.
• EC / 1 is a non-aqueous organic solvent in which EC, EMC and fluoroethylene carbonate (FEC) are mixed at a volume ratio of 3: 6: 1, and“ EC / EMC / PC3 / 5/2 ”is EC and EMC.
• FSI so as to have the concentrations shown in Table 12, the electrolyte solution No. 3A-11 to 3A-25 were obtained.
• electrolyte No. In 4A-3 as component (I), LiFSI, PS, PRS, MMDS, TFP-MDS, VEC, LiFPI, HISHICOLIN E, TFPPA, LiDFP-FPI, LiDFP-TFMSI, LiDFP-VSI, FTVSi, TVSi, LiDFP- By adding FSI so as to have the concentrations shown in Table 16, the electrolyte solution No. 4A-24 to 4A-38 were obtained.
• electrolyte No. In 5A-3 as component (I), LiFSI, PS, PRS, MMDS, TFP-MDS, VEC, LiFPI, HISHICOLIN E, TFPPA, LiDFP-FPI, LiDFP-TFMSI, LiDFP-VSI, FTVSi, TVSi, LiDFP- By adding FSI to the concentrations shown in Table 20, the electrolyte solution No. 5A-24 to 5A-38 were obtained.
• comparative electrolyte No. As shown in Tables 2 and 4, 1A-1 and 1A-24 to 1A-38 were obtained by adding VC corresponding to the monomer (V) without adding (V). Comparative electrolyte No. As shown in Table 2, the additive No. 1A-2 for non-aqueous electrolyte solution was used as (V) as shown in Table 2. 6 was added.
• Comparative electrolyte No. As shown in Table 6, the comparative electrolyte No. In 1A-1, LiPO 2 F 2 was used instead of lithium difluorobis (oxalato) phosphate. Comparative electrolyte No. As shown in Table 8, each of 2A-24 to 2A-38 was electrolyte solution No. except that VC corresponding to the monomer of (V) was added without adding (V). It was obtained in the same manner as 2A-24 to 2A-38. Comparative electrolyte No. 2A-2, as shown in Table 6, the additive No. 6 was added.
• Table 10 shows the use of lithium difluorobis (oxalato) phosphate and LiPO 2 F 2 in the ratio shown in Table 10 in place of lithium difluorobis (oxalato) phosphate, and the type of (III), etc. Except for the change to Comparative Electrolyte No. In the same manner as in 1A-1, the comparative electrolyte No. 3A-1 to 3A-6 were obtained. Comparative electrolyte No. As shown in Table 12, each of 3A-11 to 3A-25 was electrolyte solution No. except that VC corresponding to the monomer of (V) was added without adding (V). It was obtained in the same manner as 3A-11 to 3A-25.
• Comparative electrolyte No. As shown in Table 14, Comparative Electrolyte No. In 1A-1, lithium difluoro (oxalato) borate was used instead of lithium difluorobis (oxalato) phosphate. Comparative electrolyte No. 4A-2, as shown in Table 14, the additive No. 6 was added. Comparative electrolyte No. As shown in Table 16, electrolytes Nos. 4A-24 to 4A-38 were prepared by adding electrolytic solution No. 4 except that (V) was not added and VC corresponding to the monomer (V) was added. It was obtained in the same manner as 4A-24 to 4A-38.
• Comparative electrolyte No. As shown in Table 18, the comparative electrolyte No. In 1A-1, lithium tetrafluoro (oxalato) phosphate was used instead of lithium difluorobis (oxalato) phosphate. Comparative electrolyte No. As shown in Table 18, as shown in Table 18, (V) is additive No. 5 for non-aqueous electrolyte solution. 6 was added. Comparative electrolyte No. As shown in Table 20, each of 5A-24 to 5A-38 has electrolyte No. 5 except that (V) is not added but VC corresponding to the monomer (V) is added. It was obtained in the same manner as 5A-24 to 5A-38.
• lithium hexafluorophosphate LiPF 6
• LiPF 6 lithium hexafluorophosphate
• the compound [5 Pa] as (I) was dissolved in the solution.
• the concentration shown in Table 22 and the monomer of the type shown in Table 22 as (II) is added to the concentration shown in Table 22, and the non-aqueous type of the type shown in Table 22 as (V).
• the electrolytic solution additive By adding the electrolytic solution additive to the concentration shown in Table 22, the electrolytic solution No. 1B-1 to 1B-23 were obtained.
• electrolytic solution No. 16B-1 to 16B-10 were obtained.
• EC / EMC / DMC3 / 4/3 is a non-aqueous organic solvent in which EC, EMC, and dimethyl carbonate (DMC) are mixed at a volume ratio of 3: 4: 3, and “EC / EMC / FEC3 / 6”.
• EC / 1 is a non-aqueous organic solvent in which EC, EMC and fluoroethylene carbonate (FEC) are mixed at a volume ratio of 3: 6: 1, and“ EC / EMC / PC3 / 5/2 ”is EC and EMC.
• the electrolytic solution No. is used except that (I) three kinds of substances are used in the ratio shown in Table 54.
• the electrolytic solution No. 17B-1 to 17B-18 were obtained.
• comparative electrolyte No. 1B-1, 2B-1, 3B-1, 4B-1, 5B-1, 6B-1, 7B-1, 8B-1, 9B-1, 10B-1, 11B-1, 12B-1, 13B- 1, 14B-1, 15B-1, 16B-1 to 16B-6, 17B-1 to 17B-18 are shown in Tables 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, respectively.
• 42, 44, 46, 48, 50, 52, 55 it was obtained by adding VC corresponding to the monomer of (V) without adding (V).
• comparative electrolyte No. 1B-2, 2B-2, 3B-2, 4B-2, 5B-2, 6B-2, 7B-2, 8B-2, 9B-2, 10B-2, 11B-2, 12B-2, 13B- 2, 14B-2 and 15B-2 are (V) as shown in Tables 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48 and 50, respectively.
• additive No. for non-aqueous electrolyte solution. 6 was added.
• test cell (Production and evaluation of cell) Using this electrolyte, a cell was fabricated using LiNi 1/3 Co 1/3 Mn 1/3 O 2 as the positive electrode material and graphite as the negative electrode material, and the initial electric capacity, cycle characteristics, and rate characteristics of the battery were actually evaluated. did.
• the test cell was produced as follows.
• PVDF polyvinylidene fluoride
• acetylene black a conductive material
• N-methylpyrrolidone was added to make a paste.
• the paste was applied on an aluminum foil and dried to obtain a test positive electrode body.
• 90% by mass of graphite powder was mixed with 10% by mass of PVDF as a binder, and N-methylpyrrolidone was further added to form a slurry. This slurry was applied on a copper foil and dried at 150 ° C. for 12 hours to obtain a test negative electrode body. Then, an electrolytic solution was immersed in a polyethylene separator to assemble a 50 mAh cell with an aluminum laminate exterior.
• Discharge capacity maintenance rate after 500 cycles (discharge capacity after 500 cycles / initial discharge capacity) ⁇ 100
• the results are shown in Tables 3, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49. , 51, 53, 56.
• High capacity discharge capacity ratio (discharge capacity at 5 C discharge / discharge capacity at 0.2 C discharge) ⁇ 100 The results are shown in Tables 3, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49. , 51, 53, 56.
• the polystyrene-equivalent number average molecular weight of the additive for non-aqueous electrolyte of the present invention is 170 to When it is 5000, cycle characteristics and rate characteristics can be exhibited in a well-balanced manner when used in a non-aqueous electrolyte secondary battery.
• Comparative Example 1A-1 using the electrolyte solution to which the additive for non-aqueous electrolyte solution of the present invention was not added it was confirmed that the cycle characteristics and rate characteristics tend to be inferior compared with the above examples.
• Comparative Example 1A-2 to which a compound having a polystyrene-equivalent number average molecular weight exceeding 5000 was added it was confirmed that the cycle characteristics and rate characteristics tended to be inferior to those in the above Examples.
• the content of (V) with respect to 100 mass% of the total amount of (I), (II), (III), (IV), (V) is When 0.03 to 14.0% by mass, when used in a non-aqueous electrolyte secondary battery, the cycle characteristics and rate characteristics are easily exhibited in a balanced manner, and the content of (V) is 0.07 to 12%. It turns out that it is more preferable in it being 0.0 mass%.
• cycle characteristics can be obtained by using the additive for non-aqueous electrolyte of the present invention.
• rate characteristics can be exhibited in a well-balanced manner.
• the polystyrene-equivalent number average molecular weight of the non-aqueous electrolyte additive of the present invention is When it is 170 to 5000, cycle characteristics and rate characteristics can be exhibited in a well-balanced manner when used in a non-aqueous electrolyte secondary battery.
• Example 1B-1 it was confirmed that the cycle characteristics and rate characteristics tend to be inferior to those of the above-described Examples. Further, in Comparative Example 1B-2 to which a compound having a polystyrene-equivalent number average molecular weight of more than 5000 was added, it was confirmed that the cycle characteristics and rate characteristics tend to be inferior to those in the above Examples.
• the content of (V) with respect to 100% by mass of the total amount of (I), (II), (III), (IV), and (V) is as follows.
• the cycle characteristics and rate characteristics are easily exhibited in a balanced manner, and the content of (V) is 0.07 to 12%. It turns out that it is more preferable in it being 0.0 mass%.
• cyclic carbonate compounds [22b] and (II) are added by adding a predetermined amount of the non-aqueous electrolyte additive of the present invention. Even in a system containing a monomer compound of a carbonate compound containing a saturated bond, the rate characteristics can be easily improved without impairing the cycle characteristics improvement effect of the cyclic carbonate compound.
• ethoxy (pentafluoro) cyclotriphosphazene which is a cyclic phosphazene compound
• ethoxy (pentafluoro) cyclotriphosphazene which is a cyclic phosphazene compound
• a carbonate compound monomer containing an unsaturated bond impairs the cycle characteristics improvement effect of the cyclic phosphazene compound. It is easy to improve the rate characteristics without.

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