[go: up one dir, main page]

WO2018211896A1 - Composé vinylsulfone, solution électrolytique pour batterie au lithium-ion, et batterie au lithium-ion - Google Patents

Composé vinylsulfone, solution électrolytique pour batterie au lithium-ion, et batterie au lithium-ion Download PDF

Info

Publication number
WO2018211896A1
WO2018211896A1 PCT/JP2018/015854 JP2018015854W WO2018211896A1 WO 2018211896 A1 WO2018211896 A1 WO 2018211896A1 JP 2018015854 W JP2018015854 W JP 2018015854W WO 2018211896 A1 WO2018211896 A1 WO 2018211896A1
Authority
WO
WIPO (PCT)
Prior art keywords
general formula
lithium ion
ion battery
group
alkyl group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/015854
Other languages
English (en)
Japanese (ja)
Inventor
大野　香織
加藤　栄作
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to KR1020197033411A priority Critical patent/KR102297945B1/ko
Priority to CN201880031288.5A priority patent/CN110637008B/zh
Priority to JP2019519137A priority patent/JP7074131B2/ja
Publication of WO2018211896A1 publication Critical patent/WO2018211896A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C07D213/71—Sulfur atoms to which a second hetero atom is attached
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives

Definitions

  • the present invention relates to a vinyl sulfone compound, an electrolytic solution for a lithium ion battery, and a lithium ion battery, and in particular, has excellent storage stability when stored in a non-aqueous solvent for a long period of time, and has a high temperature when used in a lithium ion battery.
  • the present invention relates to a vinyl sulfone compound and the like that can improve a decrease in capacity after a storage test and improve cycle characteristics related to life and initial charge / discharge efficiency.
  • lithium ion batteries lithium ion batteries, sodium ion batteries, nickel metal hydride batteries, and the like are known.
  • lithium ion batteries are used in various applications such as in-vehicle applications and power supplies for mobile phones because of their high energy density and low cost per unit capacity.
  • Lithium ion batteries are expected to be used in various applications in addition to the above applications. For example, it is expected to be used as a power source for wearable or flexible electronics such as smart glasses, smart watches, and organic EL lighting, and in high temperature environments, and further safety is required.
  • an electrolyte type lithium ion battery including a positive electrode, a negative electrode, a separator, and a nonaqueous electrolytic solution containing a lithium salt is known.
  • a so-called all-solid-state lithium ion battery configured by an electrolyte formed of a solid material without using an electrolyte of a non-aqueous electrolyte solution.
  • a lithium ion battery using such a solid electrolyte by containing a vinyl sulfone compound having a hydroxy group (OH group) (Comparative Compound 1 having the structure shown below) in the electrolyte, the ion conductivity is high.
  • a technique for producing a secondary battery that does not leak and has excellent discharge characteristics at low temperatures see, for example, Patent Documents 1 to 3).
  • the vinyl sulfone compound having a hydroxy group described above has poor long-term storage stability in a non-aqueous solvent, and there are problems such as precipitation (precipitation) when stored in a solution state for a long time. Moreover, in the lithium ion battery using the vinyl sulfone compound having a hydroxy group, the capacity is lowered after the high temperature storage test, that is, the life is a problem.
  • the present invention has been made in view of the above problems and circumstances, and its solution is excellent in storage stability when stored for a long time in a non-aqueous solvent, and when used in a lithium ion battery, it has a high temperature.
  • An object is to provide a vinyl sulfone compound capable of improving the reduction in capacity after a storage test and improving the cycle characteristics related to life and the initial charge / discharge efficiency. Furthermore, it is providing the electrolyte solution for lithium ion batteries, and a lithium ion battery.
  • the present inventor in the vinyl sulfone compound having the above hydroxy group (Comparative Compound 1) converts the hydroxy group to a specific substituent, particularly the number of carbon atoms. By replacing with an acyl group of 4 or less, it has excellent long-term storage stability in a non-aqueous solvent by acting preferentially on the interaction or film formation on the negative electrode or positive electrode surface, and the lithium ion battery after the high temperature storage test.
  • the present inventors have found that the reduction in capacity is improved and further that the cycle characteristics and the initial charge / discharge efficiency are improved, and the present invention has been achieved. That is, the said subject which concerns on this invention is solved by the following means.
  • A represents a trivalent aliphatic hydrocarbon group, aromatic hydrocarbon group or heteroaromatic hydrocarbon group which may have a substituent.
  • R 1 represents the following general formula (II) or the following general formula (III).
  • R 2 represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a halogen atom or an alkyl group, an aryl group, an alkoxy group. Represents an aryloxy group or —NR 4 R 5 .
  • R 4 and R 5 represents an alkyl group or an aryl group.
  • R 3 is an alkenyl group, an alkynyl group, an aryl group optionally substituted with a halogen atom, an alkyl group or a cycloalkyl group, an aryl group optionally substituted with a halogen atom or an alkyl group, Represents an alkoxy group, an aryloxy group or —NR 4 R 5 ; R 4 and R 5 represent an alkyl group or an aryl group.
  • -* Represents a bond with an oxygen atom.
  • R 1 is represented by the general formula (II), The vinyl according to any one of items 1 to 3, wherein, in the general formula (II), R 2 represents an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group having 1 to 6 carbon atoms. Sulfone compounds.
  • R 1 is represented by the general formula (II), The vinyl sulfone compound according to any one of Items 1 to 4, wherein, in the general formula (II), R 2 is an alkyl group having 1 to 3 carbon atoms.
  • R 1 is represented by the general formula (III), The vinyl according to any one of items 1 to 3 , wherein, in the general formula (III), R 3 represents an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group having 1 to 6 carbon atoms. Sulfone compounds.
  • the electrolyte solution for a lithium ion battery according to item 8 which contains at least one carbonate of a chain carbonate and a cyclic carbonate.
  • Item 10 The electrolyte solution for a lithium ion battery according to Item 8 or 9, wherein the content of the vinyl sulfone compound is in the range of 0.01 to 5.0 mass% with respect to the total amount of the electrolyte solution.
  • the lithium ion battery which contains the vinyl sulfone compound as described in any one of Claim 1 to 7 in electrolyte solution.
  • Item 12 The lithium ion battery according to item 11, having a negative electrode made of an active material containing natural graphite or artificial graphite which is a carbonaceous material.
  • Item 13 The lithium ion battery according to Item 11 or 12, which has a negative electrode made of a carbonaceous material active material containing at least one atom selected from the group consisting of Si atom, Sn atom and Pb atom.
  • the lithium ion battery according to item 13 having a negative electrode made of a carbonaceous material active material containing Si atoms.
  • Item 15 The lithium ion battery according to any one of Items 11 to 14, having a positive electrode made of an active material containing any one of a lithium transition metal composite oxide or a lithium-containing transition metal phosphate compound.
  • the present invention has excellent storage stability when stored in a non-aqueous solvent for a long period of time, and when used in a lithium ion battery, improves the decrease in capacity after a high-temperature storage test. It is possible to provide a vinyl sulfone compound capable of improving cycle characteristics related to life and initial charge / discharge efficiency. Furthermore, the electrolyte solution for lithium ion batteries and the lithium ion battery using the said vinyl sulfone compound can be provided.
  • the expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
  • the vinyl sulfone compound having the hydroxy group (Comparative Compound 1) is likely to undergo polymerization due to the addition reaction due to the action of the hydroxy group.
  • the Comparative Compound 1 when the Comparative Compound 1 is contained in a non-aqueous solvent, it becomes a gel and precipitates. Things will precipitate. Therefore, as in the present invention, the hydroxy group is capped (cap formation; protective group formation) with the structure represented by the general formula (II) or general formula (III), and the general formula (I) or By adopting the structure represented by the general formula (IV), it is presumed that polymerization due to the addition reaction is suppressed. As a result, when stored for a long time in a non-aqueous solvent, precipitation is not generated and the storage stability is excellent.
  • a film formed by having a substituent represented by the general formula (II) or the general formula (III), particularly an acyl group having 4 or less carbon atoms easily interacts with the positive electrode or the negative electrode with respect to the hydroxy group.
  • a substituent represented by the general formula (II) or the general formula (III) particularly an acyl group having 4 or less carbon atoms
  • the vinyl sulfone compound of the present invention has a structure represented by the above general formula (I). This feature is a technical feature common to or corresponding to the claimed invention.
  • the compound having the structure represented by the general formula (I) is a compound having the structure represented by the general formula (IV). And preferred from the viewpoint of long-term storage stability in a non-aqueous solvent.
  • R 1 is represented by the general formula (II).
  • R 2 is an alkyl group having 1 to 6 carbon atoms or 1 to 6 carbon atoms. Is preferably from the viewpoint of solubility in a non-aqueous solvent and long-term storage stability in a non-aqueous solvent. In the case of a fluorinated alkyl group, the safety of a lithium ion battery ( It is preferable in terms of nonflammability.
  • R 1 is represented by the general formula (III)
  • R 3 is an alkyl group having 1 to 6 carbon atoms or a group having 1 to 6 carbon atoms.
  • fluorinated alkyl group it is preferable to represent a fluorinated alkyl group from the viewpoints of solubility in a non-aqueous solvent and long-term storage stability in a non-aqueous solvent.
  • a fluorinated alkyl group the safety of the lithium ion battery ( It is preferable in terms of nonflammability.
  • the compound having the structure represented by the general formula (I) is a material added to the electrolyte solution for a lithium ion battery, so that the long-term storage stability of the electrolyte solution for the lithium ion battery is excellent.
  • it is preferable at the point which can improve the fall of the capacity
  • the vinyl sulfone compound of the present invention is suitably used for an electrolyte for a lithium ion battery or a lithium ion battery.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the vinyl sulfone compound of the present invention has a structure represented by the following general formula (I).
  • A represents a trivalent aliphatic hydrocarbon group, aromatic hydrocarbon group or heteroaromatic hydrocarbon group which may have a substituent.
  • R 1 represents the following general formula (II) or the following general formula (III).
  • R 2 is a hydrogen atom, a halogen atom which may be substituted, an alkyl group, a cycloalkyl group, a halogen atom or an alkyl group, an aryl group, an alkoxy group, Represents an aryloxy group or —NR 4 R 5 ;
  • R 3 is an alkenyl group, an alkynyl group, an aryl group optionally substituted with a halogen atom, an alkyl group or a cycloalkyl group, an aryl group optionally substituted with a halogen atom or an alkyl group, Represents an alkoxy group, an aryloxy group or —NR 4 R 5 ;
  • R 4 and R 5 in general formula (II) and general formula (III) represent an alkyl group or an aryl group.
  • -* Represents a bond with an oxygen atom.
  • examples of the trivalent aliphatic hydrocarbon group represented by A include alkanes, alkenes, and alkynes having 3 or more acyclic or cyclic carbon atoms (for example, propane, propylene, propyne). , Butane, butene, butadiene, pentane, hexane, heptane, cyclohexane, hexene, hexyne, etc.). Of these, trivalent groups derived from alkanes having 3 to 6 carbon atoms are preferred.
  • trivalent aromatic hydrocarbon group examples include benzene ring, biphenyl, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m- Terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, indene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene ring And trivalent groups derived from a ring, tetralin and the like. Of these, a trivalent group derived from a benzene ring
  • Examples of the trivalent aromatic heterocyclic group include a furan ring, a dibenzofuran ring, a thiophene ring, a dibenzothiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and a benzimidazole ring.
  • Oxadiazole ring triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, indazole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, quinoline ring, isoquinoline ring ,
  • R 1 represents the general formula (II) or the general formula (III).
  • the alkyl group is preferably an alkyl group having 1 to 15 carbon atoms, particularly 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or butyl.
  • Group, t-butyl group, pentyl group, hexyl group and the like, and more preferred are methyl group, ethyl group and t-butyl group.
  • the cycloalkyl group a cyclopentyl group and a cyclohexyl group are preferable.
  • Examples of the aryl group include the same groups as the aromatic hydrocarbon group represented by A in the general formula (I), but a benzene ring group (phenyl group) is preferable.
  • the alkoxy group an alkoxy group having 1 to 6 carbon atoms is preferable, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group, and the like.
  • Examples of the aryloxy group include a phenoxy group and a naphthyloxy group.
  • R 4 and R 5 in R 5, wherein at Formula same groups as the alkyl group and the aryl group represented by R 2 in (II) and the like, alkyl groups having 1 to 6 carbon atoms Are preferable, and a methyl group and an ethyl group are more preferable.
  • R 4 and R 5 may be linked together with a nitrogen atom to form a ring.
  • the halogen atom as a substituent include a chlorine atom, a bromine atom, and a fluorine atom. Of these, fluorine atoms are preferred.
  • alkenyl group examples include a vinyl group and an allyl group.
  • Preferred examples of the alkynyl group include an ethynyl group.
  • the alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, —NR 4 R 5 and halogen atom in the general formula (III) are the same specific examples as in the general formula (II). Can be mentioned.
  • the compound having the structure represented by the general formula (I) is preferably a compound having a structure represented by the following general formula (IV).
  • R 6 represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group, aryl group or alkoxy group. Preferably, it represents a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
  • R 1 has the same meaning as R 1 in the general formula (I).
  • R 1 is represented by the general formula (II), and in the general formula (II), R 2 is an alkyl group having 1 to 6 carbon atoms or a carbon number It preferably represents a 1 to 6 fluorinated alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms.
  • R 1 is represented by the general formula (III)
  • R 3 is an alkyl group having 1 to 6 carbon atoms or a group having 1 to 6 carbon atoms. It preferably represents a fluorinated alkyl group.
  • Acetonitrile 100mL was added to this, and it heated and melt
  • Activated carbon 0.2g was added to this solution, and it stirred for 20 minutes.
  • the filtrate was allowed to stand at 10 ° C. overnight, and the precipitated crystals were washed twice with 20 mL of cold acetonitrile to obtain 13 g (yield 51%) of an acetyl compound (Exemplary Compound 1).
  • non-aqueous electrolyte solution contains a vinyl sulfone compound having a structure represented by the above general formula (I).
  • the non-aqueous electrolytic solution of the present invention is a non-aqueous electrolytic solution in which a lithium salt, the vinyl sulfone compound, and other compounds as required are dissolved in a non-aqueous solvent. Further, an organic polymer compound or the like may be added to the nonaqueous electrolytic solution to form a gel, rubber, or solid sheet.
  • the said vinyl sulfone compound contained in the non-aqueous electrolyte solution of this invention may be used independently, or may use 2 or more types together.
  • the content of the vinyl sulfone compound contained in the non-aqueous electrolyte solution of the present invention is preferably in the range of 0.01 to 5.0% by mass with respect to the whole electrolyte solution, 0.1 to 2. More preferably, it is in the range of 0% by mass. When the content is in the range of 0.1 to 2.0% by mass, it is possible to effectively improve the capacity reduction after the high-temperature storage test of the lithium ion battery.
  • the non-aqueous solvent used in the non-aqueous electrolyte solution of the present invention is not particularly limited, and a known non-aqueous solvent can be used.
  • chain carbonates such as diethyl carbonate, dimethyl carbonate and ethyl methyl carbonate
  • cyclic carbonates such as ethylene carbonate, propylene carbonate and butylene carbonate
  • chain ethers such as 1,2-dimethoxyethane
  • tetrahydrofuran 2-methyl
  • Examples include cyclic ethers such as tetrahydrofuran, sulfolane, and 1,3-dioxolane
  • chain esters such as methyl formate, methyl acetate, and methyl propionate
  • cyclic esters such as ⁇ -butyrolactone and ⁇ -valerolactone.
  • the non-aqueous solvent may be used alone or in combination of two or more.
  • a mixed solvent a combination of a mixed solvent containing a cyclic carbonate and a chain carbonate is preferable from the balance of conductivity and viscosity, and the cyclic carbonate is preferably ethylene carbonate.
  • the lithium salt used in the non-aqueous electrolyte of the present invention is not particularly limited, and a known lithium salt can be used.
  • halides such as LiCl and LiBr
  • perhalogenates such as LiClO 4 , LiBrO 4 and LiClO 4
  • inorganic lithium salts such as inorganic fluoride salts such as LiPF 6 , LiBF 4 and LiAsF 6 ; LiCF 3 SO 3
  • Examples include perfluoroalkane sulfonates such as LiC 4 F 9 SO 3
  • fluorine-containing organic lithium salts such as perfluoroalkane sulfonic acid imide salts such as Li trifluoromethanesulfonyl imide ((CF 3 SO 2 ) 2 NLi), and the like.
  • LiClO 4 , LiPF 6 , and LiBF 4 are preferable.
  • Lithium salts may be used alone or in combination of two or more.
  • concentration of the lithium salt in the non-aqueous electrolyte can be in the range of 0.5 to 2.0 mol / L.
  • organic polymer compound When the organic polymer compound is included in the above non-aqueous electrolyte solution and used in the form of a gel, rubber, or solid sheet, specific examples of the organic polymer compound include polyethylene oxide and polypropylene oxide.
  • the nonaqueous electrolytic solution of the present invention may further contain a film forming agent.
  • a film forming agent include carbonate compounds such as vinylene carbonate, vinylethyl carbonate, and methylphenyl carbonate; alkene sulfides such as ethylene sulfide and propylene sulfide; and sultone compounds such as 1,3-propane sultone and 1,4-butane sultone.
  • acid anhydrides such as maleic acid anhydride and succinic acid anhydride.
  • the non-aqueous electrolyte may further contain an overcharge inhibitor such as diphenyl ether or cyclohexyl benzene.
  • an overcharge inhibitor such as diphenyl ether or cyclohexyl benzene.
  • the total content of the additives is the total amount of the non-aqueous electrolyte so as not to adversely affect other battery characteristics such as an increase in initial irreversible capacity, low temperature characteristics, and deterioration in rate characteristics. In general, it can be 10% by mass or less, in particular, 8% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.
  • a polymer solid electrolyte which is a conductor of an alkali metal cation such as lithium ion can be used.
  • the polymer solid electrolyte include those obtained by dissolving a Li salt in the aforementioned polyether polymer compound, and polymers in which the terminal hydroxy group of the polyether is substituted with an alkoxide.
  • the nonaqueous electrolytic solution of the present invention can be prepared by dissolving a sulfone compound having a structure represented by the above general formula (I), an electrolyte, and, if necessary, other compounds in a nonaqueous solvent. .
  • each raw material is preferably dehydrated in advance in order to reduce the water content when the electrolyte solution is used.
  • it is good to dehydrate to 50 ppm or less, preferably 30 ppm or less, particularly preferably 10 ppm or less.
  • the lithium ion battery of the present invention can take various configurations, but the basic configuration is an embodiment including a positive electrode and a negative electrode capable of inserting and extracting lithium ions, and the above-described electrolyte solution of the present invention. Usually, it is obtained by housing the positive electrode and the negative electrode in a case through a porous film impregnated with an electrolytic solution.
  • the lithium ion battery of the present invention is characterized in that the electrolytic solution contains a vinyl sulfone compound.
  • the shape of the lithium ion battery of the present invention is not particularly limited, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.
  • the negative electrode according to the present invention can take various forms. Basically, the negative electrode includes a current collector and an active material layer formed on the current collector, and the active material layer includes a negative electrode active material. It is preferable that it contains. The active material layer preferably further contains a binder.
  • Negative electrode current collector It does not specifically limit as a negative electrode collector which concerns on this invention, A well-known thing can be used. Specific examples include metal thin films such as rolled copper foil, electrolytic copper foil, and stainless steel foil.
  • the thickness of the negative electrode current collector can be in the range of 4 to 30 ⁇ m. Preferably, it is in the range of 6 to 20 ⁇ m.
  • the negative electrode active material is not particularly limited as long as it can occlude and release lithium ions. Specific examples thereof include carbonaceous materials, alloy-based materials, lithium-containing metal composite oxide materials, and the like. These negative electrode active materials may be used alone or in combination of two or more. Of these, preferred are carbonaceous materials and alloy-based materials, and more preferred are carbonaceous materials. Among the carbonaceous materials, amorphous carbon materials, graphite, and those in which the surface of graphite is coated with amorphous carbon compared to graphite are preferred, and in particular, the surface of graphite or graphite is amorphous compared to graphite. Those coated with carbon are generally preferred because of their high energy density.
  • negative electrode active materials containing carbonaceous materials they contain at least one atom selected from the group consisting of Si atoms, Sn atoms, and Pb atoms because they have a large capacity per unit mass when made into batteries.
  • a carbonaceous material active material is more preferable.
  • the graphite preferably has a lattice plane (002 plane) d value (interlayer distance) of 0.335 to 0.338 nm, particularly 0.335 to 0.337 nm, as determined by X-ray diffraction using the Gakushin method.
  • the crystallite size (Lc) determined by X-ray diffraction by the Gakushin method is usually 10 nm or more, preferably 50 nm or more, and particularly preferably 100 nm or more.
  • the ash content is usually 1% by mass or less, preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less.
  • the graphite surface coated with amorphous carbon is preferably graphite having a d-value of 0.335 to 0.338 nm on the lattice plane (002 plane) in X-ray diffraction as a core material.
  • a carbonaceous material having a larger d-value on the lattice plane (002 plane) in X-ray diffraction than the core material is attached, and the d-value on the lattice plane (002 plane) in X-ray diffraction is greater than that of the core material and the core material
  • the ratio with respect to the carbonaceous material having a large is 99/1 to 80/20 in mass ratio. When this is used, a negative electrode having a high capacity and hardly reacting with the electrolytic solution can be produced.
  • the particle size of the carbonaceous material is in the range of 1 to 100 ⁇ m, preferably 3 to 50 ⁇ m, more preferably 5 to 40 ⁇ m in terms of median diameter by laser diffraction / scattering method.
  • BET specific surface area of the carbonaceous material 0.3 ⁇ 25.0m 2 / g, preferably in the range of 0.8 ⁇ 10.0m 2 / g.
  • the carbonaceous material is analyzed by Raman spectrum using argon ion laser light, the peak P in the peak intensity of the peak P A in the range of 1570 ⁇ 1620 cm -1 in the range of I A, 1300 ⁇ 1400cm -1
  • the peak intensity of B is I B
  • the half width of the peak in the range of 1570 ⁇ 1620cm -1, 26cm -1 or less, are preferred in particular 25 cm -1 or less.
  • the alloy material is not particularly limited as long as it can occlude and release lithium, and single metals and alloys that form lithium alloys, or oxides, carbides, nitrides, silicides, sulfides, and phosphides thereof. Any of these compounds may be used.
  • it is a material including a single metal and an alloy forming a lithium alloy, more preferably a material including a group 13 and group 14 metal / metalloid element (that is, excluding carbon), and further, aluminum, silicon, and It is preferably a single metal of tin (hereinafter, these may be referred to as “specific metal elements”), and an alloy or compound containing these elements.
  • Examples of the negative electrode active material having at least one element selected from the specific metal elements include a single metal of any one specific metal element, an alloy composed of two or more specific metal elements, one type, or two or more types An alloy composed of the specific metal element and one or more other metal elements, a compound containing one or more specific metal elements, and oxides, carbides, nitrides of the compounds, Examples include complex compounds such as silicides, sulfides, and phosphides. By using these simple metals, alloys or metal compounds as the negative electrode active material, the capacity of the battery can be increased.
  • compounds in which these complex compounds are complexly bonded to several kinds of elements such as simple metals, alloys, or non-metallic elements can be given as examples. More specifically, for example, in silicon and tin, an alloy of these elements and a metal that does not operate as a negative electrode can be used. In addition, for example, in the case of tin, a complex compound containing 5 to 6 kinds of elements in combination with a metal that acts as a negative electrode other than tin and silicon, a metal that does not operate as a negative electrode, and a nonmetallic element is also used. Can do.
  • any one simple metal of a specific metal element, an alloy of two or more specific metal elements, oxidation of a specific metal element A material, carbide, nitride or the like is preferable, and silicon and / or tin metal alone, an alloy, an oxide, carbide, nitride, or the like is particularly preferable because of its large capacity per unit mass.
  • the capacity per unit mass is inferior to that of using a single metal or an alloy, the following compounds containing silicon and / or tin are also preferred because of excellent cycle characteristics.
  • alloy materials may be in the form of powder or thin film, and may be crystalline or amorphous.
  • the average particle size of the alloy-based material is not particularly limited in order to exhibit the effects of the present invention, but is in the range of 0.1 to 50 ⁇ m, preferably 1 to 20 ⁇ m, particularly preferably 2 to 10 ⁇ m. This is for preventing electrode expansion and preventing cycle characteristics from deteriorating. Moreover, it is for fully expressing performance, such as current collection and a capacity
  • the lithium-containing metal composite oxide material used as the negative electrode active material is not particularly limited as long as it can occlude and release lithium.
  • a lithium-titanium composite oxide (hereinafter referred to as “lithium-titanium composite oxide”) is not limited. Is preferred).
  • a part of lithium or titanium in the lithium titanium composite oxide is selected from the group consisting of other metal elements such as Na, K, Co, Al, Fe, Mg, Cr, Ga, Cu, Zn, and Nb. Those substituted with at least one element are also preferred.
  • lithium titanium composite oxide represented by Li x Ti y M z O 4 , and 0.7 ⁇ x ⁇ 1.5, 1.5 ⁇ y ⁇ 2.3, and 0 ⁇ z ⁇ 1.6.
  • M is a group consisting of Na, K, Co, Al, Fe, Mg, Cr, Ga, Cu, Zn, and Nb). Represents at least one element selected).
  • the structure in which x, y, and z of the lithium titanium composite oxide represented by Li x Ti y M z O 4 satisfy any of the following (a) to (c) This is particularly preferable because of a good balance.
  • a particularly preferred representative composition is Li 4/3 Ti 5/3 O 4 in (a), Li 1 Ti 2 O 4 in (b), and Li 4/5 Ti 11/5 O 4 in (c). .
  • Z ⁇ 0, for example, Li 4/3 Ti 4/3 Al 1/3 O 4 is preferable.
  • a negative electrode active material disclosed in JP-A-2015-173107 can also be used.
  • Niobium electrode binder Although it does not specifically limit as a binder for negative electrodes, The thing which has an olefinically unsaturated bond in a molecule
  • numerator is preferable. Specific examples include styrene-butadiene rubber, styrene / isoprene / styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, and ethylene / propylene / diene copolymer.
  • the swellability of the active material layer with respect to the electrolytic solution can be reduced.
  • styrene-butadiene rubber is preferred because of its availability.
  • the binder having an olefinically unsaturated bond in the molecule preferably has a high molecular weight and / or a high proportion of unsaturated bonds.
  • the weight average molecular weight can be usually 10,000 or more, and can usually be 1,000,000 or less. If it is this range, both mechanical strength and flexibility can be controlled to a favorable range.
  • the weight average molecular weight is preferably 50,000 or more, and preferably 300,000 or less.
  • the ratio of olefinically unsaturated bonds in the binder molecule is usually within the range of 2.5 ⁇ 10 ⁇ 7 to 5 ⁇ 10 ⁇ 6 mol. Can do. If it is this range, the intensity
  • the degree of unsaturation can usually be in the range of 15 to 90%.
  • the degree of unsaturation is preferably in the range of 20-80%.
  • the degree of unsaturation represents the ratio (%) of the double bond to the repeating unit of the polymer.
  • a binder having no olefinically unsaturated bond can also be used.
  • the mixing ratio of the binder having no olefinically unsaturated bond is usually 150% by mass or less in order to suppress a decrease in the strength of the active material layer. Preferably, it is 120 mass% or less.
  • binders having no olefinically unsaturated bond include thickening polysaccharides such as methylcellulose, carboxymethylcellulose, starch, carrageenan, pullulan, guar gum, xanthan gum (xanthan gum); polyethers such as polyethylene oxide and polypropylene oxide; Vinyl alcohols such as polyvinyl alcohol and polyvinyl butyral; polyacids such as polyacrylic acid and polymethacrylic acid or metal salts thereof; fluorine-containing polymers such as polyvinylidene fluoride; alkane polymers such as polyethylene and polypropylene; Examples include coalescence.
  • polysaccharides such as methylcellulose, carboxymethylcellulose, starch, carrageenan, pullulan, guar gum, xanthan gum (xanthan gum); polyethers such as polyethylene oxide and polypropylene oxide; Vinyl alcohols such as polyvinyl alcohol and polyvinyl butyral; polyacids such as polyacrylic acid and polymethacryl
  • the active material layer may contain a conductive additive in order to improve the conductivity of the negative electrode.
  • the conductive aid is not particularly limited, and examples thereof include carbon black such as acetylene black, ketjen black, and furnace black, fine powder made of Cu, Ni having an average particle size of 1 ⁇ m or less, or an alloy thereof. It is preferable that the addition amount of a conductive support agent is 10 mass% or less with respect to a negative electrode active material.
  • the negative electrode according to the present invention can be formed by dispersing a negative electrode active material and optionally a binder and / or a conductive aid in a dispersion medium to form a slurry, which is applied to a current collector and dried.
  • a dispersion medium an organic solvent such as alcohol or water can be used. It does not specifically limit as a collector which apply
  • the thickness of the negative electrode active material layer (hereinafter sometimes simply referred to as “active material layer”) obtained by applying and drying the slurry is sufficient for practical use as a negative electrode and sufficient lithium ions for high-density current values. From the point of the function of occlusion / release, it can be in the range of 5 to 200 ⁇ m. Preferably, it is in the range of 20 to 100 ⁇ m.
  • the thickness of an active material layer may become the thickness of the said range by pressing after application
  • the density of the negative electrode active material in the active material layer varies depending on the application, it is within the range of 1.10 to 1.65 g / cm 3 in applications in which input / output characteristics such as in-vehicle applications and power tool applications are important. It is preferable.
  • the positive electrode according to the present invention can take various forms, but basically includes a current collector and an active material layer formed on the current collector, and the active material layer comprises a positive electrode active material. It is preferable that it contains.
  • the active material layer preferably further contains a binder.
  • Positive electrode current collector It does not specifically limit as a positive electrode electrical power collector which concerns on this invention, A well-known thing can be used. Specific examples include aluminum, nickel, and stainless steel (SUS).
  • the thickness of the positive electrode current collector can be in the range of 4 to 30 ⁇ m. Preferably, it is in the range of 6 to 20 ⁇ m.
  • the positive electrode active material is not particularly limited as long as it can occlude and release lithium ions during charge and discharge.
  • a substance containing lithium and at least one transition metal is preferable, and examples thereof include a lithium transition metal composite oxide and a lithium-containing transition metal phosphate compound.
  • V, Ti, Cr, Mn, Fe, Co, Ni, Cu, etc. are preferable as the transition metal of the lithium transition metal composite oxide.
  • Specific examples include lithium-cobalt composite oxides such as LiCoO 2 and LiNiO 2 .
  • Lithium / nickel composite oxide, lithium / manganese composite oxide such as LiMnO 2 , LiMn 2 O 4 , Li 2 MnO 3, etc., and some of the transition metal atoms that are the main components of these lithium transition metal composite oxides are Al, Ti , V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, and those substituted with other metals such as Si.
  • LiNi 1-ab Mn a Co b O 2 (a and b represent numbers of 0 or more and less than 1 except for the case where a and b are both 0)
  • LiNi 1-c -d-e Co c Al d Mg e O 2 (c, d, e each represents a number from 0 to less than 1, except in the case of c, d, e are both 0)
  • more LiNi 1- ab Mn a Co b O 2 (0 ⁇ a ⁇ 0.4, 0 ⁇ b ⁇ 0.4
  • LiNi 1- cDe Co c Al d Mg e O 2 (0 ⁇ c ⁇ 0.
  • LiNi 1/3 Co 01/3 Mn 1/3 O 2 LiNi 0.5 Co 0.3 Mn 0.2 O 2
  • LiNi 0.5 Mn 0.5 O 2 LiNi 0.85 Co 0.10 Al 0.05 O 2
  • LiNi 0.85 o 0.10 Al 0.03 Mg 0.02 O 2 is preferred.
  • transition metal of the lithium-containing transition metal phosphate compound V, Ti, Cr, Mn, Fe, Co, Ni, Cu and the like are preferable, and specific examples include, for example, LiFePO 4 , Li 3 Fe 2 (PO 4 ). 3 , iron phosphates such as LiFeP 2 O 7 , cobalt phosphates such as LiCoPO 4 , and some of the transition metal atoms that are the main components of these lithium transition metal phosphate compounds are Al, Ti, V, Cr, Mn , Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Si and the like substituted with other metals.
  • These positive electrode active materials may be used alone or in combination.
  • a material in which a substance (surface adhering substance) having a composition different from that of the substance constituting the main cathode active material is attached to the surface of the cathode active material can be used.
  • Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate And sulfates such as aluminum sulfate and carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate.
  • the amount of the surface adhering substance is not particularly limited in order to exhibit the effect of the present invention, but is preferably within the range of 0.1 to 20 ppm by mass, more preferably 1 to Used within the range of 10 ppm.
  • the surface adhering substance can suppress the oxidation reaction of the non-aqueous electrolyte on the surface of the positive electrode active material, and can improve the battery life.
  • the positive electrode active material layer may contain a conductive additive in order to improve the conductivity of the positive electrode.
  • the conductive aid is not particularly limited, and examples thereof include carbon powders such as acetylene black, carbon black, and graphite, various metal fibers, powders, and foils.
  • the binder for the positive electrode is not particularly limited, and a known binder can be arbitrarily selected and used. Examples include inorganic compounds such as silicate and water glass, and resins having no unsaturated bond such as Teflon (registered trademark) and polyvinylidene fluoride. Among them, a resin having no unsaturated bond is preferable because it is difficult to decompose during the oxidation reaction.
  • the weight average molecular weight of the binder can usually be in the range of 10,000 to 3,000,000, preferably in the range of 100,000 to 1,000,000.
  • the electrode may contain a thickener, a conductive material, a filler, etc. in order to increase mechanical strength and electrical conductivity.
  • the thickener include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein.
  • the electrode may be produced by a conventional method. For example, it can be formed by adding a binder, a thickener, a conductive material, a solvent, or the like to a negative electrode or a positive electrode active material to form a slurry, applying this to a current collector, drying it, and then pressing it.
  • a material obtained by adding a binder or a conductive material to an active material as it is is formed into a sheet electrode, formed into a pellet electrode by compression molding, or deposited on the current collector by a method such as vapor deposition, sputtering, or plating.
  • a thin film can also be formed.
  • the density of the negative electrode active material layer after drying and pressing is preferably in the range of 1.0 to 2.2 g / cm 3 . Preferably, it is within the range of 1.3 to 1.9 g / cm 3 . This is for preventing the increase in initial irreversible capacity due to the destruction of the negative electrode active material particles, preventing the electrolyte from penetrating into the active material layer from being deteriorated, and deteriorating the high rate charge / discharge characteristics. Moreover, it is for preventing the capacity
  • the density after drying and pressing of the positive electrode active material layer is preferably in the range of 1.5 to 5.0 g / cm 3 .
  • a porous film is interposed between the positive electrode and the negative electrode to prevent a short circuit.
  • the electrolytic solution is used by impregnating the porous membrane.
  • the material and shape of the porous film are not particularly limited as long as it is stable to the electrolytic solution and excellent in liquid retention, and a porous sheet or nonwoven fabric made of a polyolefin such as polyethylene or polypropylene is preferable.
  • the material of the battery case used in the lithium ion battery of the present invention is also arbitrary, and nickel-plated iron, stainless steel, aluminum or an alloy thereof, nickel, titanium, a laminate film, or the like is used.
  • the operating voltage of the above-described lithium ion battery of the present invention is usually in the range of 2 to 6V.
  • Example 1 Storage stability in solution (ethylene carbonate) ⁇ Preparation of solution 1> The above exemplified compound 1 (5 g) was dissolved in ethylene carbonate (100 mL), and then the solution was filtered with activated carbon to obtain an ethylene carbonate solution of exemplified compound 1. This solution was stored in the dark at 25 ° C. for 30 days, and then the presence or absence of precipitates was visually confirmed. The evaluation results are shown in Table I below. In the table, no precipitate is indicated by ⁇ , and the presence of precipitate is indicated by ⁇ .
  • Solutions 2 to 17 were prepared in the same manner except that Exemplified Compound 1 used in the preparation of Solution 1 was changed to the exemplified compounds shown in Table I below, and the presence or absence of precipitates was confirmed.
  • a solution 18 was prepared in the same manner except that the exemplified compound 1 used in the preparation of the solution 1 was changed to the following comparative compound 1, and the presence or absence of precipitates was confirmed.
  • Example 2 Storage stability (capacity) of a battery ⁇ Preparation of non-aqueous electrolyte solution>
  • 0.05% by mass of the exemplified compound 1 and 2% by mass of vinylene carbonate were mixed in a mixed solvent of ethylene carbonate and ethyl methyl carbonate (mass ratio 3: 7).
  • fully dried LiPF 6 was dissolved at a rate of 1 mol / liter to obtain a non-aqueous electrolyte.
  • the positive electrode, the negative electrode, and the polyethylene separator were laminated in the order of the positive electrode, the separator, the negative electrode, the separator, and the positive electrode to produce a battery element.
  • This battery element was inserted into a bag made of a laminate film in which both surfaces of aluminum (thickness: 40 ⁇ m) were coated with a resin layer while projecting positive and negative terminals, and then the non-aqueous electrolyte was poured into the bag. Then, vacuum sealing was performed to produce a sheet-like lithium ion battery 1.
  • the sheet-like lithium ion battery 1 was used for the evaluation shown below, and the evaluation results are shown in Table II below.
  • Lithium ion batteries 4 to 19 were produced in the same manner as the lithium ion battery 3, except that the exemplified compound 1 was changed as shown in Table II below in the production of the lithium ion battery 3, and the same as the lithium ion battery 3. Was evaluated.
  • the lithium ion battery 20 was produced in the same manner as the lithium ion battery 3 except that the exemplified compound 1 was replaced with the comparative compound 1 and evaluated in the same manner as the lithium ion battery 3.
  • Example 3 Cycle test ⁇ Preparation of non-aqueous electrolyte solution 1> 1 mass% of the exemplified compound 1 was mixed in a mixed solvent (mass ratio 1: 1) of ethylene carbonate (EC) and diethyl carbonate (DEC) in a dry argon atmosphere. Next, fully dried LiPF 6 was dissolved at a rate of 1 mol / liter to obtain a non-aqueous electrolyte.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • lithium nickel cobalt manganese composite oxide ternary highNi type-LiNi 5/10 Co 2/10 Mn 3/10 O 2
  • acetylene black 3 as a conductive additive %
  • PVdF polyvinylidene fluoride
  • a negative electrode active material 93 parts by mass of artificial graphite powder KS-44 (trade name, manufactured by Timcal) was mixed with 8 parts by mass of PVdF, and N-methylpyrrolidone was added and mixed with a disperser to form a slurry. This slurry was uniformly applied to one side of a 10 ⁇ m thick copper foil, dried, and then pressed so that the density of the negative electrode active material was 1.6 g / cm 3 to prepare a negative electrode.
  • a negative electrode active material 91 parts by mass of SiO-containing artificial graphite powder (manufactured by Nippon Carbon Co., Ltd.) and 9 parts by mass of PVdF were mixed, and N-methylpyrrolidone was added and mixed with a disperser to form a slurry. This slurry was uniformly applied to one side of a 10 ⁇ m thick copper foil, dried, and then pressed so that the density of the negative electrode active material was 1.6 g / cm 3 to prepare a negative electrode.
  • the positive electrode 1, the negative electrode 1, and a polyethylene separator were laminated in the order of the positive electrode, the separator, the negative electrode, the separator, and the positive electrode to prepare a battery element.
  • the battery element was inserted into a bag made of a laminate film in which both surfaces of aluminum (thickness: 40 ⁇ m) were coated with a resin layer while projecting positive and negative terminals, and the non-aqueous electrolyte 1 was injected into the bag. Then, vacuum sealing was performed to produce a sheet-like lithium ion battery 1. Using this sheet-like lithium ion battery 21, the following evaluation was performed, and the evaluation results are shown in Table III below.
  • Lithium ion batteries 21 were prepared in the same manner as the lithium ion battery 21 except that the content of the exemplified compound 1 contained in the non-aqueous electrolyte solution was changed to 0.01% by mass instead of 1% by mass.
  • a battery 22 was produced and evaluated in the same manner as the lithium ion battery 21.
  • Lithium ion batteries 21 were prepared in the same manner as the lithium ion battery 21 except that the content of the exemplified compound 1 contained in the non-aqueous electrolyte solution was changed to 4.95% by mass instead of 1% by mass.
  • a battery 23 was produced and evaluated in the same manner as the lithium ion battery 21.
  • a lithium ion battery 24 was produced in the same manner as the lithium ion battery 21 except that the negative electrode 1 was replaced with the negative electrode 2 in the production of the lithium ion battery 21, and the same evaluation as the lithium ion battery 21 was performed.
  • a lithium ion battery 25 was produced in the same manner as the lithium ion battery 21 except that the nonaqueous electrolyte solution 1 was replaced with the nonaqueous electrolyte solution 2 in the production of the lithium ion battery 21. was evaluated.
  • lithium ion batteries 26 to 28 were produced in the same manner as the lithium ion battery 21, except that the exemplified compound 1 contained in the non-aqueous electrolyte was replaced with a compound corresponding to each of the following Table III. The same evaluation as that of the lithium ion battery 21 was performed.
  • lithium ion batteries 29 to 31 were produced in the same manner as the lithium ion battery 21, except that the exemplified compound 1 contained in the nonaqueous electrolytic solution was replaced with a compound corresponding to Table III below. The same evaluation as that of the lithium ion battery 21 was performed.
  • Lithium ion batteries 21 were prepared in the same manner as the lithium ion battery 21 except that the content of the exemplified compound 1 contained in the non-aqueous electrolyte solution was changed to 0.05% by mass instead of 1% by mass.
  • a battery 32 was produced and evaluated in the same manner as the lithium ion battery 21.
  • the lithium ion battery 33 is the same as the lithium ion battery 21 except that the content of the exemplary compound 1 contained in the non-aqueous electrolyte is 6 mass% instead of 1 mass%. The same evaluation as that of the lithium ion battery 21 was performed.
  • Example 4 Initial charge / discharge efficiency test ⁇ Initial charge / discharge efficiency test> The sheet-like lithium ion battery produced as described above was charged to 4.2 V at 25 ° C., discharged to 3 V, and conditioned until the capacity was stabilized. Thereafter, the battery was charged to 4.2 V at a current value of 1.2 mA at 25 ° C., and discharged to 3 V, and an initial charge / discharge efficiency test was performed.
  • the present invention provides a vinyl sulfone compound that is excellent in storage stability when stored in a non-aqueous solvent for a long period of time, and that can improve a decrease in capacity after a high-temperature storage test when used in a lithium ion battery. Can be used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Secondary Cells (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Le but de la présente invention est de fournir un composé vinylsulfone et similaire présentant une excellente stabilité au stockage lorsqu'il est stocké à long terme dans un solvant non aqueux et, lorsqu'il est utilisé dans une batterie au lithium-ion, présente moins de diminution de volume après un test de stockage à haute température par rapport à l'état de la technique. L'invention concerne un composé vinylsulfone qui a une structure représentée par la formule générale (I), A étant un groupe hydrocarboné aliphatique trivalent éventuellement substitué, un groupe hydrocarboné aromatique ou un groupe hydrocarboné hétéroaromatique, et R1 représentant la formule générale (II) ou la formule générale (III).
PCT/JP2018/015854 2017-05-15 2018-04-17 Composé vinylsulfone, solution électrolytique pour batterie au lithium-ion, et batterie au lithium-ion Ceased WO2018211896A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020197033411A KR102297945B1 (ko) 2017-05-15 2018-04-17 비닐술폰 화합물, 리튬 이온 전지용 전해액 및 리튬 이온 전지
CN201880031288.5A CN110637008B (zh) 2017-05-15 2018-04-17 乙烯基砜化合物、锂离子电池用电解液及锂离子电池
JP2019519137A JP7074131B2 (ja) 2017-05-15 2018-04-17 ビニルスルホン化合物、リチウムイオン電池用電解液及びリチウムイオン電池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017096260 2017-05-15
JP2017-096260 2017-05-15

Publications (1)

Publication Number Publication Date
WO2018211896A1 true WO2018211896A1 (fr) 2018-11-22

Family

ID=64273528

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/015854 Ceased WO2018211896A1 (fr) 2017-05-15 2018-04-17 Composé vinylsulfone, solution électrolytique pour batterie au lithium-ion, et batterie au lithium-ion

Country Status (4)

Country Link
JP (1) JP7074131B2 (fr)
KR (1) KR102297945B1 (fr)
CN (1) CN110637008B (fr)
WO (1) WO2018211896A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113764728B (zh) * 2020-06-01 2023-11-14 比亚迪股份有限公司 电解液以及锂金属电池
CN113937358B (zh) * 2021-09-29 2022-07-26 广东工业大学 一种锂离子电池电解液添加剂及其制备方法与锂电池电解液
CN116031491A (zh) * 2023-03-29 2023-04-28 宁德新能源科技有限公司 电解液、电化学装置和电子装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63123039A (ja) * 1986-11-12 1988-05-26 Konica Corp 高分子硬膜剤で硬膜されたハロゲン化銀写真感光材料
JP2000017076A (ja) * 1998-07-01 2000-01-18 Fuji Photo Film Co Ltd 架橋重合体およびこれを用いた電解質とその製造方法
JP2000021446A (ja) * 1998-07-03 2000-01-21 Fuji Photo Film Co Ltd 非水二次電池
JP2002190323A (ja) * 2000-12-22 2002-07-05 Fuji Photo Film Co Ltd 電解質組成物及び非水電解質二次電池
WO2008133112A1 (fr) * 2007-04-20 2008-11-06 Ube Industries, Ltd. Solution non aqueuse d'électrolyte pour une batterie secondaire au lithium et une batterie secondaire au lithium utilisant celle-ci.

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11214001A (ja) * 1998-01-23 1999-08-06 Fuji Elelctrochem Co Ltd 非水電解液二次電池
JP3820748B2 (ja) * 1998-05-15 2006-09-13 宇部興産株式会社 リチウム二次電池用電解液およびそれを用いたリチウム二次電池
JP2015173107A (ja) * 2014-02-18 2015-10-01 三菱化学株式会社 非水系二次電池負極用活物質、それを用いた負極及び非水系二次電池
JP2017168347A (ja) * 2016-03-17 2017-09-21 富山薬品工業株式会社 蓄電デバイス用非水電解液

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63123039A (ja) * 1986-11-12 1988-05-26 Konica Corp 高分子硬膜剤で硬膜されたハロゲン化銀写真感光材料
JP2000017076A (ja) * 1998-07-01 2000-01-18 Fuji Photo Film Co Ltd 架橋重合体およびこれを用いた電解質とその製造方法
JP2000021446A (ja) * 1998-07-03 2000-01-21 Fuji Photo Film Co Ltd 非水二次電池
JP2002190323A (ja) * 2000-12-22 2002-07-05 Fuji Photo Film Co Ltd 電解質組成物及び非水電解質二次電池
WO2008133112A1 (fr) * 2007-04-20 2008-11-06 Ube Industries, Ltd. Solution non aqueuse d'électrolyte pour une batterie secondaire au lithium et une batterie secondaire au lithium utilisant celle-ci.

Also Published As

Publication number Publication date
CN110637008B (zh) 2021-09-17
JPWO2018211896A1 (ja) 2020-03-19
CN110637008A (zh) 2019-12-31
KR102297945B1 (ko) 2021-09-02
JP7074131B2 (ja) 2022-05-24
KR20190132533A (ko) 2019-11-27

Similar Documents

Publication Publication Date Title
CN110383566B (zh) 非水电解液用添加剂、非水电解液及蓄电装置
KR101049829B1 (ko) 리튬 이차 전지용 음극 활물질 및 이를 포함하는 리튬 이차 전지
JP5366909B2 (ja) リチウム二次電池用正極活物質およびこれを含むリチウム二次電池
CN103594677B (zh) 可再充电锂电池用负极活性物质、负极和可再充电锂电池
CN111527636A (zh) 非水电解液电池用电解液和使用其的非水电解液电池
JP2019102459A (ja) 非水電解液電池用電解液及びそれを用いた非水電解液電池
KR20110123095A (ko) 에너지 저장 장치용 음극 및 이를 포함하는 에너지 저장 장치
KR101181841B1 (ko) 고전압 리튬 이차 전지용 양극 및 이를 포함하는 고전압 리튬 이차 전지
JP2020072023A (ja) 非水系電解液及びリチウムイオン二次電池
CN113906604B (zh) 非水电解液及非水电解质电池
EP2821408B1 (fr) Borate bis(hydroxyacetato) comme électrolyte d'une batterie secondaire au lithium
KR20240034157A (ko) 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차전지
JP7074131B2 (ja) ビニルスルホン化合物、リチウムイオン電池用電解液及びリチウムイオン電池
JP2020187973A (ja) 非水系電解液及びリチウムイオン二次電池
JP5472952B1 (ja) 非水二次電池
WO2018016767A1 (fr) Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant
KR20240015482A (ko) 양극, 및 이를 포함하는 리튬 이차 전지
CN112542608B (zh) 可再充电锂电池及其制造方法
JP6270634B2 (ja) 活物質、それを用いたナトリウムイオン電池およびリチウムイオン電池
EP3435453B1 (fr) Matériau actif positif pour batterie au lithium rechargeable et batterie au lithium rechargeable le comprenant
US20250300228A1 (en) Electrolyte of rechargeable lithium battery and rechargeable lithium battery including same
KR102908014B1 (ko) 리튬 이차 전지용 전해질 및 이를 포함하는 리튬 이차 전지
KR102908016B1 (ko) 리튬 이차 전지용 전해질 및 이를 포함하는 리튬 이차 전지
KR20130102907A (ko) 전해액 첨가제, 이를 포함하는 전해액 및 리튬 이차 전지
KR20230162240A (ko) 리튬 이차 전지용 전해질 및 이를 포함하는 리튬 이차 전지

Legal Events

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

Ref document number: 18802399

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019519137

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20197033411

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18802399

Country of ref document: EP

Kind code of ref document: A1