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WO2018198618A1 - Solution électrolytique non aqueuse et dispositif de stockage d'électricité l'utilisant - Google Patents

Solution électrolytique non aqueuse et dispositif de stockage d'électricité l'utilisant Download PDF

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Publication number
WO2018198618A1
WO2018198618A1 PCT/JP2018/011747 JP2018011747W WO2018198618A1 WO 2018198618 A1 WO2018198618 A1 WO 2018198618A1 JP 2018011747 W JP2018011747 W JP 2018011747W WO 2018198618 A1 WO2018198618 A1 WO 2018198618A1
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Prior art keywords
carbonate
group
lithium
methyl
electrolytic solution
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English (en)
Japanese (ja)
Inventor
大希 木戸
近藤　正英
雄一 古藤
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Ube Corp
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Ube Industries Ltd
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Priority to JP2019515159A priority Critical patent/JP7082613B2/ja
Publication of WO2018198618A1 publication Critical patent/WO2018198618A1/fr
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/64—Liquid electrolytes characterised by 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a nonaqueous electrolytic solution capable of improving continuous charging characteristics under a high temperature and high voltage environment, and an electricity storage device using the same.
  • lithium ion secondary batteries and lithium ion capacitors have attracted attention as power sources for automobiles such as electric cars and hybrid cars, and power supplies for idling stops.
  • Patent Document 1 proposes a non-aqueous electrolytic solution containing an alkenyl group-containing chain ester such as allyl methyl carbonate in combination with an ionic liquid, which improves the safety of an electricity storage device at room temperature.
  • the battery characteristics can be improved.
  • the battery when a lithium secondary battery is kept in a continuously charged state for a long time in a high temperature and high voltage environment, the battery has a portion of the nonaqueous solvent in the nonaqueous electrolyte on the surfaces of the positive electrode and the negative electrode.
  • the non-aqueous electrolyte is consumed due to oxidation or reductive decomposition, deposition of decomposed products, and gas generation, resulting in liquid drainage.
  • the non-aqueous electrolyte is withered, the interface resistance between the positive electrode and the negative electrode is increased, and the desirable electrochemical characteristics of the battery are reduced.
  • An object of the present invention is to provide a nonaqueous electrolytic solution capable of improving continuous charging characteristics under a high temperature and high voltage environment, and an electricity storage device using the same.
  • the present invention provides the following (1) to (2).
  • a nonaqueous electrolytic solution for an electricity storage device comprising 0.1 to 30% by mass of at least one selected from the group consisting of a fluorine atom-containing cyclic carbonate and an unsaturated bond-containing cyclic carbonate as an additive.
  • a power storage device including a positive electrode, a negative electrode, and a non-aqueous electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent, wherein the non-aqueous electrolyte is the non-aqueous electrolyte described in (1).
  • nonaqueous electrolytic solution capable of improving the continuous charging characteristics under a high temperature and high voltage environment, and an electricity storage device such as a lithium battery using the nonaqueous electrolytic solution.
  • the nonaqueous electrolytic solution for an electricity storage device of the present invention is a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent, and the nonaqueous electrolytic solution contains a compound represented by the following general formula (I): Containing 0.1 to 4% by mass, and containing 0.1 to 30% by mass of at least one selected from the group consisting of a fluorine atom-containing cyclic carbonate and an unsaturated bond-containing cyclic carbonate as an additive .
  • R 1 represents an alkyl group having 1 to 7 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms
  • R 2 to R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, Or —CH 2 OC ( ⁇ O) OR 7 group
  • R 7 represents an alkyl group having 1 to 4 carbon atoms
  • n 0 or 1
  • the nonaqueous electrolytic solution of the present invention can improve the continuous charging characteristics under a high temperature and high voltage environment. Since the compound represented by the general formula (I) used in the present invention has a cyclohexyl group, the decomposition reaction on the electrode active surface is promoted and a film is rapidly formed. Stability was insufficient. Therefore, when a specific amount of the compound represented by the general formula (I) is used in combination with a specific amount of at least one selected from the group consisting of a fluorine atom-containing cyclic carbonate and an unsaturated bond-containing cyclic carbonate as an additive.
  • one of the carbonates contains not a cyclohexyl group but a phenyl group, sufficient strength cannot be obtained because the formation rate of the resulting film is slow or the constituent components are different.
  • the coating is composed of a compound in which the other substituent R 1 of the carbonate represented by the general formula (I) is an alkyl group or a cycloalkyl group, the film does not interfere with permeation of lithium ions.
  • the continuous charge characteristics under a high temperature and high voltage environment are further improved.
  • the compound contained in the nonaqueous electrolytic solution of the present invention is represented by the following general formula (I).
  • R 1 represents an alkyl group or cycloalkyl group having 1 to 7 carbon atoms, and among them, an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 4 to 6 carbon atoms is preferable, A 1 to 2 alkyl group or a cycloalkyl group having 5 to 6 carbon atoms is preferred.
  • alkyl group having 1 to 7 carbon atoms or the cycloalkyl group having 3 to 6 carbon atoms represented by R 1 specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and n-butyl. Preferred examples include a straight-chain alkyl group, or a branched alkyl group such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl, and cyclohexylmethyl group.
  • cycloalkyl group examples include a cyclopropyl group And a cyclic alkyl group such as a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.
  • a methyl group, an ethyl group, an n-propyl group, or a cyclohexyl group is preferable, and a methyl group, an ethyl group, or a cyclohexyl group is more preferable.
  • R 2 to R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a —CH 2 OC ( ⁇ O) OR 7 group,
  • An alkyl group having 1 to 4 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is more preferred, and a hydrogen atom is still more preferred.
  • R 2 to R 6 are an alkyl group having 1 to 4 carbon atoms
  • a linear alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, an isopropyl group
  • Preferred examples include branched alkyl groups such as isobutyl group, sec-butyl group, hydrogen atom, and tert-butyl group.
  • a methyl group, an ethyl group, or an n-propyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • R 7 represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 2 carbon atoms.
  • R 4 is preferable.
  • R 7 include alkyl groups having 1 to 4 carbon atoms, such as a straight-chain alkyl group such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, isopropyl Preferred examples thereof include branched alkyl groups such as a group, isobutyl group, sec-butyl group, and tert-butyl group. Among these, a methyl group, an ethyl group, or an n-propyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • n represents 0 or 1
  • n is preferably 1 from the viewpoint of enhancing the effect of continuous charge characteristics under a high temperature and high voltage environment.
  • preferred examples when n is 0 or 1 include the following compounds.
  • methylcyclohexyl carbonate (compound A1), methyl (2-methylcyclohexyl) carbonate (compound A2), methyl (3-methylcyclohexyl) carbonate (compound A3), methyl (4-methylcyclohexyl) carbonate (compound A4) ), Methyl (2,3-dimethylcyclohexyl) carbonate (compound A5), methyl (2,4-dimethylcyclohexyl) carbonate (compound A6), methyl (2,5-dimethylcyclohexyl) carbonate (compound A7), methyl (2 , 6-dimethylcyclohexyl) carbonate (compound A8), ethylcyclohexyl carbonate (compound A14), ethyl (2-methylcyclohexyl) carbonate (compound A15), ethyl (3-methylcyclohexane)
  • cyclohexylmethyl methyl carbonate (compound B1), cyclohexylmethyl ethyl carbonate (compound B3), bis (cyclohexylmethyl) carbonate (compound B5), cyclohexane-1,4-diylbis (methylene) dimethylbis (carbonate) ( One or more selected from the group consisting of Compound B6) and cyclohexane-1,4-diylbis (methylene) diethylbis (carbonate) (Compound B7) is preferred, and cyclohexylmethyl methyl carbonate (Compound B1), cyclohexylmethyl ethyl carbonate (Compound One or more selected from the group consisting of B3) and cyclohexane-1,4-diylbis (methylene) dimethylbis (carbonate) (compound B6) is more preferred.
  • the content of the compound represented by the general formula (I) is preferably 0.1 to 4% by mass in the non-aqueous electrolyte. If the content is 4% by mass or less, there is little possibility that the film is excessively formed on the electrode and the electrochemical characteristics are lowered, and if it is 0.1% by mass or more, the formation of the film is sufficient and the temperature is high. And the effect of the continuous charge characteristic in a high voltage environment increases.
  • the content is more preferably 0.3% by mass or more, and particularly preferably 0.6% by mass or more.
  • the upper limit is more preferably 3% by mass or less, further preferably 2.2% by mass or less, and particularly preferably 1.7% by mass or less.
  • the additive used in combination with the compound represented by the general formula (I) contains at least one selected from the group consisting of a fluorine atom-containing cyclic carbonate and an unsaturated bond-containing cyclic carbonate. To do. In these, a fluorine atom containing cyclic carbonate is more preferable.
  • Fluorine atom-containing cyclic carbonates include 4-fluoro-1,3-dioxolan-2-one (FEC), trans or cis-4,5-difluoro-1,3-dioxolan-2-one (hereinafter collectively referred to as both) One or more selected from the group consisting of “DFEC” and the like, and 4-fluoro-1,3-dioxolan-2-one is more preferable.
  • Suitable combinations selected from the group consisting of these fluorine atom-containing cyclic carbonates and unsaturated bond-containing cyclic carbonates include VC and FEC combinations, FEC and DFEC combinations, VC and DFEC combinations, VEC and DFEC combinations, VC And a combination of EC and EEC and a combination of EC and EEC are preferable.
  • a combination of VC and FEC, a combination of VC and DFEC, a combination of VEC and DFEC, and the like are more preferable.
  • the total content of at least one selected from the group consisting of the fluorine atom-containing cyclic carbonate and the unsaturated bond-containing cyclic carbonate is preferably 0.1 to 30% by mass in the non-aqueous electrolyte. If the content is 30% by mass or less, there is little possibility that the film is excessively formed on the electrode and the electrochemical characteristics are lowered, and if it is 0.1% by mass or more, the film is sufficiently formed, and the temperature is high. And the effect of the continuous charge characteristic in a high voltage environment increases.
  • the content is preferably 0.5% by mass or more, more preferably 1% by mass or more in the nonaqueous electrolytic solution. Further, the upper limit is preferably 25% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 6% by mass or less, and particularly preferably 4% by mass or less.
  • the content ratio (mass ratio) of the compound represented by the general formula (I) and at least one compound selected from the group consisting of a fluorine atom-containing cyclic carbonate and an unsaturated bond-containing cyclic carbonate is the general formula (I).
  • a / B is preferably in the range of 0.01-3.
  • the content ratio is 3 or less, there is little possibility that the film is excessively formed on the electrode and the electrochemical characteristics are lowered, and if it is 0.01 or more, the film is sufficiently formed, and the high temperature and high voltage The effect of continuous charging characteristics in the environment is enhanced.
  • the content ratio is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably 0.2 or more.
  • the upper limit is preferably 3 or less, more preferably 1.8 or less, and the case where the upper limit is 0.6 or less is more preferable because continuous charging characteristics at a higher temperature and a high voltage environment are further improved.
  • Nonaqueous solvent As the non-aqueous solvent used in the non-aqueous electrolyte of the present invention, a cyclic carbonate (however, the non-aqueous solvent excludes a fluorine atom-containing cyclic carbonate and an unsaturated bond-containing cyclic carbonate; the same shall apply hereinafter), a chain form.
  • a cyclic carbonate Although, the non-aqueous solvent excludes a fluorine atom-containing cyclic carbonate and an unsaturated bond-containing cyclic carbonate; the same shall apply hereinafter, a chain form.
  • One type or two or more types selected from the group consisting of esters, lactones, ethers and amides are preferred.
  • a cyclic carbonate and a chain ester In order to synergistically improve the continuous charge characteristics in a high temperature and high voltage environment, it is most preferable that both a cyclic carbonate and a chain ester are included.
  • cyclic carbonate examples include one or more selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, and 2,3-butylene carbonate. One or two selected from the group consisting of propylene carbonate are more preferable.
  • the chain ester may be one or more asymmetric chains selected from the group consisting of methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate, and ethyl propyl carbonate.
  • One or more symmetrical linear carbonates selected from the group consisting of linear carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, and dibutyl carbonate, methyl pivalate, ethyl pivalate, pivalic acid Pivalate esters such as propyl, methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), and vinegar
  • One or more chain carboxylate selected from the group consisting of butyl suitably.
  • chain esters dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, propyl acetate (PA), butyl acetate, methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), and pivalic acid
  • PA propyl acetate
  • MP propionate
  • EP ethyl propionate
  • PP propyl propionate
  • pivalic acid A chain ester having a molecular weight of 90 or more and 120 or less selected from the group consisting of methyl is preferable.
  • a chain carbonate As the chain ester, it is preferable to use two or more. Further, it is more preferable that both a symmetric chain carbonate and an asymmetric chain carbonate are contained, and it is further more preferable that the content of the symmetric chain carbonate is more than that of the asymmetric chain carbonate.
  • the proportion of the volume occupied by the symmetrical linear carbonate in the linear carbonate is preferably 51% by volume or more, and more preferably 55% by volume or more. As the upper limit, 95 volume% or less is preferable and 85 volume% or less is more preferable. It is particularly preferred that the symmetric chain carbonate contains dimethyl carbonate.
  • the asymmetric chain carbonate preferably has a methyl group, and methyl ethyl carbonate is particularly preferable. In the above case, continuous charging characteristics at a higher temperature and a higher voltage environment are improved, which is preferable.
  • the content of the chain ester is not particularly limited, but it is preferably used in the range of 60 to 90% by volume with respect to the total volume of the nonaqueous solvent. If the content is 60% by volume or more, the viscosity of the non-aqueous electrolyte does not become too high, and if it is 90% by volume or less, the electrical conductivity of the non-aqueous electrolyte may decrease and the electrochemical characteristics may decrease. Since it is few, it is preferable that it is the said range.
  • the ratio between the cyclic carbonate and the chain ester is preferably 10:90 to 45:55, and preferably 15:85 to cyclic carbonate: chain ester (volume ratio) from the viewpoint of continuous charge characteristics under a high temperature and high voltage environment. 40:60 is more preferable, and 20:80 to 35:65 is more preferable.
  • nonaqueous solvents include cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, and the like Preferred is one or more selected from the group consisting of a chain ether, amides such as dimethylformamide, sulfones such as sulfolane, and lactones such as ⁇ -butyrolactone (GBL) or ⁇ -valerolactone, ⁇ -angelicalactone It is mentioned in.
  • ⁇ -butyrolactone GBL
  • ⁇ -valerolactone ⁇ -angelicalactone
  • the other non-aqueous solvents are usually used as a mixture in order to achieve appropriate physical properties.
  • a combination of a cyclic carbonate, a chain ester, and a lactone, or a combination of a cyclic carbonate, a chain ester, and an ether is preferably exemplified, and a combination of a cyclic carbonate, a chain ester, and a lactone is more preferable.
  • lactones ⁇ -butyrolactone (GBL) is more preferred.
  • the content of the other nonaqueous solvent is usually 1% or more, preferably 2% or more, and usually 40% or less, preferably 30% or less, more preferably 20%, based on the total volume of the nonaqueous solvent. It is as follows.
  • additives In the present invention, it is preferable to add other additives to the non-aqueous electrolyte for the purpose of improving the continuous charge characteristics at a higher temperature and a higher voltage environment.
  • additives include the following compounds (A) to (H).
  • (A) Among the polyvalent nitrile compounds at least one selected from the group consisting of adiponitrile, pimelonitrile, suberonitrile, and sebaconitrile having 4 or more carbon chains between the —CN group and the —CN group is more preferable.
  • aromatic compounds one selected from the group consisting of biphenyl, terphenyl (o-, m-, p-isomer), fluorobenzene, cyclohexylbenzene, tert-butylbenzene, and tert-amylbenzene Alternatively, two or more are more preferable, and one or more selected from the group consisting of biphenyl, o-terphenyl, fluorobenzene, cyclohexylbenzene, and tert-amylbenzene are particularly preferable.
  • (C) Among the isocyanate compounds, one or more selected from the group consisting of hexamethylene diisocyanate, octamethylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate are more preferable.
  • Triple bond-containing compounds include 2-propynyl-methyl carbonate, 2-propynyl methacrylate, 2-propynyl methanesulfonate, 2-propynyl vinylsulfonate, 2- (methanesulfonyloxy) propionic acid Selected from the group consisting of 2-propynyl, di (2-propynyl) oxalate, methyl-2-propynyl oxalate, ethyl-2-propynyl oxalate, and 2-butyne-1,4-diyl-dimethanesulfonate 1 type or 2 types or more are preferable, and 2-propynyl methanesulfonate, 2-propynyl vinylsulfonate, 2-propynyl 2- (methanesulfonyloxy) propionate, di (2-propynyl) oxalate, and 2- Butyne-1,4-diyl
  • (E) a non-lithium compound containing a cyclic or chain S ⁇ O group selected from the group consisting of sultone, cyclic sulfite, cyclic sulfate, sulfonic acid ester, and vinyl sulfone (however, a triple bond-containing compound, It is preferable to use a specific compound represented by any of the formulas).
  • Examples of the cyclic S ⁇ O group-containing compound include 1,3-propane sultone, 1,3-butane sultone, 1,4-butane sultone, 2,4-butane sultone, 1,3-propene sultone, 2,2-dioxide- 1,2-oxathiolan-4-yl-acetate, 5,5-dimethyl-1,2-oxathiolane-4-one-2,2-dioxide, methylenemethane disulfonate, ethylene sulfite, ethylene sulfate, and 4- ( Preferable examples include one or more selected from the group consisting of (methylsulfonylmethyl) -1,3,2-dioxathiolane-2-oxide.
  • chain-containing S ⁇ O group-containing compound examples include butane-2,3-diyl-dimethanesulfonate, butane-1,4-diyl-dimethanesulfonate, dimethylmethane disulfonate, pentafluorophenylmethanesulfonate, divinyl
  • One or more kinds selected from the group consisting of sulfone and bis (2-vinylsulfonylethyl) ether are preferred.
  • 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, 2,2-dioxide-1,2-oxathiolan-4-yl- 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, 2,2-dioxide-1,2-oxathiolan-4-yl-
  • 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, 2,2-dioxide-1,2-oxathiolan-4-yl- One or more selected from the group consisting of acetate, ethylene sulfate, pentafluorophenyl methanesulfonate, and divinylsulfone are more preferable.
  • 1,3-dioxolane, 5,5-dimethyl-1,3-dioxane, and 5-ethyl-5-methyl-1,3-dioxane are preferable, and 1,3-dioxane and More preferred is 5,5-dimethyl-1,3-dioxane.
  • Phosphorus-containing compounds include tris phosphate (2,2,2-trifluoroethyl), tris phosphate (1,1,1,3,3,3-hexafluoropropan-2-yl), methyl -2- (dimethylphosphoryl) acetate, ethyl-2- (dimethylphosphoryl) acetate, methyl-2- (diethylphosphoryl) acetate, ethyl-2- (diethylphosphoryl) acetate, 2-propynyl-2- (dimethylphosphoryl) acetate 2-propynyl-2- (diethylphosphoryl) acetate, methyl-2- (dimethoxyphosphoryl) acetate, ethyl-2- (dimethoxyphosphoryl) acetate, methyl-2- (diethoxyphosphoryl) acetate, ethyl-2- (di Ethoxyphosphoryl) acetate, 2-propynyl-2- (dimetho Cyphosphoryl) acetate and 2-propyn
  • the total content of the compounds (A) to (H) is preferably 0.01 to 7% by mass in the non-aqueous electrolyte. In this range, the coating film is sufficiently formed without becoming too thick, and the continuous charging characteristics at a higher temperature and a higher voltage environment are further enhanced.
  • the total content is more preferably 0.05% by mass or more, more preferably 0.1% by mass or more in the non-aqueous electrolyte, and the upper limit thereof is more preferably 5% by mass or less, and further preferably 3% by mass or less. preferable.
  • Electrode salt Preferred examples of the electrolyte salt used in the present invention include the following lithium salts.
  • lithium salts include inorganic lithium salts such as LiPF 6 , LiBF 4 and LiClO 4 , LiCF 3 SO 3 , LiC (SO 2 CF 3 ) 3 , LiPF 4 (CF 3 ) 2 , LiPF 3 (C 2 F 5 ) 3.
  • Preferred examples include lithium salts containing a chain-like fluorinated alkyl group, such as LiPF 3 (CF 3 ) 3 , LiPF 3 (iso-C 3 F 7 ) 3 , LiPF 5 (iso-C 3 F 7 ).
  • Favorable examples include at least one lithium salt selected from these, and one or more of these may be used in combination.
  • LiPF 6 and LiBF 4 are preferable, and it is most preferable to use LiPF 6 .
  • the concentration of the electrolyte salt is usually preferably 0.3 M or higher, more preferably 0.7 M or higher, and even more preferably 1.1 M or higher in the nonaqueous electrolytic solution.
  • the upper limit is preferably 2.5M or less, more preferably 2.0M or less, and still more preferably 1.6M or less.
  • the non-aqueous electrolyte further includes a lithium salt (I) having an oxalic acid structure, a lithium salt (II) having a phosphoric acid structure, It is preferable to include at least one lithium salt selected from the group consisting of a lithium salt (III) having an S ⁇ O group and a lithium imide salt (IV) having a fluorine atom.
  • lithium salt (I) having an oxalic acid structure examples include lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), lithium tetrafluoro (oxalato) phosphate (LiTFOP), and lithium difluorobis (oxalato).
  • LiBOB lithium bis (oxalato) borate
  • LiDFOB lithium difluoro (oxalato) borate
  • LiTFOP lithium tetrafluoro (oxalato) phosphate
  • LiDFOP lithium difluorobis
  • lithium salt (II) having a phosphoric acid structure examples include lithium difluorophosphate (LiPO 2 F 2 ), lithium fluorophosphate (Li 2 PO 3 F), lithium bis (difluorophosphoryl) amide, lithium (difluorophosphoryl) ( Suitable examples include lithium salts having a phosphoric acid structure such as fluorooxide phosphoryl) amide, among which LiPO 2 F 2 and Li 2 PO 3 F are more preferred, and LiPO 2 F 2 is even more preferred.
  • lithium salt (III) having an S ⁇ O group examples include lithium fluorosulfate (FSO 3 Li), lithium methyl sulfate (LMS), lithium ethyl sulfate (LES), lithium 2,2,2-trifluoroethyl sulfate (LFES). ), Lithium trifluoro ((methanesulfonyl) oxy) borate (LiTFMSB), lithium pentafluoro ((methanesulfonyl) oxy) phosphate (LiPFMSP), and among them, LMS, LES, FSO 3 Li, LFES And LiTFMSB are preferred, and LMS and LES are more preferred.
  • LiTFMSB Lithium trifluoro ((methanesulfonyl) oxy) borate
  • LiPFMSP lithium pentafluoro ((methanesulfonyl) oxy) phosphate
  • the content of each salt of lithium salt (I), (II) or (III) is preferably 0.001 to 0.2 M in the non-aqueous electrolyte. If the content is 0.2 M or less, there is little possibility that the film is excessively formed on the electrode and the electrochemical characteristics are lowered. If 0.001 M or more, the content after continuous charging in a high temperature and high voltage environment is low. The effect of suppressing the decrease in average discharge voltage is sufficient, and the effect of improving battery characteristics after continuous charging is enhanced.
  • the content is preferably 0.01 M or more, more preferably 0.03 M or more, and particularly preferably 0.04 M or more in the nonaqueous electrolytic solution.
  • the upper limit is preferably 0.15M or less, and more preferably 0.12M or less.
  • lithium imide salt (IV) having a fluorine atom As the lithium imide salt (IV) having a fluorine atom, (CF 2 ) 2 (SO 2 ) 2 NLi, (CF 2 ) 3 (SO 2 ) 2 NLi, LiN (SO 2 F) 2 (LiFSI), LiN ( One or more types selected from the group consisting of SO 2 CF 3 ) 2 (LiTFSI) and LiN (SO 2 C 2 F 5 ) 2 are preferably mentioned, and among these, one or more types selected from LiTFSI and LiFSI Is more preferable, and LiFSI is more preferable.
  • the content of the lithium imide salt (IV) is preferably 0.01 to 1M in the nonaqueous electrolytic solution. If the content is 1M or less, there is little possibility that the film is excessively formed on the electrode and the electrochemical characteristics are lowered, and if it is 0.01M or more, the average discharge after continuous charging in a high temperature and high voltage environment The effect of suppressing the voltage drop is sufficient, and the effect of improving battery characteristics after continuous charging is enhanced.
  • the content is preferably 0.03M or more, more preferably 0.05M or more in the non-aqueous electrolyte, and the upper limit thereof is preferably 0.9M or less, more preferably 0.7M or less.
  • the nonaqueous electrolytic solution of the present invention is prepared, for example, by mixing the nonaqueous solvent described above with the electrolyte salt and the compound represented by the general formula (I) with respect to the nonaqueous electrolytic solution and a fluorine atom-containing cyclic carbonate. And at least one selected from the group consisting of unsaturated bond-containing cyclic carbonates.
  • the compound added to the non-aqueous solvent and the non-aqueous electrolyte to be used is one that is purified in advance and has as few impurities as possible within a range that does not significantly reduce the productivity.
  • the nonaqueous electrolytic solution of the present invention can be used in the following first to fourth electric storage devices, and as the nonaqueous electrolyte, not only a liquid but also a gelled one can be used. Furthermore, the non-aqueous electrolyte of the present invention can be used for a solid polymer electrolyte.
  • the 1st electrical storage device which uses lithium salt for electrolyte salt (namely, for lithium batteries) or 4th electrical storage device (namely, for lithium ion capacitors), and it uses for lithium batteries More preferably, it is most suitable to be used for a lithium secondary battery.
  • the lithium battery which is the first power storage device according to the present invention, is a generic term for a lithium primary battery and a lithium secondary battery, and the term lithium secondary battery is used as a concept including a so-called lithium ion secondary battery.
  • the lithium battery of the present invention comprises the nonaqueous electrolyte solution in which an electrolyte salt is dissolved in a positive electrode, a negative electrode, and a nonaqueous solvent.
  • Components other than the non-aqueous electrolyte, such as a positive electrode and a negative electrode, can be used without particular limitation.
  • Positive electrode active material for a lithium secondary battery, a composite metal oxide with lithium containing one or more selected from the group consisting of cobalt, manganese, and nickel is used. These positive electrode active materials can be used alone or in combination of two or more.
  • lithium composite metal oxide examples include LiCoO 2 , LiCo 1-x M x O 2 (where M is Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, and One or more elements selected from the group consisting of Cu, 0.001 ⁇ x ⁇ 0.05, LiMn 2 O 4 , LiNiO 2 , LiCo 1-x Ni x O 2 (0.01 ⁇ x ⁇ 1), LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.5 Mn 0.3 Co 0.2 O 2 , LiNi 0.8 Mn 0.1 Co 0.1 O 2 , LiNi 0 .8 Co 0.15 Al 0.05 O 2 , Li 2 MnO 3 and LiMO 2 (M is a transition metal such as Co, Ni, Mn, and Fe), and LiNi 1/2 Mn 3/2 O one or selected from the group consisting of 4 The above is the more suitable. Moreover, LiCoO 2 and LiMn 2 O 4, LiCoO 2 and LiNiO 2,
  • the continuous charge characteristics under a high temperature and high voltage environment are likely to deteriorate due to a reaction with the electrolyte during charging.
  • the secondary battery it is possible to suppress the deterioration of these electrochemical characteristics.
  • the nonaqueous solvent is generally decomposed on the surface of the positive electrode due to the catalytic action of Ni, and the battery resistance tends to increase.
  • the continuous charge characteristics tend to be deteriorated under a high temperature and high voltage environment.
  • the lithium secondary battery according to the present invention is preferable because it can suppress a decrease in these electrochemical characteristics.
  • the above effect is significant, and more preferably 20 atomic% or more. 30% or more is particularly preferable.
  • LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.5 Mn 0.3 Co 0.2 O 2 , LiNi 0.8 Mn 0.1 Co 0.1 O 2 , One or more selected from the group consisting of LiNi 0.8 Co 0.15 Al 0.05 O 2 and the like are preferable.
  • lithium-containing olivine-type phosphate can also be used as the positive electrode active material.
  • a lithium-containing olivine-type phosphate containing at least one selected from iron, cobalt, nickel and manganese is preferable. Specific examples thereof include LiFePO 4 , LiCoPO 4 , LiNiPO 4 , LiMnPO 4 , and LiFe 1-x Mn x PO 4 (0.1 ⁇ x ⁇ 0.9).
  • Some of these lithium-containing olivine-type phosphates may be substituted with other elements, and some of iron, cobalt, nickel, and manganese are replaced with Co, Mn, Ni, Mg, Al, B, Ti, V, and Nb.
  • LiFePO 4 and LiMnPO 4 are preferable.
  • mold phosphate can also be mixed with the said positive electrode active material, for example, and can be used. Lithium-containing olivine-type phosphate forms a stable phosphoric acid (PO 4 ) structure and is excellent in thermal stability during charging. Therefore, continuous charging characteristics under high temperature and high voltage environment can be improved.
  • the positive electrode for lithium primary battery CuO, Cu 2 O, Ag 2 O, Ag 2 CrO 4, CuS, CuSO 4, TiO 2, TiS 2, SiO 2, SnO, V 2 O 5, V 6 O 12 , VO x , Nb 2 O 5 , Bi 2 O 3 , Bi 2 Pb 2 O 5 , Sb 2 O 3 , CrO 3 , Cr 2 O 3 , MoO 3 , WO 3 , SeO 2 , MnO 2 , Mn 2 O 3 , Fe 2 O 3 , FeO, Fe 3 O 4 , Ni 2 O 3 , NiO, CoO 3 , CoO and other oxides of one or more metal elements or chalcogen compounds, SO 2 , SOCl 2, etc.
  • Examples thereof include sulfur compounds, and fluorocarbons (fluorinated graphite) represented by the general formula (CF x ) n .
  • fluorocarbons fluorinated graphite represented by the general formula (CF x ) n .
  • MnO 2 , V 2 O 5 , graphite fluoride and the like are preferable.
  • the positive electrode conductive agent is not particularly limited as long as it is an electron conductive material that does not cause a chemical change.
  • Examples thereof include graphite such as natural graphite (such as flake graphite) and artificial graphite, carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black. Further, graphite and carbon black may be appropriately mixed and used.
  • the addition amount of the conductive agent to the positive electrode mixture is preferably 1 to 10% by mass, and particularly preferably 2 to 5% by mass.
  • the positive electrode is composed of a conductive agent such as acetylene black and carbon black, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), a copolymer of styrene and butadiene (SBR), acrylonitrile and butadiene.
  • a conductive agent such as acetylene black and carbon black, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), a copolymer of styrene and butadiene (SBR), acrylonitrile and butadiene.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • SBR styrene and butadiene
  • SBR styrene and butadiene
  • acrylonitrile and butadiene acrylonitrile and butadiene.
  • binder such as copolymer (NBR), carb
  • this positive electrode mixture was applied to a current collector aluminum foil, a stainless steel lath plate, etc., dried and pressure-molded, and then subjected to vacuum at a temperature of about 50 ° C. to 250 ° C. for about 2 hours. It can be manufactured by heat treatment.
  • the density of the part except the collector of the positive electrode is usually at 1.5 g / cm 3 or more, for further increasing the capacity of the battery, it is preferably 2 g / cm 3 or more, more preferably, 3 g / cm 3 It is above, More preferably, it is 3.6 g / cm 3 or more.
  • the upper limit is preferably 4 g / cm 3 or less.
  • Examples of the negative electrode active material for a lithium secondary battery include lithium metal, lithium alloy, and carbon material capable of occluding and releasing lithium [easily graphitized carbon and difficult to have a (002) plane spacing of 0.37 nm or more.
  • Graphitized carbon graphite with (002) plane spacing of 0.34 nm or less, etc.], tin (single), tin compound, silicon (single), silicon compound (SiOx: x ⁇ 2), silicon alloy (Si— M alloy: M contains at least one selected from the group consisting of Al, Ni, Cu, Fe, Ti and Mn.), And a group consisting of lithium titanate compounds such as Li 4 Ti 5 O 12 1 type or 2 types or more selected are preferable.
  • a highly crystalline carbon material such as artificial graphite or natural graphite in terms of the ability to occlude and release lithium ions
  • the plane spacing (d 002 ) of the lattice plane ( 002 ) is 0.
  • a carbon material having a graphite type crystal structure of 340 nm (nanometer) or less, particularly 0.335 to 0.337 nm.
  • a mechanical action such as compression force, friction force, shear force, etc. is repeatedly applied to artificial graphite particles having a massive structure in which a plurality of flat graphite fine particles are assembled or bonded non-parallel to each other, for example, scaly natural graphite particles, Using graphite particles that have been subjected to spheroidization treatment, the density of the portion excluding the current collector of the negative electrode can be obtained from X-ray diffraction measurement of the negative electrode sheet when pressed to a density of 1.5 g / cm 3 or more.
  • the graphite crystal It is preferable because the metal elution amount is improved and the charge storage characteristics are improved, more preferably 0.05 or more, and still more preferably 0.1 or more. Moreover, since it may process too much and crystallinity may fall and the discharge capacity of a battery may fall, an upper limit is preferable 0.5 or less, and 0.3 or less is more preferable.
  • the highly crystalline carbon material (core material) is coated with a carbon material that is less crystalline than the core material because continuous charge characteristics under a high temperature and high voltage environment are further improved.
  • the crystallinity of the coating carbon material can be confirmed by a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • Examples of the metal compound capable of inserting and extracting lithium ions as the negative electrode active material include Si, Ge, Sn, Pb, P, Sb, Bi, Al, Ga, In, Ti, Mn, Fe, Co, Ni, Examples thereof include compounds containing at least one metal element such as Cu, Zn, Ag, Mg, Sr, or Ba. These metal compounds may be used in any form such as a simple substance, an alloy, an oxide, a nitride, a sulfide, a boride, and an alloy with lithium, but any of a simple substance, an alloy, an oxide, and an alloy with lithium. Is preferable because the capacity can be increased. Among these, those containing at least one element selected from Si, Ge and Sn are preferable, and those containing at least one element selected from Si and Sn are particularly preferable because the capacity of the battery can be increased.
  • the negative electrode is kneaded using the same conductive agent, binder, and high-boiling solvent as in the production of the positive electrode, and then the negative electrode mixture is applied to the copper foil of the current collector. After being dried and pressure-molded, it can be produced by heat treatment under vacuum at a temperature of about 50 ° C. to 250 ° C. for about 2 hours.
  • the density of the portion excluding the current collector of the negative electrode is usually 1.1 g / cm 3 or more, and is preferably 1.5 g / cm 3 or more, particularly preferably 1.7 g in order to further increase the capacity of the battery. / Cm 3 or more.
  • the upper limit is preferably 2 g / cm 3 or less.
  • examples of the negative electrode active material for a lithium primary battery include lithium metal and lithium alloy.
  • the structure of the lithium battery is not particularly limited, and a coin-type battery, a cylindrical battery, a square battery, a laminated battery, or the like having a single-layer or multi-layer separator can be applied. Although it does not restrict
  • the lithium secondary battery of the present invention is excellent in continuous charge characteristics under a high temperature and high voltage environment even when the end-of-charge voltage is 4.2 V or higher, particularly 4.3 V or higher, and is also characteristic at 4.4 V or higher. Is good.
  • the end-of-discharge voltage is usually 2.8 V or higher, and more preferably 2.5 V or higher, but the lithium secondary battery in the present invention can be 2.0 V or higher.
  • the current value is not particularly limited, but is usually used in the range of 0.1 to 30C. Further, the lithium battery in the present invention can be charged / discharged at ⁇ 40 to 100 ° C., preferably ⁇ 10 to 80 ° C.
  • a method of providing a safety valve on the battery lid or cutting a member such as a battery can or a gasket can be employed.
  • the battery lid can be provided with a current interruption mechanism that senses the internal pressure of the battery and interrupts the current.
  • the 2nd electrical storage device which concerns on this invention is an electrical storage device which stores the energy using the electric double layer capacity
  • An example of the present invention is an electric double layer capacitor.
  • the most typical electrode active material used for this electricity storage device is activated carbon. Double layer capacity increases roughly in proportion to surface area.
  • the 3rd electrical storage device which concerns on this invention is an electrical storage device which stores the energy using the dope / dedope reaction of an electrode including the non-aqueous electrolyte of this invention.
  • the electrode active material used in this power storage device include metal oxides such as ruthenium oxide, iridium oxide, tungsten oxide, molybdenum oxide, and copper oxide, and ⁇ -conjugated polymers such as polyacene and polythiophene derivatives. Capacitors using these electrode active materials can store energy associated with electrode doping / dedoping reactions.
  • the 4th electrical storage device which concerns on this invention is an electrical storage device which stores the energy using the intercalation of the lithium ion to carbon materials, such as graphite which is a negative electrode, containing the non-aqueous electrolyte of this invention. It is called a lithium ion capacitor (LIC).
  • the positive electrode include those using an electric double layer between an activated carbon electrode and an electrolytic solution, and those using a ⁇ -conjugated polymer electrode doping / dedoping reaction.
  • the electrolyte contains at least a lithium salt such as LiPF 6 .
  • Examples 1 to 45, Comparative Examples 1 to 4 [Production of lithium ion secondary battery] 92% by mass of LiNi 0.8 Co 0.1 Mn 0.1 O 2 and 5% by mass of acetylene black (conductive agent) are mixed, and 3% by mass of polyvinylidene fluoride (binder) is previously added to 1-methyl-2-
  • a positive electrode mixture paste was prepared by adding to and mixing with the solution dissolved in pyrrolidone. This positive electrode mixture paste was applied to one side of an aluminum foil (current collector), dried and pressurized, and cut into a predetermined size to produce a positive electrode sheet. The density of the portion excluding the current collector of the positive electrode was 3.6 g / cm 3 .
  • a negative electrode mixture paste was prepared by adding to the dissolved solution and mixing. This negative electrode mixture paste was applied to one side of a copper foil (current collector), dried and pressurized, and cut into a predetermined size to produce a negative electrode sheet. The density of the portion excluding the current collector of the negative electrode was 1.5 g / cm 3 .
  • Average discharge voltage change rate (relative value) (%) (initial average discharge voltage ⁇ average discharge voltage after continuous charge) / (initial average discharge voltage in comparative example 1 ⁇ average discharge after continuous charge in comparative example 1) Voltage) x 100
  • the capacity recovery rate and the average discharge voltage reduction rate after high-temperature storage were also insufficient.
  • the effects of the present invention are as follows.
  • a specific amount of the compound represented by the general formula (I) of the present invention, a fluorine atom-containing cyclic carbonate It has been found that the effect is unique when at least one selected from the group consisting of saturated bond-containing cyclic carbonates is contained in combination.
  • non-aqueous electrolyte of the present invention also has an effect of improving the capacity recovery rate and average discharge voltage reduction rate after high-temperature storage such as lithium ion capacitors and lithium air batteries.

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Abstract

La présente invention concerne : une solution électrolytique non aqueuse pour un dispositif de stockage d'électricité dans lequel un sel électrolytique est dissous dans un solvant non aqueux, la solution électrolytique non aqueuse étant caractérisée en ce qu'elle contient 0,1 à 4 % en masse d'un composé représenté par la formule générale (I), et contenant 0,1 à 30 % en masse d'au moins un composé choisi dans le groupe constitué par des carbonates cycliques contenant du fluor et des carbonates cycliques contenant des liaisons insaturées en tant qu'additif; et un dispositif de stockage d'électricité dans lequel il est possible d'améliorer les caractéristiques de charge continue dans un environnement à haute température et haute tension. (Dans la formule, R1 représente un groupe alkyle en C1-7 ou un groupe cycloalkyle en C3-6; R2 à R6 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle en C1-4, ou un groupe -CH2OC(=O)OR7; R7 représente un groupe alkyle en C1-4; et n est égale à 0 ou 1.)
PCT/JP2018/011747 2017-04-28 2018-03-23 Solution électrolytique non aqueuse et dispositif de stockage d'électricité l'utilisant Ceased WO2018198618A1 (fr)

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WO2025108540A1 (fr) * 2023-11-22 2025-05-30 Symrise Ag 5-méthylcyclohexanols et dérivés utilisés en tant que parfums

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WO2023286885A1 (fr) * 2021-07-14 2023-01-19 동화일렉트로라이트 주식회사 Nouveau composé, électrolyte pour batterie secondaire comprenant ce composé et batterie secondaire comprenant cet électrolyte

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WO2025108540A1 (fr) * 2023-11-22 2025-05-30 Symrise Ag 5-méthylcyclohexanols et dérivés utilisés en tant que parfums

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