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WO2017047554A1 - Solution électrolytique non aqueuse pour dispositifs de stockage d'électricité et dispositif de stockage d'électricité utilisant celle-ci - Google Patents

Solution électrolytique non aqueuse pour dispositifs de stockage d'électricité et dispositif de stockage d'électricité utilisant celle-ci Download PDF

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Publication number
WO2017047554A1
WO2017047554A1 PCT/JP2016/076865 JP2016076865W WO2017047554A1 WO 2017047554 A1 WO2017047554 A1 WO 2017047554A1 JP 2016076865 W JP2016076865 W JP 2016076865W WO 2017047554 A1 WO2017047554 A1 WO 2017047554A1
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Prior art keywords
lithium
storage device
carbonate
electricity storage
nonaqueous
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Japanese (ja)
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安部　浩司
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Ube Corp
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Ube Industries Ltd
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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
    • H01G11/64—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
    • 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 for an electricity storage device capable of improving electrochemical characteristics over a wide temperature range and an electricity storage device using the same.
  • power storage devices particularly lithium secondary batteries
  • small electronic devices such as mobile phones and laptop computers, electric vehicles, and power storage sources.
  • these electronic devices and automobiles may be used in a wide temperature range such as a high temperature in midsummer or a low temperature in extremely cold, it is required to improve electrochemical characteristics in a wide range of temperatures. .
  • CO 2 emissions there is an urgent need to reduce CO 2 emissions.
  • environmentally friendly vehicles equipped with power storage devices consisting of power storage devices such as lithium secondary batteries and lithium ion capacitors
  • hybrid electricity Early spread of automobiles (HEV), plug-in hybrid electric vehicles (PHEV), and battery electric vehicles (BEV) is required.
  • lithium secondary battery Due to the long travel distance of automobiles, automobiles may be used in areas with a wide temperature range from extremely hot areas in the tropics to extremely cold areas. Therefore, in particular, these in-vehicle power storage devices are required not to deteriorate in electrochemical characteristics even when used in a wide temperature range from high temperature to low temperature.
  • the term lithium secondary battery is used as a concept including a so-called lithium ion secondary battery.
  • a lithium secondary battery is mainly composed of a positive electrode and a negative electrode containing a material capable of occluding and releasing lithium ions, a lithium salt, and a non-aqueous electrolyte composed of a non-aqueous solvent.
  • a non-aqueous solvent ethylene carbonate (EC ), Carbonates such as propylene carbonate (PC) are used.
  • EC ethylene carbonate
  • PC propylene carbonate
  • negative electrodes of lithium secondary batteries metal lithium, metal compounds capable of inserting and extracting lithium ions (metal simple substance, metal oxide, alloy with lithium, etc.) and carbon materials are known.
  • lithium secondary batteries using carbon materials such as coke, artificial graphite, and natural graphite capable of inserting and extracting lithium ions have been widely put into practical use.
  • a lithium secondary battery using a highly crystallized carbon material such as natural graphite or artificial graphite as a negative electrode material is a decomposition product generated by reductive decomposition of a solvent in a non-aqueous electrolyte on the negative electrode surface during charging. It has been found that the gas interferes with the desired electrochemical reaction of the battery, resulting in poor cycle characteristics. Further, when a decomposition product of a nonaqueous solvent accumulates on the electrode surface, lithium cannot be smoothly occluded and released from the negative electrode, and the electrochemical characteristics when used in a wide temperature range are liable to deteriorate.
  • lithium secondary batteries using lithium metal, alloys thereof, simple metals such as tin or silicon, and metal oxides as negative electrode materials have high initial capacities, but fine powders progress during the cycle. It is known that reductive decomposition of a nonaqueous solvent occurs at an accelerated rate as compared with a negative electrode, and battery performance such as battery capacity and cycle characteristics is greatly reduced. In addition, due to the pulverization of these negative electrode materials and the accumulation of decomposition products of nonaqueous solvents, the insertion and extraction of lithium into the negative electrode cannot be performed smoothly, and the electrochemical characteristics when used over a wide temperature range are likely to deteriorate. .
  • a positive electrode material for example, a lithium secondary battery using LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiFePO 4, etc.
  • the non-aqueous solvent in the non-aqueous electrolyte is charged and the positive electrode material and the non-aqueous electrolyte are used.
  • the battery performance has been deteriorated due to the movement of lithium ions or the expansion of the battery due to the decomposition product or gas when the non-aqueous electrolyte is decomposed on the positive electrode or the negative electrode.
  • electronic devices equipped with lithium secondary batteries are becoming more and more multifunctional and power consumption is increasing.
  • the capacity of lithium secondary batteries has been increasing, and the density of the electrodes has been increased and the useless space in the battery has been reduced.
  • the volume occupied by the nonaqueous electrolyte in the battery has been reduced. It has become.
  • Patent Document 1 describes that a nonaqueous electrolytic solution containing a cyclic sulfate such as ethylene glycol sulfate can suppress capacity deterioration associated with a charge / discharge cycle.
  • Patent Document 2 hexahydro 1,3,2-benzodioxathiol 2,2-dioxide (6-membered cyclic sulfate), 1,2-cyclohexanediol cyclic sulfite (6-membered cyclic sulfite) and the like 1 , 2-cyclohexanediol derivatives (6-membered ring compounds) are described as being excellent in long-term cycle characteristics and capable of suppressing gas generation.
  • Patent Document 3 discloses that a non-aqueous electrolyte containing a cyclic (5-membered ring) carbonate ester compound such as 1,2-cyclopentanediol cyclic carbonate is a normal temperature cycle characteristic, storage characteristic and low temperature of a secondary battery. It is described to improve cycle characteristics.
  • JP-A-10-189042 International Publication No. 2007/020876 JP 2011-124008 A
  • An object of the present invention is to provide a nonaqueous electrolytic solution for an electricity storage device that can improve electrochemical characteristics in a wide temperature range and an electricity storage device using the same.
  • the present invention provides the following (1) and (2).
  • X represents an S ( ⁇ O) 2 group or an S ⁇ O group
  • R 1 to R 8 each independently represents a hydrogen atom, a halogen atom, or a part of the hydrogen atom is substituted with a halogen atom.
  • 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).
  • An electricity storage device characterized by the above.
  • a nonaqueous electrolytic solution for an electricity storage device capable of improving the electrochemical characteristics of the electricity storage device in a wide temperature range, particularly a low temperature discharge property after high temperature storage, and an electricity storage device such as a lithium battery using the same. be able to.
  • non-aqueous electrolyte for power storage devices is a non-aqueous electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent, and the general formula (I)
  • the compound represented by the formula is characterized by containing 0.01 to 10% by mass in the non-aqueous electrolyte.
  • the compound used by this invention is a compound chosen from the sulfate ester and sulfite ester containing a cyclopentane structure as described in the said general formula (I).
  • This cyclopentane ring (five-membered ring) has a larger strain energy than the cyclohexane ring (six-membered ring).
  • the hexahydro 1,3 described in Patent Document 2 is a sulfate or sulfite containing a cyclopentane structure represented by the general formula (I), which is a sulfate or sulfite containing a cyclohexane (six-membered ring) structure.
  • 2-benzodioxathiol 2,2-dioxide and 1,2-cyclohexanediol cyclic sulfite are more susceptible to electrochemical decomposition, and a dense and highly heat-resistant film is formed on the positive and negative electrodes.
  • the nonaqueous electrolytic solution of the present invention can improve electrochemical characteristics in a wide temperature range such as low temperature discharge characteristics after high temperature storage, compared with the nonaqueous electrolytic solutions of Patent Documents 1 and 2. Conceivable.
  • the compound selected from sulfate and sulfite contained in the non-aqueous electrolyte of the present invention is represented by the following general formula (I).
  • X represents an S ( ⁇ O) 2 group or an S ⁇ O group
  • R 1 to R 8 each independently represents a hydrogen atom, a halogen atom, or a part of the hydrogen atom is substituted with a halogen atom.
  • R 1 to R 8 are each independently a hydrogen atom, a halogen atom such as a fluorine atom, or a part of the hydrogen atom which may be substituted with a halogen atom. 3, preferably an alkyl group having 1 or 2 carbon atoms, more preferably a hydrogen atom or a fluorine atom, and still more preferably a hydrogen atom.
  • the number of substituents of the alkyl group which may be partially substituted with a halogen atom or a hydrogen atom is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.
  • substitution position of the alkyl group in which a halogen atom or a part of the hydrogen atom may be substituted with a halogen atom is the 4-position, as viewed from X (S ( ⁇ O) 2 group or S ⁇ O group), that is, R 2. Or it is preferable that it is a position of R ⁇ 3 > or R ⁇ 6 > or R ⁇ 7 >.
  • R 1 to R 8 are an alkyl group in which a part of hydrogen atoms may be substituted with a halogen atom include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.
  • Some hydrogen atoms such as propyl group, 2,2,3,3-tetrafluoropropyl group, and 2,2,3,3,3-pentafluoropropyl group are substituted with halogen atoms.
  • Alkyl group is preferably exemplified. Among these, a methyl group, an ethyl group, an n-propyl group, a trifluoromethyl group, or a 2,2,2-trifluoroethyl group is preferable, a methyl group, an ethyl group, or a trifluoromethyl group is more preferable. Further preferred are groups or ethyl groups.
  • the sulfate ester or sulfite ester having a cyclopentane structure represented by the general formula (I) is a cis-type compound represented by the following general formula (II) and a trans-type compound represented by the following general formula (III). Include.
  • the compound represented by the general formula (I) may be a mixture of a cis-type compound represented by the general formula (II) and a trans-type compound represented by the general formula (III).
  • the cis-type compound / trans-type compound (mass ratio) is preferably 50/50 to 100/0, more preferably 60/40 to 100/0, still more preferably 70/30 to 100/0, and still more preferably 80 / 20 to 100/0, more preferably 90/10 to 100/0, and particularly preferably a cis-type compound alone.
  • Specific examples of the sulfate represented by the general formula (I) include the following compounds 1 to 22.
  • Specific examples of the sulfite ester represented by the general formula (I) include the following compounds 23 to 44.
  • tetrahydro-4H-cyclopenta [d] [1,3,2] dioxathiol-2,2-dioxide (Compound 1), 4-fluorotetrahydro-4H-cyclopenta [d] [ 1,3,2] dioxathiol-2,2-dioxide (compound 3), 4-methyltetrahydro-4H-cyclopenta [d] [1,3,2] dioxathiol-2,2-dioxide (compound 8) ), Tetrahydro-4H-cyclopenta [d] [1,3,2] dioxathiol-2-oxide (compound 23), 4-fluorotetrahydro-4H-cyclopenta [d] [1,3,2] dioxathiol -2-oxide (compound 25), and 4-methyltetrahydro-4H-cyclopenta [d] [1,3,2] dioxathiol-2-oxide (compound 3) ) Is chosen one or more kinds from.
  • tetrahydro-4H-cyclopenta [d] [1,3,2] dioxathiol-2,2-dioxide Compound 1
  • 4-fluorotetrahydro-4H-cyclopenta [d] [1,3,2 ] One or more selected from dioxathiol-2,2-dioxide (compound 3) and tetrahydro-4H-cyclopenta [d] [1,3,2] dioxathiol-2-oxide (compound 23)
  • Particularly preferred is tetrahydro-4H-cyclopenta [d] [1,3,2] dioxathiol-2,2-dioxide (Compound 1).
  • the total content of the compound represented by the general formula (I) (sulfuric ester and sulfite) contained in the non-aqueous electrolytic solution is 0.01 in the non-aqueous electrolytic solution. ⁇ 10% by mass.
  • the content is more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more in the non-aqueous electrolyte.
  • the upper limit is preferably 5% by mass or less, and more preferably 3% by mass or less.
  • the compound represented by the general formula (I) can be combined with a non-aqueous solvent, an electrolyte salt, and other additives described below to have electrochemical characteristics over a wide temperature range. It produces a unique effect of synergistic improvement.
  • Nonaqueous solvent As the non-aqueous solvent used in the non-aqueous electrolyte solution of the present invention, one or more selected from cyclic carbonates, chain esters, lactones, ethers and amides are preferably mentioned. In order to synergistically improve electrochemical properties over a wide temperature range, it is preferable that a chain ester is included, more preferably a chain carbonate is included, and both a cyclic carbonate and a chain ester are further included. It is particularly preferable that both cyclic carbonate and chain carbonate are included.
  • chain ester is used as a concept including a chain carbonate and a chain carboxylic acid ester.
  • Cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 4-fluoro-1,3-dioxolan-2-one (FEC), trans or Cis-4,5-difluoro-1,3-dioxolan-2-one (hereinafter collectively referred to as “DFEC”), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and 4-ethynyl-1 , 3-dioxolan-2-one (EEC), or two or more kinds selected from ethylene carbonate (EC), propylene carbonate (PC), 4-fluoro-1,3-dioxolan-2-one (FEC) ), Vinylene carbonate (VC), and 4-ethynyl-1,3-dioxo One or two or more selected from the emission-2-one (EEC) is more preferable.
  • DFEC ethylene carbonate
  • PC propylene carbonate
  • FEC 1,
  • cyclic carbonates having a fluorine atom use of at least one of unsaturated bonds such as carbon-carbon double bonds or carbon-carbon triple bonds, or cyclic carbonates having a fluorine atom is preferable because the electrochemical properties in a high temperature environment are further improved. More preferably, both a cyclic carbonate containing an unsaturated bond such as a carbon double bond or a carbon-carbon triple bond and a cyclic carbonate having a fluorine atom are included.
  • VC, VEC, or EEC is more preferable
  • the cyclic carbonate having a fluorine atom FEC or DFEC is more preferable.
  • the content of the cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond is preferably 0.07% by volume or more, more preferably 0.8%, based on the total volume of the nonaqueous solvent.
  • the upper limit is preferably 7% by volume or less, more preferably 4% by volume or less, and still more preferably 2.5% by volume or less. It is preferable for the content to be in the above-mentioned range since the electrochemical characteristics can be increased in a wider temperature range without impairing Li ion permeability.
  • the content of the cyclic carbonate having a fluorine atom is preferably 0.07% by volume or more, more preferably 0.7% by volume or more, still more preferably 4% by volume or more, and most preferably based on the total volume of the nonaqueous solvent.
  • the upper limit is preferably 35% by volume or less, more preferably 25% by volume or less, and further 15% by volume or less. It is preferable for the content to be in the above range since the electrochemical characteristics in a wider temperature range can be improved without impairing the Li ion permeability.
  • the content of the cyclic carbonate having an unsaturated bond with respect to the content of the cyclic carbonate having a fluorine atom is preferably 0.2% by volume or more, more preferably 3% by volume or more, further preferably 7% by volume or more, and the upper limit thereof is preferably 40% by volume or less, more preferably 30% by volume or less, and further 15% by volume or less. is there.
  • the content within the above range is particularly preferable because electrochemical characteristics in a wider temperature range can be improved without impairing Li ion permeability.
  • the non-aqueous solvent contains both the cyclic carbonate having the unsaturated bond, since the electrochemical characteristics in a wide temperature range of the film formed on the electrode can be improved.
  • the content of the cyclic carbonate having a bond is preferably 3% by volume or more, more preferably 5% by volume or more, and still more preferably 7% by volume or more with respect to the total volume of the non-aqueous solvent. Preferably it is 45 volume% or less, More preferably, it is 35 volume% or less, More preferably, it is 25 volume% or less.
  • cyclic carbonates include EC and PC, EC and VC, PC and VC, VC and FEC, EC and FEC, PC and FEC, FEC and DFEC, EC and DFEC, PC and DFEC, VC and DFEC , VEC and DFEC, VC and EEC, EC and EEC, EC and PC and VC, EC and PC and FEC, EC and VC and FEC, EC and VC and VEC, EC and VC and EEC, EC and EEC and FEC, PC And VC and FEC, EC and VC and DFEC, PC and VC and DFEC, EC and PC and VC and FEC, or EC and PC, VC and DFEC are examples of these cyclic carbonates.
  • one or more asymmetric chain carbonates selected from methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate, and ethyl propyl carbonate; dimethyl
  • One or more symmetrical linear carbonates selected from carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, and dibutyl carbonate
  • pivalate esters such as methyl pivalate, ethyl pivalate, and propyl pivalate
  • propion Preferable examples include one or more chain carboxylic acid esters selected from methyl acid, ethyl propionate (EP), propyl propionate, methyl acetate, and ethyl acetate (EA).
  • chain esters dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate, methyl propionate, methyl acetate and ethyl acetate (EA)
  • DMC dimethyl carbonate
  • MEC methyl ethyl carbonate
  • MPC methyl propyl carbonate
  • MIPC methyl isopropyl carbonate
  • EA methyl butyl carbonate
  • chain carbonate it is preferable to use 2 or more types.
  • it is more preferable that both a symmetric chain carbonate and an asymmetric chain carbonate are contained, and it is further more preferable that more symmetric chain carbonate is contained than the asymmetric chain carbonate.
  • 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 is lowered and the electrochemistry in a wide temperature range is achieved. Since there is little possibility that a characteristic will fall, it is preferable that it is the said range.
  • 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.
  • the upper limit is more preferably 95% by volume or less, and still more preferably 85% by volume or less. It is particularly preferred that dimethyl carbonate (DMC) is contained in the symmetric chain carbonate.
  • the asymmetric chain carbonate preferably has a methyl group, and methyl ethyl carbonate (MEC) is particularly preferable. The above case is preferable because electrochemical characteristics in a wider temperature range are improved.
  • the ratio between the cyclic carbonate and the chain ester is preferably 10/90 to 45/55, and preferably 15/85 to 40/60, from the viewpoint of improving electrochemical properties at high temperatures. Is more preferable, and 20/80 to 35/65 is particularly preferable.
  • non-aqueous solvents include cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and 1,4-dioxane, chains such as 1,2-dimethoxyethane, 1,2-diethoxyethane and 1,2-dibutoxyethane.
  • Preferable examples include one or two or more selected from amides such as cyclic ethers, amides such as dimethylformamide, sulfones such as sulfolane, and lactones such as ⁇ -butyrolactone (GBL), ⁇ -valerolactone, and ⁇ -angelicalactone.
  • 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.
  • the above non-aqueous solvents are usually used as a mixture in order to achieve appropriate physical properties.
  • the combination includes, for example, a combination of a cyclic carbonate and a chain carbonate, a combination of a cyclic carbonate and a chain carboxylic acid ester, a combination of a cyclic carbonate, a chain ester (particularly a chain carbonate) and a lactone, and a cyclic carbonate and a chain.
  • Preferred examples include a combination of a chain ester (particularly a chain carbonate) and an ether, a combination of a cyclic carbonate, a chain carbonate and a chain carboxylic acid ester, etc., and a combination of a cyclic carbonate, a chain ester and a lactone is more preferable.
  • lactones ⁇ -butyrolactone (GBL) is more preferred.
  • additives can be added to the non-aqueous electrolyte.
  • specific examples of other additives include the following compounds (A) to (I).
  • nitriles selected from acetonitrile, propionitrile, succinonitrile, glutaronitrile, adiponitrile, pimeonitrile, suberonitrile, and sebacononitrile.
  • Aroma Compound. (C) selected from methyl isocyanate, ethyl isocyanate, butyl isocyanate, phenyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, 1,4-phenylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate
  • One or more isocyanate compounds selected from methyl isocyanate, ethyl isocyanate, butyl isocyanate, phenyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, 1,4-phenylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate
  • Cyclic phosphazene compounds such as methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, or ethoxyheptafluorocyclotetraphosphazene.
  • nitriles one or more selected from succinonitrile, glutaronitrile, adiponitrile, and pimelonitrile are more preferable.
  • aromatic compounds one or more selected from biphenyl, terphenyl (o-, m-, p-isomer), fluorobenzene, cyclohexylbenzene, tert-butylbenzene, and tert-amylbenzene are more preferable, and one or more selected from biphenyl, o-terphenyl, fluorobenzene, cyclohexylbenzene, and tert-amylbenzene are particularly preferable.
  • isocyanate compounds (C) one or more selected from hexamethylene diisocyanate, octamethylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate are more preferable.
  • each of the compounds (A) to (C) is preferably 0.01 to 7% by mass in the non-aqueous electrolyte. In this range, the film is sufficiently formed without becoming too thick, and the electrochemical characteristics in a wider temperature range are enhanced.
  • the 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, further preferably 3% by mass or less. .
  • (D) Triple bond-containing compound, (E) Sultone, cyclic sulfite, sulfonic acid ester, cyclic S O group-containing compound selected from vinyl sulfone, (F) cyclic acetal compound, (G) It is preferable to include a phosphorus-containing compound, (H) a cyclic acid anhydride, and (I) a cyclic phosphazene compound because the electrochemical properties in a wider temperature range are further improved.
  • Triple bond-containing compounds include 2-propynyl methyl carbonate, 2-propynyl methacrylate, 2-propynyl methanesulfonate, 2-propynyl vinylsulfonate, 2-propynyl 2- (methanesulfonyloxy) propionate, di Preferably, one or more selected from (2-propynyl) oxalate, methyl 2-propynyl oxalate, ethyl 2-propynyl oxalate, and 2-butyne-1,4-diyl dimethanesulfonate, 2-propynyl methanesulfonate, One or more selected from 2-propynyl vinyl sulfonate, 2-propynyl 2- (methanesulfonyloxy) propionate, di (2-propynyl) oxalate, and 2-butyne-1,4-diyl dimethanesulfonate,
  • 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-oxathiolan-4-one 2,2-dioxide, methylene methane disulfonate, ethylene sulfite, ethylene sulfate, and 4- (methylsulfonyl)
  • Preferable examples include one or more selected from methyl) -1,3,2-dioxathiolane 2-oxide.
  • the chain-like S ⁇ O group-containing compounds include butane-2,3-diyl dimethanesulfonate, butane-1,4-diyl dimethanesulfonate, dimethyl methane disulfonate, pentafluorophenyl methanesulfonate, divinylsulfone, And one or more selected from 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 acetate , Ethylene sulfate, pentafluorophenyl methanesulfonate, and one or more selected from divinylsulfone are more preferable.
  • 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
  • the cyclic acid anhydride is preferably succinic anhydride, maleic anhydride, or 3-allyl succinic anhydride, more preferably succinic anhydride or 3-allyl succinic anhydride.
  • a cyclic phosphazene compound such as methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, or phenoxypentafluorocyclotriphosphazene is preferable, and methoxypentafluorocyclotriphosphazene or ethoxypentafluorocyclo Triphosphazene is more preferred.
  • each of the compounds (D) to (I) is preferably 0.001 to 5% by mass in the non-aqueous electrolyte. In this range, the film is sufficiently formed without becoming too thick, and the electrochemical characteristics in a wider temperature range are enhanced.
  • the content is more preferably 0.01% 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 3% by mass or less, and further preferably 2% by mass or less. .
  • a lithium salt having an oxalic acid skeleton, a lithium salt having a phosphoric acid skeleton, and a lithium salt having an S ⁇ O group are further included in the non-aqueous electrolyte. It is preferable to include one or more lithium salts selected from the inside. Specific examples of lithium salts include lithium bis (oxalato) borate [LiBOB], lithium difluoro (oxalato) borate [LiDFOB], lithium tetrafluoro (oxalato) phosphate [LiTFOP], and lithium difluorobis (oxalato) phosphate [LiDFOP].
  • the proportion of the lithium salt in the non-aqueous solvent is preferably 0.001M or more and 0.5M or less. Within this range, the effect of improving electrochemical characteristics over a wide temperature range is further exhibited. Preferably it is 0.01M or more, More preferably, it is 0.03M or more, More preferably, it is 0.04M or more.
  • the upper limit is preferably 0.4M or less, more preferably 0.2M or less. (However, M represents mol / L.)
  • Electrode salt Preferred examples of the electrolyte salt used in the present invention include the following lithium salts.
  • the lithium salt include inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiN (SO 2 F) 2 [LiFSI], LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiCF 3 SO 3 , LiC (SO 2 CF 3 ) 3 , LiPF 4 (CF 3 ) 2 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (CF 3 ) 3 , LiPF 3 (iso-C 3 F 7 ) 3 , lithium salt containing a chain-like fluorinated alkyl group such as LiPF 5 (iso-C 3 F 7 ), (CF 2 ) 2 (SO 2 ) 2 NLi, (CF 2 ) 3 (SO 2 ) 2 NLi Preferred examples include at least one lithium salt selected from lithium salts having a cycl
  • LiPF 6 LiBF 4 , LiN (SO 2 F) 2 [LiFSI], LiN (SO 2 CF 3 ) 2 , and LiN (SO 2 C 2 F 5 ) 2 are included.
  • LiPF 6 is most preferably used.
  • the concentration of the electrolyte salt is usually preferably 0.3 M or more, more preferably 0.7 M or more, and further preferably 1.1 M or more with respect to the non-aqueous solvent. Moreover, the upper limit is preferably 2.5M or less, more preferably 2.0M or less, and still more preferably 1.6M or less.
  • these electrolyte salts include LiPF 6, further LiBF 4, LiN (SO 2 CF 3) 2, and at least one lithium salt selected from LiN (SO 2 F) 2 [LiFSI] Is preferably contained in the non-aqueous electrolyte.
  • the proportion of the lithium salt other than LiPF 6 in the non-aqueous solvent is 0.001M or more, the effect of improving the electrochemical characteristics in a wide temperature range is easily exhibited, and if it is 1.0M or less, the wide temperature range. This is preferable because there is little concern that the effect of improving the electrochemical characteristics of the material will decrease.
  • it is 0.01M or more, More preferably, it is 0.03M or more, More preferably, it is 0.04M or more.
  • the upper limit is preferably 0.8M or less, more preferably 0.6M or less, and still more preferably 0.4M or less.
  • the non-aqueous electrolyte of the present invention is, for example, a compound containing the cyclopentane structure represented by the general formula (I) with respect to the electrolyte salt and the non-aqueous electrolyte mixed with the non-aqueous solvent. Can be obtained.
  • the compound represented by the general formula (I) to be added to the nonaqueous solvent and the nonaqueous electrolytic solution to be used should be purified in advance within a range that does not significantly reduce the productivity, and should have a minimum amount of impurities. preferable.
  • 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. In particular, it is preferably used for the first electricity storage device (that is, for a lithium battery) or the fourth electricity storage device (that is, for a lithium ion capacitor) that uses a lithium salt as an electrolyte salt, and is used for a lithium battery. More preferably, it is more preferably used for a lithium secondary battery.
  • the lithium battery as the first power storage device is a general term for a lithium primary battery and a lithium secondary battery, and the 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.
  • the 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 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 0.6 Mn 0.2 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, Fe) , and LiNi 1/2 Mn 3/2 O One or two or more selected from 4 are more preferable.
  • LiCoO 2 and LiMn 2 O 4 LiCoO 2 and Li
  • the electrochemical characteristics are generally likely to deteriorate in a high temperature environment due to a reaction with the electrolyte during charging.
  • the deterioration of these electrochemical characteristics can be suppressed.
  • the nonaqueous solvent is generally decomposed on the surface of the positive electrode due to the catalytic action of Ni, and the resistance of the battery tends to increase.
  • the electrochemical characteristics in a high temperature environment tend to be deteriorated.
  • the lithium secondary battery according to the present invention is preferable because it can suppress the deterioration of these electrochemical characteristics.
  • the positive electrode active material having a ratio of the atomic concentration of Ni to the atomic concentration of all transition metal elements in the positive electrode active material exceeding 10 atomic% is preferable because the above-described effect becomes remarkable, and the positive electrode active of 20 atomic% or more is preferable. It is more preferable to use a substance, and it is more preferable to use a positive electrode active material of 30 atomic% or more. Specifically, LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.5 Mn 0.3 Co 0.2 O 2 , LiNi 0.6 Mn 0.2 Co 0.2 O 2 , One type or two or more types selected from LiNi 0.8 Mn 0.1 Co 0.1 O 2 and LiNi 0.8 Co 0.15 Al 0.05 O 2 are preferable.
  • lithium-containing olivine-type phosphate can also be used as the positive electrode active material.
  • lithium-containing olivine-type phosphate containing one or more selected from iron, cobalt, nickel and manganese is preferable. Specific examples thereof include one or more selected from 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 or LiMnPO 4 is 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 skeleton (PO 4 ) structure and is excellent in thermal stability during charging, and therefore can improve electrochemical characteristics in a wide temperature range.
  • 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 or chalcogen compounds of one or more metal elements, sulfur such as SO 2 and SOCl 2 Examples thereof include a compound and fluorocarbon (fluorinated graphite) represented by the general formula (CF x ) n . Among these, MnO 2, V 2 O 5 , fluorinated graphite 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 more 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 portion excluding the current collector of the positive electrode is usually 1.5 g / cm 3 or more, and in order to further increase the capacity of the battery, preferably 2 g / cm 3 or more, more preferably 3 g / cm 3 or more, 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, lithium titanate compound such as Li 4 Ti 5 O 12 1 type or 2 types or more chosen from etc. are mentioned.
  • a highly crystalline carbon material such as artificial graphite or natural graphite in terms of the ability to occlude and release lithium ions
  • the lattice spacing ( 002 ) has an interplanar spacing (d 002 ) of 0.1.
  • a carbon material having a graphite type crystal structure of 340 nm (nanometer) or less, particularly 0.335 to 0.337 nm.
  • 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, and mechanical actions such as compressive force, frictional force, shearing force, etc. are repeatedly applied, and scaly natural graphite is spherical. It is preferable to use particles that have been treated.
  • plane peak intensity I (004) ratio I (110) / I (004) is preferably 0.01 or more, because the electrochemical characteristics in a wider temperature range are further improved. More preferably, it is more preferably 0.1 or more.
  • the upper limit of the peak intensity ratio I (110) / I (004) is preferably 0.5 or less. 3 or less is more preferable.
  • the highly crystalline carbon material (core material) is coated with a carbon material having lower crystallinity than the core material because electrochemical characteristics in a wide temperature range are further improved.
  • the crystallinity of the carbon material of the coating can be confirmed by TEM.
  • Examples of the metal compound capable of inserting and extracting lithium as the negative electrode active material include Si, Ge, Sn, Pb, P, Sb, Bi, Al, Ga, In, Ti, Mn, Fe, Co, Ni, and Cu. , Zn, Ag, Mg, Sr, or a compound containing at least one metal element such as 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.
  • 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, more preferably 1.7 g in order to further increase the battery capacity. / 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.
  • the battery separator is not particularly limited, and a single layered or laminated microporous film of polypropylene, polyethylene, ethylene-propylene copolymer or the like, a woven fabric, a nonwoven fabric, or the like can be used.
  • the polyolefin laminate is preferably a laminate of polyethylene and polypropylene, more preferably a three-layer structure of polypropylene / polyethylene / polypropylene. The thickness of a separator becomes like this.
  • it is 2 micrometers or more, More preferably, it is 3 micrometers or more, More preferably, it is 4 micrometers or more, and the upper limit is 30 micrometers or less, Preferably it is 20 micrometers or less, More preferably, it is 15 micrometers or less.
  • the lithium secondary battery according to the present invention has excellent electrochemical characteristics in a wide temperature range even when the end-of-charge voltage is 4.2 V or more, particularly 4.3 V or more, and the characteristics are also good at 4.4 V or more. is there.
  • the end-of-discharge voltage is usually 2.8 V or more, and further 2.5 V or more, but the lithium secondary battery in the present invention can be 2.0 V or more.
  • the current value is not particularly limited, but is usually used in the range of 0.1 to 30C.
  • 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 of 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 of 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 of this invention is an electrical storage device which stores the energy using the intercalation of lithium ion to carbon materials, such as a 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 electrolytic solution contains at least a lithium salt such as LiPF 6 .
  • Examples 1 to 16 Comparative Examples 1 to 4 [Production of lithium ion secondary battery] LiNi 0.6 Mn 0.2 Co 0.2 O 2 93% by mass and acetylene black (conductive agent) 4% by mass are mixed, and 3% by mass of polyvinylidene fluoride (binder) is preliminarily 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 .
  • 5% by mass was added to a solution dissolved in 1-methyl-2-pyrrolidone and mixed to prepare a negative electrode mixture paste.
  • 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 1.6 g / cm 3 .
  • the ratio of the peak intensity I (110) of the (110) plane of the graphite crystal to the peak intensity I (004) of the (004) plane [I (110) / I (004)] was 0.1.
  • a positive electrode sheet, a separator made of a microporous polyethylene film, and a negative electrode sheet were laminated in this order, and a non-aqueous electrolyte solution having the composition shown in Tables 1 and 2 was added to produce a laminated battery.
  • Examples 17 to 18 and Comparative Example 5 In place of the negative electrode active material used in Example 1, a negative electrode sheet was prepared using lithium titanate Li 4 Ti 5 O 12 (negative electrode active material). 85% by mass of lithium titanate and 10% by mass of acetylene black (conductive agent) are mixed and added to a solution in which 5% by mass of polyvinylidene fluoride (binder) is previously dissolved in 1-methyl-2-pyrrolidone. The mixture was mixed to prepare a negative electrode mixture paste.
  • lithium titanate Li 4 Ti 5 O 12 negative electrode active material
  • acetylene black conductive agent
  • This negative electrode mixture paste was applied onto a copper foil (current collector), dried, pressurized and cut into a predetermined size to produce a negative electrode sheet, and the end-of-charge voltage during battery evaluation was 2
  • a laminated battery was prepared and evaluated in the same manner as in Example 1 except that the voltage was .75 V, the discharge end voltage was 1.1 V, and the composition of the nonaqueous electrolyte was changed to a predetermined value. The results are shown in Table 3.
  • the effect of the present invention is a unique effect when the sulfate or sulfite represented by the general formula (I) is contained in the non-aqueous electrolyte in which the electrolyte salt is dissolved in the non-aqueous solvent. It turned out to be. Further, from the comparison between Examples 17 to 18 and Comparative Example 5, it is clear that the same effect is observed when lithium titanate is used for the negative electrode, and therefore it is not an effect dependent on the specific positive electrode or the negative electrode. .
  • the non-aqueous electrolyte of the present invention has an effect of improving the discharge characteristics in a wide temperature range of the lithium primary battery.
  • the nonaqueous electrolytic solution for an electricity storage device of the present invention is used, an electricity storage device having excellent electrochemical characteristics in a wide temperature range can be obtained. Especially when used as a non-aqueous electrolyte for electricity storage devices such as lithium secondary batteries mounted on hybrid electric vehicles, plug-in hybrid electric vehicles, battery electric vehicles, etc., the electricity storage devices are unlikely to deteriorate in electrochemical characteristics over a wide temperature range. Can be obtained.

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Abstract

La présente invention concerne : une solution électrolytique non aqueuse pour dispositifs de stockage d'électricité qui permet d'améliorer les caractéristiques électrochimiques sur une large plage de températures, la solution électrolytique non aqueuse comprenant un sel d'électrolyte dissous dans un solvant non aqueux et étant caractérisée par le fait qu'elle contient, dans la solution électrolytique non aqueuse, 0,01 à 10 % en masse d'un composé exprimé par la formule générale (I) ; et un dispositif de stockage d'électricité utilisant la solution électrolytique non aqueuse. (Dans la formule, X représente un groupe S(=O)2 ou un groupe S=O et R1 à R8 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène ou un groupe alkyle comprenant 1 à 4 atomes de carbone dans lequel certains des atomes d'hydrogène peuvent être substitués par des atomes d'halogène).
PCT/JP2016/076865 2015-09-15 2016-09-12 Solution électrolytique non aqueuse pour dispositifs de stockage d'électricité et dispositif de stockage d'électricité utilisant celle-ci Ceased WO2017047554A1 (fr)

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JP2021096914A (ja) * 2019-12-13 2021-06-24 三井化学株式会社 電池用非水電解液及びリチウムイオン二次電池
JP7423889B2 (ja) 2019-12-13 2024-01-30 三井化学株式会社 電池用非水電解液及びリチウムイオン二次電池
JP2024517274A (ja) * 2021-09-30 2024-04-19 エルジー エナジー ソリューション リミテッド 非水電解質用添加剤を含む非水電解質およびそれを含むリチウム二次電池
JP7729918B2 (ja) 2021-09-30 2025-08-26 エルジー エナジー ソリューション リミテッド 非水電解質用添加剤を含む非水電解質およびそれを含むリチウム二次電池
WO2023246279A1 (fr) * 2022-06-21 2023-12-28 深圳新宙邦科技股份有限公司 Batterie secondaire au lithium

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