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WO2016076327A1 - Solution électrolytique non aqueuse et dispositif de stockage d'électricité dans lequel cette solution électrolytique non aqueuse est utilisée - Google Patents

Solution électrolytique non aqueuse et dispositif de stockage d'électricité dans lequel cette solution électrolytique non aqueuse est utilisée Download PDF

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Publication number
WO2016076327A1
WO2016076327A1 PCT/JP2015/081644 JP2015081644W WO2016076327A1 WO 2016076327 A1 WO2016076327 A1 WO 2016076327A1 JP 2015081644 W JP2015081644 W JP 2015081644W WO 2016076327 A1 WO2016076327 A1 WO 2016076327A1
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Prior art keywords
carbonate
aqueous electrolyte
compound
group
lithium
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Japanese (ja)
Inventor
三好　和弘
雄一 古藤
近藤　正英
敦允 中川
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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
    • H01G11/60—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
    • H01G11/64—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 (first invention) relates to a non-aqueous electrolyte capable of improving electrochemical characteristics in a wide temperature range, in particular, charge storage characteristics and low-temperature output characteristics after charge storage, and an electricity storage device using the same.
  • the present invention (second invention) also relates to a nonaqueous electrolytic solution that can improve electrochemical characteristics over a wide temperature range, and in particular, can improve electrochemical characteristics at high temperatures, 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.
  • the battery characteristics are likely to deteriorate particularly when used in a high temperature environment such as midsummer. Therefore, the demand for the charge storage characteristics under a high temperature environment is increasing, and further improvement of the battery characteristics is required.
  • the term lithium secondary battery is used as a concept including a so-called lithium ion secondary battery.
  • the lithium secondary battery is mainly composed of a positive electrode and a negative electrode containing a material capable of occluding and releasing lithium, a non-aqueous electrolyte composed of a lithium salt and a non-aqueous solvent, and the non-aqueous solvent includes ethylene carbonate (EC), Carbonates such as propylene carbonate (PC) are used.
  • EC ethylene carbonate
  • PC propylene carbonate
  • As negative electrodes of lithium secondary batteries metal lithium, metal compounds capable of occluding and releasing lithium (metal simple substance, metal oxide, alloys with lithium, etc.) and carbon materials are known, and in particular, lithium is occluded. Lithium secondary batteries using carbon materials such as coke, artificial graphite, and natural graphite that can be released 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 such that the solvent in the non-aqueous electrolyte is oxidized and decomposed on the positive electrode surface during charging, and reduced on the negative electrode surface.
  • Decomposition products and gas generated by decomposition inhibit the desired electrochemical reaction of the battery, resulting in degradation of electrochemical characteristics over a wide temperature range, and insertion and extraction of lithium into the positive and negative electrodes. Since it cannot be smoothly performed, the electrochemical characteristics are liable to deteriorate.
  • lithium secondary batteries using lithium metal, alloys thereof, simple metals such as tin or silicon, and oxides as negative electrode materials have high initial capacities, but are increasingly pulverized during use as power storage devices. It is known that reductive decomposition of a non-aqueous solvent occurs at an accelerated rate as compared with the negative electrode, and the electrochemical characteristics in a wide temperature range are greatly deteriorated. When these anode materials are pulverized or decomposition products of nonaqueous solvents accumulate, lithium cannot be smoothly occluded and released, and electrochemical characteristics in a wide temperature range are likely to deteriorate.
  • lithium secondary batteries using, for example, LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiNi 1/3 Mn 1/3 Co 1/3 O 2 , LiFePO 4, etc. as positive electrode materials are non-aqueous at high temperatures. It has been found that non-aqueous solvents in the electrolyte solution are oxidatively decomposed in the charged state, and by-products generated at that time are deposited on the negative electrode, resulting in a decrease in electrochemical properties by forming a film with high electrical resistance. .
  • Patent Document 1 proposes a nonaqueous electrolytic solution containing 5% by mass or more of a biphenyl group-containing phosphate ester compound as a flame retardant, and a nonaqueous electrolytic solution capable of imparting flame retardancy and overcharge prevention properties It can be provided. It is described that when the amount of the flame retardant added is less than 5% by mass, the polymerization reaction cannot be promoted and the effect of preventing overcharge of the secondary battery becomes insufficient.
  • Non-Patent Document 1 improves the cycle characteristics of a coin cell using an electrolytic solution to which 4-phenylphenyl diethyl phosphate is not added by using a positive electrode previously oxidized with 4-phenylphenyl diethyl phosphate. It has been suggested.
  • a battery mounted on an electronic device or an electric vehicle is likely to be used under a high temperature in midsummer or in an environment warmed by heat generated by the electronic device.
  • laminated batteries and square batteries that use a laminated film such as an aluminum laminated film are often used for exterior members, but these batteries are thin. There is a problem that it is likely to be deformed easily due to a slight expansion of the exterior member, and the influence of the deformation on the electronic device is very large.
  • a lithium secondary battery is mainly composed of a positive electrode and a negative electrode containing a material capable of occluding and releasing lithium, and a non-aqueous electrolyte composed of a lithium salt and a non-aqueous solvent.
  • the non-aqueous solvent include ethylene carbonate (EC) and propylene. Carbonates such as carbonate (PC) are used.
  • EC ethylene carbonate
  • PC propylene
  • Carbonates such as carbonate
  • negative electrodes of lithium secondary batteries lithium metal, metal compounds capable of inserting and extracting lithium ions (metal simple substance, metal oxide, alloys with lithium, etc.) and carbon materials are known.
  • non-aqueous electrolyte secondary batteries using carbon materials that can occlude and release lithium such as coke and graphite (artificial graphite, natural graphite), are widely used.
  • the negative electrode material stores and releases lithium and electrons at an extremely low potential equivalent to that of lithium metal, there is a possibility that many solvents undergo reductive decomposition, particularly at high temperatures. Therefore, regardless of the type of negative electrode material, a part of the solvent in the electrolyte solution undergoes reductive decomposition on the negative electrode, and the migration of lithium ions is hindered by decomposition product deposition, gas generation, and electrode swelling, especially at high temperatures.
  • 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 are finely pulverized during cycles.
  • reductive decomposition of nonaqueous solvents occurs at an accelerated rate, and there are known problems such as battery performance such as battery capacity and cycle characteristics being greatly degraded at high temperatures, and battery deformation due to electrode swelling. ing.
  • materials capable of inserting and extracting lithium such as LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiFePO 4 used as positive electrode materials store lithium ions and electrons at a noble voltage of 3.5 V or more on the basis of lithium. And many solvents have the potential to undergo oxidative degradation, especially at high temperatures, for release. Therefore, regardless of the type of positive electrode material, a part of the solvent in the electrolyte solution is oxidatively decomposed on the positive electrode. There was a problem of deteriorating characteristics.
  • Patent Document 2 proposes a non-aqueous electrolyte containing an aromatic carbonate such as bis (4-phenoxyphenyl) carbonate, and a non-aqueous electrolyte secondary battery using the non-aqueous electrolyte. It is described that safety is improved.
  • Non-aqueous electrolyte (A) containing diphenyl carbonate and vinylene carbonate (C) enhances safety during overcharge and suppresses deterioration of battery performance during continuous charge Is described.
  • JP 2014-164801 A JP 2004-111169A International Publication No. 2009/107786
  • An object of the first invention is to provide a non-aqueous electrolyte capable of improving electrochemical characteristics in a wide temperature range, in particular, charge storage characteristics and low-temperature output characteristics after charge storage, and an electricity storage device using the same.
  • the second invention provides a non-aqueous electrolyte capable of improving electrochemical characteristics over a wide temperature range, particularly at high temperatures, and further reducing the rate of increase in electrode thickness after a high-temperature cycle, and an electricity storage device using the same The task is to do.
  • the resistance increase caused by the decomposition products of the non-aqueous electrolyte on the positive electrode and the negative electrode is remarkably suppressed, so that electrochemical characteristics in a wide temperature range, particularly charge storage characteristics and after charge storage
  • Patent Document 3 discloses nothing about the problem of reducing the rate of increase in electrode thickness associated with charge / discharge, and is a partial hydrogen atom of a benzene ring of a compound group represented by methylphenyl carbonate. However, although it is suggested that it may be substituted with a halogen atom, there is no example.
  • Patent Document 3 describes the improvement of overcharge safety, the suppression of deterioration during continuous charging, and the ability to suppress the generation of gas to some extent, the problem of reducing the electrode thickness due to charging and discharging is described. Is not disclosed at all. Therefore, as a result of intensive studies to solve the above problems, the present inventors have determined that a compound in which the hydrogen atom of one benzene ring of diphenyl carbonate is substituted with a specific number of halogen atoms is a non-aqueous electrolyte. It has been found that the rate of increase in electrode thickness after a high-temperature cycle can be reduced by containing it in the inside, and the second invention has been completed.
  • the present invention provides the following (1) to (4).
  • First invention> (1) In a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous electrolytic solution, the biphenyl compound containing a phosphate structure represented by the following general formula (I) is included, and the content of the biphenyl compound is: A non-aqueous electrolyte characterized by being 0.1 to 4.5 mass in the non-aqueous electrolyte.
  • R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 3 to 8 carbon atoms, or a carbon number. 6 to 20 aryl groups, wherein each of the alkyl group, alkenyl group, alkynyl group or aryl group may have at least one hydrogen atom substituted with a halogen atom.
  • X 1 and X 2 each independently represent a halogen atom or a halogenated alkyl group having 1 to 6 carbon atoms, m is an integer of 0 to 4, and n is an integer of 0 to 5.
  • an electricity 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
  • the non-aqueous electrolyte is the non-aqueous electrolyte described in (1).
  • a power storage device characterized.
  • ⁇ Second invention> In a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent, the composition contains an asymmetric halogenated phenylcarbonate compound represented by the following general formula (II), and the content of the halogenated phenylcarbonate compound is:
  • X 11 to X 15 each independently represents a hydrogen atom or a halogen atom, and 1 to 4 of X 11 to X 15 are halogen atoms.
  • the non-aqueous electrolyte is the non-aqueous electrolyte described in (3).
  • a non-aqueous electrolyte capable of improving electrochemical characteristics in a wide temperature range, in particular, charge storage characteristics and low-temperature output characteristics after charge storage, and an electricity storage device such as a lithium battery using the same. be able to.
  • a non-aqueous electrolyte that can improve electrochemical characteristics in a wide temperature range, particularly a non-aqueous electrolyte that can reduce the rate of increase in electrode thickness after a high-temperature cycle, and lithium using the same
  • An electricity storage device such as a battery can be provided.
  • Non-aqueous electrolyte of the first invention is a non-aqueous electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent.
  • a nonaqueous electrolytic solution comprising a compound, wherein the content of the biphenyl compound is 0.1 to 4.5% by mass in the nonaqueous electrolytic solution.
  • nonaqueous electrolytic solution of the first invention can improve electrochemical characteristics in a wide temperature range, in particular, charge storage characteristics and low-temperature output characteristics after charge storage is not necessarily clear, but is considered as follows.
  • a part of the phosphoric ester structure in the biphenyl compound represented by the general formula (I) contained in the nonaqueous electrolytic solution of the first invention is electrochemically reduced on the negative electrode side to form a film. Since the coating film includes both a coating component having high thermal stability derived from the biphenyl structure and a coating component excellent in lithium ion conductivity derived from the phosphate ester structure, an increase in electrical resistance of the coating film is suppressed.
  • the charge storage characteristic of electrical storage devices improves.
  • a part of the reductive decomposition product of the biphenyl compound represented by the general formula (I) also forms a film on the positive electrode. Since the coating film is excellent in lithium ion conductivity even after being stored under charge, it is considered that the low-temperature output characteristics after storage under charge are improved.
  • Such an effect is manifested when the biphenyl compound containing the phosphate structure represented by the general formula (I) is used in a non-aqueous electrolyte solution. This is an exceptional effect of the present invention that cannot be realized by the method of previously forming a polymer film on the positive electrode.
  • the biphenyl compound containing a phosphate structure contained in the nonaqueous electrolytic solution of the first invention is represented by the following general formula (I).
  • R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkynyl group having 3 to 8 carbon atoms, or a carbon number. 6 to 20 aryl groups, wherein each of the alkyl group, alkenyl group, alkynyl group or aryl group may have at least one hydrogen atom substituted with a halogen atom.
  • X 1 and X 2 each independently represent a halogen atom or a halogenated alkyl group having 1 to 6 carbon atoms, m is an integer of 0 to 4, and n is an integer of 0 to 5.
  • X 1 and X 2 include linear alkyl such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, or n-hexyl group.
  • a branched alkyl group of a group, isopropyl group, sec-butyl group, tert-butyl group, or tert-amyl group is preferred.
  • m is preferably 3 or less, more preferably 2 or less, still more preferably 1 or less, and most preferably 0 from the viewpoint of improving electrochemical characteristics in a wide temperature range.
  • n is preferably 4 or less, more preferably 2 or less, still more preferably 1 or less, and most preferably 0.
  • R 1 and R 2 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, or linear alkyl group such as n-octyl group; branched alkyl group of isopropyl group, sec-butyl group, tert-butyl group, tert-amyl group, or 2-ethylhexyl group; vinyl group, 2-propenyl group A straight-chain alkenyl group having 3 to 6 carbon atoms such as 2-butenyl group or 3-butenyl group; a branched alkenyl group of 2-methyl-2-propenyl group; 2-propynyl group, 2-butynyl group, 3 A straight-chain alkynyl group having 2 to 6 carbon atoms such as -butynyl group, 4-pentyny
  • methyl group, ethyl group, n-propyl group, isopropyl group, vinyl group, 2-propenyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, phenyl group, 2,4-dimethylphenyl Group, 2-fluorophenyl group, 3-fluorophenyl group or 4-fluorophenyl group is preferable, and methyl group, ethyl group, 2-propenyl group, 2-propynyl group and phenyl group are more preferable.
  • the effect of improving electrochemical characteristics in a wide temperature range, in particular, charge storage characteristics and low-temperature output characteristics after charge storage also depends on the substitution position of the phosphate ester structure.
  • a compound in which the phosphate ester structure is substituted at the 2-position or 3-position of the biphenyl structure is more preferred, and a compound substituted at the 2-position is more preferred.
  • biphenyl compound containing the phosphate structure represented by the general formula (I) include the following compounds.
  • compounds A1 to A13, A23 to A33, and A35 to A42 in which the biphenyl group is not substituted with a halogen atom or a haloalkyl group are more preferable.
  • Further preferred compounds are 2-phenylphenyl dimethyl phosphate (compound A1), 2-phenylphenyl diethyl phosphate (compound A2), 2-phenylphenyl diisopropyl phosphate (compound A3), 2-phenylphenyl dibutyl phosphate (compound) A4), 2-phenylphenyl divinyl phosphate (compound A5), 2-phenylphenyl diallyl phosphate (compound A6), 2-phenylphenyl di (2-propynyl) phosphate (compound A7), 2-phenylphenyl phosphate Diphenyl (compound A8), 2-phenylphenyl bis (2,2,2-trifluoroethyl) phosphate (compound A1),
  • 2-phenylphenyl dimethyl phosphate compound A1
  • 2-phenylphenyl diethyl phosphate compound A2
  • 2-phenylphenyl diisopropyl phosphate compound A3
  • 2-phosphate phosphate Phenylphenyl divinyl compound A5
  • 2-phenylphenyl diallyl phosphate compound A6
  • 2-phenylphenyl di (2-propynyl) phosphate compound A7
  • 2-phenylphenyl diphenyl phosphate compound A8
  • One or more compounds selected from 2-phenylphenyl bis (2,2,2-trifluoroethyl) phosphate Compound A9
  • the content of the biphenyl compound represented by the general formula (I) contained in the non-aqueous electrolyte is 0.1 to 4.5% by mass in the non-aqueous electrolyte. It is. If the content is 4.5% by mass or less, there is little possibility that a 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. The effect of improving the charge storage characteristics is enhanced.
  • the content is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more in the nonaqueous electrolytic solution.
  • the upper limit is preferably 4% by mass or less, more preferably 3.5% by mass or less, and particularly preferably 3% by mass or less.
  • the biphenyl compound represented by the general formula (I) is combined with a nonaqueous solvent, an electrolyte salt, and other additives described below to combine electrochemical characteristics in a wide temperature range.
  • a nonaqueous solvent an electrolyte salt, and other additives described below to combine electrochemical characteristics in a wide temperature range.
  • it exhibits a unique effect that the effect of improving the charge storage characteristics and the low-temperature output characteristics after storage is synergistically improved.
  • the non-aqueous electrolyte of the second invention is a non-aqueous electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent, and an asymmetric halogenated phenyl carbonate compound represented by the following general formula (II) And a non-aqueous electrolyte characterized in that the content of the halogenated phenyl carbonate compound is 0.001 to 5 mass% in the non-aqueous electrolyte.
  • X 11 to X 15 each independently represents a hydrogen atom or a halogen atom, and 1 to 4 of X 11 to X 15 are halogen atoms.
  • the reason why the nonaqueous electrolytic solution of the second invention can improve the electrochemical characteristics in a wide temperature range, particularly at a high temperature, and further reduce the increase rate of the electrode thickness after the high temperature cycle is not necessarily clear, but is as follows. Can be considered.
  • the asymmetric halogenated phenyl carbonate compound contained in the non-aqueous electrolyte solution of the second invention has one of two benzene rings bonded to an oxygen atom having 1 to 4 halogen atoms, and the other benzene ring has a substituent. There is no asymmetric carbonate.
  • the asymmetric halogenated phenyl carbonate compound is intermediate between the case where all of one benzene ring is a compound substituted with a halogen atom and the case where the compound is not substituted with a halogen atom at all.
  • a strong film SEI
  • SEI strong film
  • the asymmetric halogenated phenyl carbonate compound contained in the nonaqueous electrolytic solution of the second invention is represented by the following general formula (II).
  • X 11 to X 15 each independently represents a hydrogen atom or a halogen atom, and 1 to 4 of X 11 to X 15 are halogen atoms.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a fluorine atom or a chlorine atom is preferable, and a chlorine atom is more preferable from the viewpoint of easily forming a film that is stable on both the positive electrode and the negative electrode and excellent in lithium ion permeability upon oxidation and reduction.
  • compounds B1 to B15 and B19 to B38 are preferable, compounds B1 to B9 and B19 to B27 are more preferable, 2-fluorophenyl phenyl carbonate (compound B1), 4-fluorophenyl phenyl carbonate (compound B3), 2 , 4-difluorophenyl phenyl carbonate (compound B5), 2,6-difluorophenyl phenyl carbonate (compound B7), 2-chlorophenyl phenyl carbonate (compound B19), 3-chlorophenyl phenyl carbonate (compound B20), 4-chlorophenyl phenyl carbonate (Compound B21), 2,4-dichlorophenyl phenyl carbonate (Compound B23), and 2,6-dichlorophenyl phenyl carbonate (Compound B25)
  • One or more compounds barrel more preferred. When these compounds are used, it is easy to form a coating film that is stable and excellent in
  • the content of the asymmetric halogenated phenyl carbonate compound represented by the general formula (II) contained in the non-aqueous electrolyte is 0.001 to 5 mass in the non-aqueous electrolyte. % Is preferred. If the content is 5% by mass or less, there is little possibility that the film is excessively formed on the electrode and the thickness of the electrode increases, and if it is 0.001% by mass or more, the film is sufficiently formed, and the high temperature cycle Since the characteristics are enhanced, the above range is preferable.
  • 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 more preferably 3% by mass or less, and further preferably 2% by mass or less.
  • the non-aqueous electrolyte of the present invention further contains a symmetric phenyl carbonate compound because the coating becomes stronger and exhibits a specific effect that the rate of increase in electrode thickness after a high-temperature cycle can be further reduced.
  • symmetric phenyl carbonate compound if two benzene rings are the same, they may be substituted with a halogen atom.
  • symmetric phenyl carbonate examples include diphenyl carbonate, bis (2-fluorophenyl) carbonate, bis (3-fluorophenyl) carbonate, bis (4-fluorophenyl) carbonate, bis (2,4-difluorophenyl) carbonate.
  • Preferred examples include at least one selected from the group consisting of bis (2-chlorophenyl) carbonate, bis (3-chlorophenyl) carbonate, bis (4-chlorophenyl) carbonate, and bis (2,4-dichlorophenyl) carbonate.
  • diphenyl carbonate, bis (4-fluorophenyl) carbonate, bis (2,4-difluorophenyl) carbonate, bis (2-chlorophenyl) carbonate, bis (3-chlorophenyl) carbonate, bis (4-chlorophenyl) carbonate, bis (2,4-Dichlorophenyl) carbonate is preferred, and diphenyl carbonate, bis (2-chlorophenyl) carbonate, bis (3-chlorophenyl) carbonate, bis (4-chlorophenyl) carbonate, and bis (2,4-dichlorophenyl) carbonate are more preferred.
  • Bis (2-chlorophenyl) carbonate, bis (3-chlorophenyl) carbonate, and bis (4-chlorophenyl) carbonate are more preferable.
  • the content of the symmetric phenyl carbonate contained in the non-aqueous electrolyte is such that the mass ratio of [asymmetric halogenated phenyl carbonate compound / symmetric phenyl carbonate compound] is 50/50 to 99.9 / 0.1
  • the film is 80/20 to 99.5 / 0.5, and more preferably 95/5 to 99.3 / 0.7.
  • the specific asymmetric halogenated phenyl carbonate represented by the general formula (II) is combined with a non-aqueous solvent, an electrolyte salt, and other additives described below at a high temperature. Electrochemical properties are synergistically improved and a unique effect of reducing the increase rate of the electrode thickness is exhibited.
  • Nonaqueous solvent As the nonaqueous solvent used in the nonaqueous electrolytic solution of the present invention, one or more selected from cyclic carbonates, chain esters, lactones, ethers, and amides are preferably exemplified. In order to synergistically improve electrochemical characteristics in a wide temperature range and electrochemical characteristics at high temperatures, it is preferable that a chain ester is included, more preferably a chain carbonate is included, and a cyclic carbonate and a chain carbonate are included. More preferably, both carbonates 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), ethylene carbonate, propylene carbonate, 4-fluoro-1,3-dioxolan-2-one, vinylene carbonate and 4-ethynyl -1,3-dioxolan-2-one (EEC) More species or of two or more preferred.
  • cyclic carbonates containing a cyclic carbonate containing an unsaturated bond such as a carbon-carbon double bond or carbon-carbon triple bond and a fluorine atom are included. More preferably, both carbonates are included.
  • cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or carbon-carbon triple bond
  • VC, VEC, or EEC is more preferable
  • 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 based on the total volume of the nonaqueous solvent. More preferably, it is 0.2% by volume or more, more preferably 0.7% by volume or more, and the upper limit thereof is preferably 7% by volume or less, more preferably 4% by volume or less, still more preferably 2. 5 vol% or less is preferable because electrochemical characteristics in a wider temperature range can be further improved 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 4% by volume or more, still more preferably 6% by volume or more, 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, electrochemical characteristics in a wider temperature range can be improved without impairing Li ion permeability. It is preferable because it is possible.
  • the carbon 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, and further preferably 7% by volume or more.
  • the upper limit is preferably 40% by volume or less, more preferably 30% by volume or less, and even more preferably 15% by volume or less, and the electrochemical characteristics in a wider temperature range can be obtained without impairing Li ion permeability. Since it can improve, it is especially preferable.
  • the nonaqueous solvent contains both ethylene carbonate and a cyclic carbonate having an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond
  • the electrochemistry over a wide temperature range of the film formed on the electrode is preferably with respect to the total volume of the non-aqueous solvent. 3 volume% or more, more preferably 5 volume% or more, more preferably 7 volume% or more, and the upper limit thereof is preferably 45 volume% or less, more preferably 35 volume% or less, still more preferably 25 volume%. % Or less.
  • 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 based on the total volume of the nonaqueous solvent. More preferably, it is 0.2% by volume or more, more preferably 0.7% by volume or more, and the upper limit thereof is preferably 9% by volume or less, more preferably 6% by volume or less, still more preferably 5% by volume. % Or less is preferable because the stability of the coating at high temperatures can be increased.
  • the content of the cyclic carbonate having a fluorine atom is preferably 0.07% by volume or more, more preferably 4% by volume or more, still more preferably 7% by volume or more, 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 even more preferably 15% by volume or less, which can further increase the stability of the coating at high temperatures and increase the increase rate of the electrode thickness. Since it can reduce, it is preferable.
  • the carbon 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, and further preferably 7% by volume or more.
  • the upper limit is preferably 40% by volume or less, more preferably 30% by volume or less, and even more preferably 15% by volume or less, which can further increase the stability of the coating at high temperatures, This is preferable because the rate of increase can be reduced.
  • the non-aqueous solvent contains ethylene carbonate and / or propylene carbonate
  • the stability of the film formed on the electrode is increased, and the rate of increase in the electrode thickness can be reduced, and the content of ethylene carbonate and / or propylene carbonate is preferable.
  • the above solvents may be used alone or in combination of two or more, since the effect of improving electrochemical properties over a wide temperature range is further improved, or the stability of the coating at high temperatures It is preferable to use three or more types in combination, because the properties increase further, the rate of increase in electrode thickness can be reduced, and the electrochemical characteristics over a wide temperature range are further improved.
  • Preferred combinations of these 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 preferable.
  • 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
  • MEC methyl ethyl carbonate
  • MPC methyl propyl carbonate
  • MIPC methyl isopropyl carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • dipropyl carbonate dibutyl carbonate
  • pivalate esters such as methyl pivalate, ethyl pivalate, and propyl pivalate
  • Preferable examples include one or more chain carboxylic acid esters selected from methyl propionate, ethyl propionate, propyl propionate, methyl acetate, and ethyl acetate (EA).
  • chain esters having a methyl group selected from dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate, methyl propionate, methyl acetate and ethyl acetate (EA) are preferable.
  • a chain carbonate having a methyl group is preferred.
  • chain carbonate it is preferable to use 2 or more types. 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 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.
  • the above range is preferable because there is little possibility that the characteristics will deteriorate, or there is little possibility that the electrochemical characteristics at a wide temperature range, particularly at high temperatures, will decrease.
  • 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.
  • 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, it is preferable because the electrochemical characteristics at a wider temperature range, particularly at high temperature, are improved, or the stability of the coating at high temperature is increased, the rate of increase in electrode thickness can be reduced, and a wider temperature range, especially It is preferable because electrochemical characteristics at high temperature are improved.
  • the ratio between the cyclic carbonate and the chain ester is such that the cyclic carbonate / chain ester (volume ratio) is from the viewpoint of improving the electrochemical properties at high temperatures or from the viewpoint of improving the electrochemical properties at a wide temperature range, particularly at high temperatures. 10/90 to 45/55 are preferable, 15/85 to 40/60 are more preferable, and 20/80 to 35/65 are particularly preferable.
  • nonaqueous 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 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 other 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 (chain carbonate) and a lactone, and a cyclic carbonate and a chain.
  • Preferred examples include combinations of esters (chain carbonates) and ethers, and combinations of cyclic carbonates, chain carbonates and chain carboxylic acid esters, etc., and combinations of cyclic carbonates, chain esters and lactones are more preferred. Of these, ⁇ -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 case of the first invention, it is preferable to add other additives to the non-aqueous electrolyte for the purpose of improving electrochemical characteristics in a wider temperature range.
  • specific examples of other additives include the following compounds (A) to (I).
  • (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.
  • nitrile one or more selected from succinonitrile, glutaronitrile, adiponitrile, and pimelonitrile are more preferable.
  • aromatic compounds one or two selected from biphenyl, terphenyl (o-, m-, p-isomer), fluorobenzene, cyclohexylbenzene, tert-butylbenzene, and tert-amylbenzene
  • biphenyl, o-terphenyl, fluorobenzene, cyclohexylbenzene, and tert-amylbenzene are particularly preferable.
  • (C) isocyanate compounds one or more selected from hexamethylene diisocyanate, octamethylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate are more preferable.
  • the content 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 characteristics 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, di (2-propynyl) oxalate, and 2-butyne-1 , 4-diyl dimethanesulfonate is preferably selected from one or two or more, 2-propynyl methanesulfonate, 2-propynyl vinylsulfonate, di (2-propynyl) oxalate, and 2-butyne-1,4- One or more selected from diyl dimethanesulfonate is more preferable.
  • a cyclic or chain-containing S ⁇ O group-containing compound selected from sultone, cyclic sulfite, cyclic sulfate, sulfonic acid ester, and vinyl sulfone (provided that the triple bond-containing compound and any one of the above general formulas) It is preferable to use a specific compound).
  • 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-
  • Preferable examples include one or more selected from 1,2-oxathiolan-4-yl acetate, methylene methane disulfonate, ethylene sulfite, and ethylene sulfate.
  • 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.
  • the cyclic acetal compound 1,3-dioxolane or 1,3-dioxane is preferable, and 1,3-dioxane is more preferable.
  • the phosphorus-containing compound is more preferably tris (2,2,2-trifluoroethyl) phosphate, ethyl 2- (diethoxyphosphoryl) acetate, or 2-propynyl 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 More preferred is triphosphazene.
  • the content 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].
  • a lithium salt having at least one oxalic acid skeleton selected from Lithium salt having a phosphoric acid skeleton such as LiPO 2 F 2 or Li 2 PO 3 F, lithium trifluoro ((methanesulfonyl) oxy) borate [LiTFMSB], Lithium pentafluoro ((methanesulfonyl) oxy) phosphate [LiPFMSP], lithium methyl sulfate [LMS], lithium ethyl sulfate [LES], lithium 2,2,2-tri Le Oro ethylsulfate [LFES], and lithium salts suitably having 1 or more S O group selected from FSO 3 Li.
  • 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, Most preferably, it is 0.04M or more.
  • the upper limit is more preferably 0.4M or less, and particularly preferably 0.2M or less. (However, M represents mol / L.)
  • a mixed SEI film is formed by four or five or more functional groups or characteristic groups, and the rate of increase in electrode thickness after high-temperature cycling is increased. The effect of reducing can be further enhanced.
  • the (a) SO 2 group-containing compound is not particularly limited as long as it is a compound having an “SO 2 group” in the molecule. Specific examples thereof include 1,3-propane sultone, 1,3-butane sultone, 2,4-butane sultone, 1,4-butane sultone, 1,3-propene sultone, 2,2-dioxide-1,2-oxathiolane- Sultone such as 4-yl acetate or 5,5-dimethyl-1,2-oxathiolane-4-one 2,2-dioxide, ethylene sulfite, butane-2,3-diyl dimethanesulfonate, butane-1,4 -One or more selected from the group consisting of diyl dimethane sulfonate, pentane-1,5-diyl dimethane sulfonate, methylene methane disulfonate, divinyl sulfone, and the like are
  • 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, 2,2-dioxy-1,2-oxathiolan-4-yl acetate, 5,5-dimethyl -1,2-oxathiolane-4-one More preferred is one or more selected from the group consisting of 2,2-dioxide, butane-2,3-diyl dimethanesulfonate, and divinylsulfone.
  • the type of (b) fluorinated benzene compound is not particularly limited as long as it is a compound having a “phenyl group in which at least a part of the benzene ring is substituted with fluorine” in the molecule.
  • Specific examples thereof include fluorobenzene, difluorobenzene (o, m, p isomer), 2,4-difluoroanisole, 1-fluoro-2-cyclohexylbenzene, 1-fluoro-3-cyclohexylbenzene, 1-fluoro-4.
  • fluorinated benzene compound examples include fluorobenzene, 2,4-difluoroaniol, 1-fluoro-4-cyclohexylbenzene, pantafluorophenylmethanesulfonate, 2-fluorophenylmethanesulfonate, 2,4-difluorophenylmethanesulfonate, And one or more selected from the group consisting of 4-fluoro-3-trifluoromethylphenylmethanesulfonate.
  • the type of the phosphate ester compound is not particularly limited as long as it is a compound having a “P ( ⁇ O) group” in the molecule. Specific examples thereof include trimethyl phosphate, tributyl phosphate, and trioctyl phosphate, tris (2,2,2-trifluoroethyl) phosphate, bis (2,2,2-trifluoroethyl) methyl phosphate, Bis (2,2,2-trifluoroethyl) phosphate, bis (2,2,2-trifluoroethyl) phosphate, 2,2-difluoroethyl phosphate, bis (2,2,2-trifluoroethyl phosphate) ) 2,2,3,3-tetrafluoropropyl, bis (2,2-difluoroethyl) phosphate 2,2,2-trifluoroethyl, bis (2,2,3,3-tetrafluoropropyl) phosphate 2,2,2-trifluoroethyl and
  • tris phosphate (2,2,2-trifluoroethyl), tris phosphate (1,1,1,3,3,3-hexafluoropropan-2-yl), methyl 2 -(Dimethoxyphosphoryl) acetate, ethyl 2- (dimethoxyphosphoryl) acetate, methyl 2- (diethoxyphosphoryl) acetate, ethyl 2- (diethoxyphosphoryl) acetate, 2-propynyl 2- (dimethoxyphosphoryl) acetate, 2-propynyl 2- (Diethoxyphosphoryl) acetate is preferred
  • One or more selected from the group consisting of diethoxyphosphoryl) acetate is more preferable.
  • the carbon-carbon triple bond-containing compound is not particularly limited as long as it is a compound having a “carbon-carbon triple bond” in the molecule.
  • the type of (e) carboxylic acid anhydride is not particularly limited as long as it is a compound having a “C ( ⁇ O) —O—C ( ⁇ O) group” in the molecule.
  • Specific examples thereof include chain carboxylic acid anhydrides such as acetic anhydride and propionic anhydride, succinic anhydride, maleic anhydride, allyl succinic anhydride, glutaric anhydride, itaconic anhydride, and 3-sulfo-propionic acid.
  • 1 or more types chosen from the group which consists of cyclic acid anhydrides, such as an anhydride, are mentioned suitably, 2 or more types are more suitable.
  • carboxylic acid anhydrides one or more selected from succinic anhydride, maleic anhydride, and allyl succinic anhydride are preferable, and one selected from succinic anhydride and allyl succinic anhydride is more preferable.
  • the type of isocyanate compound is not particularly limited as long as it is a compound having “N ⁇ C ⁇ O group”. Specific examples thereof include methyl isocyanate, ethyl isocyanate, butyl isocyanate, phenyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, 1,4-phenylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl.
  • One or more kinds selected from the group consisting of methacrylate and the like are preferably mentioned, and two or more kinds are more preferred.
  • isocyanate compounds one or more selected from hexamethylene diisocyanate, octamethylene diisocyanate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate are preferable, hexamethylene diisocyanate, 2-isocyanatoethyl acrylate, and One or more selected from 2-isocyanatoethyl methacrylate is more preferable.
  • the lithium-containing ionic compound is not particularly limited as long as it is a compound having “lithium” as a cation species. Specific examples thereof include lithium difluorophosphate, lithium fluorophosphate, lithium fluorosulfonate, difluorobis [oxalate-O, O ′] lithium phosphate (LiPFO), and tetrafluoro [oxalate-O, O ′] phosphate.
  • lithium-containing ionic compounds lithium difluorophosphate, lithium fluorosulfonate, difluorobis [oxalate-O, O ′] lithium phosphate (LiPFO), lithium tetrafluoro [oxalate-O, O ′] lithium phosphate,
  • LiPFO lithium tetrafluoro [oxalate-O, O ′] lithium phosphate
  • LiBOB lithium bis [oxalate-O, O ′] lithium borate
  • difluoro [oxalate-O, O ′] lithium borate lithium methyl sulfate, lithium ethyl sulfate, and lithium propyl sulfate are more preferable. Two or more are particularly preferred.
  • lithium ethyl sulfate lithium difluorophosphate, difluorobis [oxalate-O, O ′] lithium phosphate (LiPFO), lithium tetrafluoro [oxalate-O, O ′] lithium phosphate, bis [ Oki Rate -O, O '] lithium borate (LiBOB), and it is
  • the type of (h) nitrile compound is not particularly limited as long as it is a compound having a “nitrile group”. Specifically, at least one selected from the group consisting of acetonitrile, propionitrile, succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, and sebacononitrile is preferable, and two or more are more preferable. is there. Among the nitrile compounds, one or more selected from succinonitrile, glutaronitrile, adiponitrile, and pimelonitrile are more preferable.
  • the type of benzene compound is not particularly limited as long as it is a compound having a “phenyl group” in the molecule. Specific examples thereof include aromatic compounds having a branched alkyl group such as cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, biphenyl, terphenyl (o-, m-, p-isomer), diphenyl ether, anisole.
  • Terphenyl hydrides (1,2-dicyclohexylbenzene, 2-phenylbicyclohexyl, 1,2-diphenylcyclohexane, o-cyclohexylbiphenyl), and phenyl carbonate compounds such as methylphenyl carbonate or ethylphenyl carbonate
  • phenyl carbonate compounds such as methylphenyl carbonate or ethylphenyl carbonate
  • benzene compounds one or two selected from cyclohexylbenzene, tert-butylbenzene, tert-amylbenzene, biphenyl, terphenyl (o-, m-, p-isomer), methylphenyl carbonate, and ethylphenyl carbonate
  • cyclohexylbenzene, tert-amylbenzene, biphenyl, o-terphenyl, methylphenyl carbonate, and ethylphenyl carbonate is particularly preferable.
  • the type of the cyclic acetal compound is not particularly limited as long as it is a compound having an “acetal group” in the molecule. Specifically, one or more selected from the group consisting of 1,3-dioxolane, 1,3-dioxane, 1,3,5-trioxane and the like are preferable, and two or more are more preferable. . Among the cyclic acetal compounds, 1,3-dioxolane or 1,3-dioxane is preferable, and 1,3-dioxane is more preferable.
  • the type of (k) phosphazene compound is not particularly limited as long as it is a compound having “N ⁇ PN group” in the molecule. Specific examples thereof include one or more selected from the group consisting of methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, ethoxyheptafluorocyclotetraphosphazene, and the like. Two or more types are more preferable.
  • phosphazene compounds such as methoxypentafluorocyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, or phenoxypentafluorocyclotriphosphazene are preferable, and are selected from methoxypentafluorocyclotriphosphazene and ethoxypentafluorocyclotriphosphazene. One or more are more preferable.
  • A SO 2 group-containing compound, (b) fluorinated benzene compound, (c) phosphate ester compound, (d) carbon-carbon triple bond-containing compound, (e) carboxylic acid anhydride, (f) isocyanate compound , (G) lithium-containing ionic compound, (h) nitrile compound, (i) benzene compound, (j) cyclic acetal compound, or (k) phosphazene compound content is 0.001 in the non-aqueous electrolyte, respectively. ⁇ 5% by weight is preferred.
  • the film is sufficiently formed without becoming too thick, and not only the effect of improving the electrochemical characteristics in a wide temperature range, particularly at a high temperature, but also the increase rate of the electrode thickness can be further reduced.
  • 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 3.5% by mass or less, and 2.5% by mass. The following is more preferable.
  • lithium-containing ionic compound (a) SO 2 group-containing compound, (b) fluorinated benzene compound, (c) phosphate ester compound, (d) carbon-carbon triple bond-containing compound , (E) carboxylic acid anhydride, (f) isocyanate compound, (h) nitrile compound, (i) benzene compound, (j) cyclic acetal compound, and (k) phosphazene compound.
  • 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 , LiPF 5 (iso-C 3 F 7 ) -containing lithium salt containing a fluorinated alkyl group, (CF 2 ) 2 (SO 2 ) 2 NLi, (CF 2 ) 3 (SO 2 ) 2 Preferred examples include lithium salts having a cyclic fluor
  • 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.
  • LiPF 6 is most preferred.
  • the concentration of the electrolyte salt is usually preferably 0.3 M or more, more preferably 0.7 M or more, still more preferably 1.1 M or more, particularly preferably 1.2 M or more, and 1.3 M with respect to the non-aqueous solvent.
  • the above is most preferable.
  • 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 F ) 2 [LiFSI], LiN (SO 2 CF 3) 2, and LiN (SO 2 C 2 F 5 )
  • LiPF 6 LiPF 6
  • LiFSI LiN (SO 2 F ) 2 [LiFSI]
  • LiN (SO 2 CF 3) 2 LiN (SO 2 C 2 F 5 )
  • the upper limit is preferably 0.8M or less, more preferably 0.6M or less, still more preferably 0.5M or less, and particularly preferably 0.4M or less.
  • the ratio of the molar concentration of the asymmetric halogenated phenyl carbonate compound represented by the general formula (II) to LiPF 6 is 0.0005 or more at a high temperature.
  • the effect of improving the electrochemical characteristics is easily exhibited, and if it is 0.3 or less, the effect of improving the electrochemical characteristics at high temperatures is less likely to decrease, which is preferable.
  • the lower limit is more preferably 0.001 or more, and still more preferably 0.005 or more.
  • the upper limit is more preferably 0.2 or less, and still more preferably 0.1 or less.
  • the non-aqueous electrolyte of the present invention is, for example, mixed with the non-aqueous solvent, and the biphenyl compound represented by the general formula (I) with respect to the electrolyte salt and the non-aqueous electrolyte. It can be obtained by adding an asymmetric halogenated phenyl carbonate compound represented by the formula (II). At this time, it is preferable that 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. 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 particularly 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 secondary battery of the present invention is composed of the nonaqueous electrolytic 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.
  • a 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 Mn 0.3 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 1 or more is preferably used selected from 4 2 or more are more preferable.
  • LiCoO 2 and LiMn 2 O 4, LiCoO 2 and LiNiO 2 may be used in
  • the electrochemical characteristics of the lithium secondary battery according to the present invention are likely to deteriorate over a wide temperature range due to reaction with the electrolyte during charging.
  • the deterioration of characteristics can be suppressed.
  • the nonaqueous solvent is 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 in which the ratio of the atomic concentration of Ni to the atomic concentration of all transition metal elements in the positive electrode active material exceeds 30 atomic% is used, the above effect is significant, and more preferably 50 atomic% or more. 75% or more is particularly preferable.
  • Preferable examples include 1 O 2 and LiNi 0.8 Co 0.15 Al 0.05 O 2 .
  • a part of the lithium composite metal oxide may be substituted with another element.
  • a part of cobalt, manganese, nickel is replaced with at least one element such as Sn, Mg, Fe, Ti, Al, Zr, Cr, V, Ga, Zn, Cu, Bi, Mo, La, etc.
  • a part of O may be substituted with S or F, or a compound containing these other elements may be coated.
  • Ni ions are eluted from the positive electrode.
  • the decomposition of the electrolytic solution on the negative electrode is promoted by the catalytic effect of Ni deposited on the negative electrode, and electrochemical characteristics such as high-temperature cycle characteristics are reduced, and the thickness of the negative electrode is likely to increase.
  • an electricity storage device using the non-aqueous electrolyte of the present invention is preferable because it can suppress a decrease in electrochemical characteristics and an increase in electrode thickness.
  • 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 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).
  • LiFePO 4 or LiFe 1-x Mn x PO 4 (0.1 ⁇ x ⁇ 0.9) are more preferable, LiFePO 4 is more preferred.
  • 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. , Cu, Zn, Mo, Ca, Sr, W and Zr can be substituted with one or more elements selected from these, or can be coated with a compound or carbon material containing these other elements.
  • 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 phosphate skeleton (PO 4 ) structure and has excellent thermal stability during charging, thus improving electrochemical characteristics over a wide temperature range, and after high-temperature cycling The increase rate of the electrode thickness can be further reduced.
  • 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, 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 , fluorinated graphite and the like are preferable.
  • the pH of the supernatant liquid when 10.0 g of the positive electrode active material is dispersed in 100 ml of distilled water is 10.0 to 12.5, the effect of improving the electrochemical characteristics in a wider temperature range can be easily obtained.
  • the case of 10.9 to 12.0 is more preferable.
  • impurities such as LiOH in the positive electrode active material tend to increase. Therefore, the electricity storage using the non-aqueous electrolyte of the present invention
  • the device is preferable because an effect of improving electrochemical characteristics and an effect of suppressing an increase in electrode thickness are easily obtained in a wider temperature range.
  • the case where the atomic concentration of Ni in the positive electrode active material is 5 to 25 atomic% is more preferable, and the case where it is 11 to 21 atomic% is particularly 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 (flaky graphite and the like) 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 active material is made of a conductive agent such as acetylene black or carbon black, and polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), a copolymer of styrene and butadiene (SBR), acrylonitrile and butadiene.
  • a conductive agent such as acetylene black or carbon black
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • SBR styrene and butadiene
  • SBR styrene and butadiene
  • acrylonitrile and butadiene acrylonitrile and butadiene.
  • binder such as copolymer (NBR), carboxymethyl cellulose (CMC), ethylene propylene diene terpolymer, etc.
  • high boiling point solvent such as 1-methyl-2-pyrrolidone.
  • 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 a carbon material capable of occluding and releasing lithium (easily graphitized carbon and a (002) plane spacing of 0.37 nm or more).
  • Non-graphitizable carbon, graphite with (002) plane spacing of 0.34 nm or less, etc.] tin (single), tin compound, silicon (single), silicon compound, lithium titanate such as Li 4 Ti 5 O 12 A compound etc. can be used individually by 1 type or in combination of 2 or more types. Particularly preferred combinations are graphite and silicon, or graphite and silicon compound.
  • 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.
  • 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. In addition, it is preferable that 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.
  • a highly crystalline carbon material reacts with the non-aqueous electrolyte during charging and tends to lower the electrochemical properties at low or high temperatures due to an increase in interfacial resistance, but in the lithium secondary battery according to the present invention, Excellent electrochemical characteristics over a wide temperature range.
  • 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, Ba, and other compounds containing at least one metal element. 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.
  • a particularly preferable metal compound is an oxide containing silicon, which is represented by SiOx (0 ⁇ x ⁇ 2).
  • the lithium secondary material according to the present invention has a content of silicon and silicon compound in the total negative electrode active material of 1 to 45% by mass. It is preferable because the capacity can be increased while suppressing the decrease in the electrochemical characteristics of the battery and the increase in the electrode thickness.
  • the content of silicon and silicon compounds in all negative electrode active materials is more preferably 2 to 15% by mass.
  • 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.
  • the battery separator is not particularly limited, and a single layer or laminated microporous film, woven fabric, nonwoven fabric or the like of polyolefin such as polypropylene, polyethylene, ethylene-propylene copolymer and 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 thickness of the heat-resistant layer is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 1.5 ⁇ m or more, and the upper limit thereof is 7 ⁇ m or less, preferably 6 ⁇ m or less, more preferably 5 ⁇ m or less. .
  • an oxide or hydroxide containing an element selected from Al, Si, Ti, and Zr is preferably exemplified.
  • Specific examples of the inorganic particles include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), zirconia (ZrO 2 ), oxides such as BaTiO 3 , and boehmite (Al 2 O 3. one or more selected from 3H 2 O) hydroxide and the like.
  • At least one selected from silica (SiO 2 ), alumina (Al 2 O 3 ), zirconia (ZrO 2 ), BaTiO 3 , and boehmite (Al 2 O 3 .3H 2 O) is preferable.
  • SiO 2 ), alumina (Al 2 O 3 ), BaTiO 3 , or boehmite (Al 2 O 3 .3H 2 O) is more preferable, and alumina (Al 2 O 3 ), BaTiO 3 , or boehmite (Al 2 O 3. 3H 2 O) is more preferred.
  • Examples of the organic particles contained in the heat-resistant layer include one or more selected from polymer particles such as polyamide, aramid, and polyimide. Among these, at least one selected from polyamide, aramid, and polyimide is preferable, and polyamide or aramid is more preferable.
  • binder included in the heat-resistant layer examples include ethylene-acrylic acid copolymers such as ethylene-vinyl acetate copolymer (EVA) and ethylene-ethyl acrylate copolymer, polytetrafluoroethylene (PTFE), and polyvinylidene fluoride.
  • EVA ethylene-vinyl acetate copolymer
  • PTFE polytetrafluoroethylene
  • PVDF fluorinated rubber
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • HEC hydroxyethyl cellulose
  • PVA polyvinyl alcohol
  • PVB polyvinyl butyral
  • PVP polyvinyl pyrrolidone
  • ethylene-acrylic acid copolymers such as ethylene-ethyl acrylate copolymers, polyvinylpyrrolidone (PVP), poly N-vinylacetamide, polyvinylidene fluoride (PVDF), styrene and butadiene copolymer (SBR) And one or more selected from carboxymethylcellulose (CMC) are preferred.
  • PVP polyvinylpyrrolidone
  • PVDF poly N-vinylacetamide
  • PVDF polyvinylidene fluoride
  • SBR styrene and butadiene copolymer
  • CMC carboxymethylcellulose
  • 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).
  • LIC lithium ion capacitor
  • Examples of 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 .
  • 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 punched 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 .
  • 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 microporous polyethylene film separator, and a negative electrode sheet were laminated in this order, and a non-aqueous electrolyte solution having the composition shown in Tables 1 to 3 was added to produce a 2032 type coin battery.
  • Capacity recovery rate (%) (recovery discharge capacity / initial discharge capacity) ⁇ 100 ⁇ Low-temperature discharge capacity maintenance rate after high-temperature charge storage> Thereafter, the coin battery was charged in a constant temperature bath at 25 ° C.
  • Low temperature discharge capacity retention rate after high temperature storage was determined by the following formula.
  • Low temperature discharge capacity retention rate after high temperature storage (%) (discharge capacity at ⁇ 20 ° C. after high temperature storage / initial discharge capacity) ⁇ 100
  • Tables 1 to 3 show battery fabrication conditions and battery characteristics.
  • Comparative Example I-3 The same positive electrode and negative electrode used in Example I-1 were used as in Example I-1, except that Li metal and non-aqueous electrolyte were added in an amount of 0.3% by mass of 4-phenylphenyl diethyl phosphate.
  • a coin battery was produced. As described in Non-Patent Document 1, the potential of the positive electrode was swept up to 4.65 V at a rate of 0.1 mV / sec in a constant temperature bath at 25 ° C. and held at that potential for 20 minutes. Thereafter, the voltage was lowered to 3.0 V at 0.1 mV / sec, the battery was once disassembled in the glove box, and the positive electrode was taken out. A coin battery was made in the same manner as in Comparative Example I-1 except that the extracted positive electrode was used. As a result of the battery measurement, the capacity recovery rate was 54%, and the low temperature discharge capacity maintenance rate after high temperature storage was 98%.
  • Example I-23, Comparative Example I-4 instead of the negative electrode active material used in Example I-1, a negative electrode sheet was prepared using lithium titanate Li 4 Ti 5 O 12 (negative electrode active material). 90% by mass of lithium titanate Li 4 Ti 5 O 12 and 5 % by mass of acetylene black (conductive material) are mixed, and 5% by mass of polyvinylidene fluoride (binder) is previously dissolved in 1-methyl-2-pyrrolidone. A negative electrode mixture paste was prepared by adding to the solution and mixing.
  • This negative electrode mixture paste was applied onto an aluminum foil (current collector), dried, pressed and punched to a predetermined size to produce a negative electrode sheet, and the charge end voltage during battery evaluation was 2
  • a coin battery was fabricated and evaluated in the same manner as in Example I-1, except that the voltage was 0.7 V and the discharge end voltage was 2.0 V. The results are shown in Table 4.
  • Example I-24, Comparative Example I-5 A positive electrode sheet was prepared using LiFePO 4 (positive electrode active material) coated with amorphous carbon instead of the positive electrode active material used in Example I-1. 90% by mass of LiFePO 4 coated with amorphous carbon and 5% by mass of acetylene black (conductive agent) are mixed, and 5% by mass of polyvinylidene fluoride (binder) is previously dissolved in 1-methyl-2-pyrrolidone.
  • a positive electrode mixture paste was prepared by adding to and mixing with the previously prepared solution. This positive electrode mixture paste was applied onto an aluminum foil (current collector), dried, pressurized and punched to a predetermined size to produce a positive electrode sheet, and the end-of-charge voltage during battery evaluation was 3.
  • a coin battery was prepared and evaluated in the same manner as in Example I-1, except that the voltage was 6 V and the discharge end voltage was 2.0 V. The results are shown in Table 5.
  • Patent Document 1 The capacity recovery rate after storage at high temperature and the low temperature discharge capacity retention rate are significantly improved as compared with the non-aqueous electrolyte lithium secondary battery to which the phosphate compound used in the method described in 1 is added.
  • the effect of the first invention is unique when the specific compound of the first invention is contained in an amount of 0.1 to 4.5% by mass in the nonaqueous electrolytic solution in which the electrolyte salt is dissolved in the nonaqueous solvent. It turned out to be an effect.
  • Li metal or lithium titanate Li 4 Ti 5 was used as the negative electrode.
  • O 12 negative electrode active material
  • LiFePO 4 positive electrode active material coated with amorphous carbon
  • the effect of the present invention is not an effect dependent on a specific positive electrode or negative electrode.
  • the non-aqueous electrolyte of the first invention also has an effect of improving discharge characteristics in a wide temperature range such as a lithium primary battery, a lithium ion capacitor, and a lithium air battery.
  • 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 heat-resistant layer (3 ⁇ m) having boehmite particles and an ethylene-vinyl acetate copolymer was formed on both surfaces of a laminated microporous film having a three-layer structure of polypropylene (3 ⁇ m) / polyethylene (5 ⁇ m) / polypropylene (3 ⁇ m)
  • a separator having a thickness of 17 ⁇ m was produced.
  • the positive electrode sheet obtained above, the separator, and the negative electrode sheet obtained above were laminated in this order, and a non-aqueous electrolyte solution having the composition shown in Tables 1 to 5 was added to produce a laminate type battery.
  • Discharge capacity retention ratio (%) (discharge capacity at the 200th cycle / discharge capacity at the first cycle) ⁇ 100 ⁇ Initial anode thickness>
  • the battery cycled by the above method was disassembled and the initial negative electrode thickness was measured.
  • ⁇ Negative electrode thickness after high-temperature cycle> The battery that had been subjected to 200 cycles by the above method was disassembled, and the negative electrode thickness after the high-temperature cycle was measured.
  • Negative electrode thickness increase value negative electrode thickness after cycle ⁇ initial negative electrode thickness
  • the negative electrode thickness increase rate (%) was determined based on the negative electrode thickness increase value of Comparative Example II-1 as 100%. The results are shown in Tables 6-9.
  • Example II-3 except that this negative electrode mixture paste was applied to one side of a copper foil (current collector), dried and pressurized to be cut into a predetermined size to produce a negative electrode sheet.
  • a laminate type battery was prepared in the same manner as in Comparative Example II-1, battery evaluation was performed, and the negative electrode thickness increase rate was determined based on the negative electrode thickness increase value of Comparative Example II-4 as 100%. The results are shown in Table 10.
  • Example II-27 and Comparative Example II-5 A positive electrode sheet was produced using LiFePO 4 (positive electrode active material) coated with amorphous carbon instead of the positive electrode active material used in Example II-3 and Comparative Example II-1. 90% by mass of LiFePO 4 coated with amorphous carbon and 5% by mass of acetylene black (conductive agent) are mixed, and 5% by mass of polyvinylidene fluoride (binder) is previously dissolved in 1-methyl-2-pyrrolidone. A positive electrode mixture paste was prepared by adding to and mixing with the previously prepared solution.
  • This positive electrode mixture paste was applied to one side of an aluminum foil (current collector), dried, pressurized and cut into a predetermined size to produce a positive electrode sheet, and the end-of-charge voltage during battery evaluation
  • a laminate type battery was prepared in the same manner as in Example II-3 and Comparative Example II-1, except that the discharge end voltage was 2.0 V and the discharge end voltage was 2.0 V.
  • the battery was evaluated and the rate of increase in thickness of the negative electrode was Was obtained on the basis of the case where the negative electrode thickness increase value of Comparative Example II-5 was 100%. The results are shown in Table 11.
  • the non-aqueous electrolyte of the first invention is used, an electricity storage device having excellent electrochemical characteristics in a wide temperature range can be obtained.
  • an electricity storage device capable of improving electrochemical characteristics in a wide temperature range. it can.
  • nonaqueous electrolytic solution of the second invention it is possible to obtain an electricity storage device that is excellent in electrochemical characteristics in a wide temperature range, particularly at a high temperature, and that further suppresses an increase in electrode thickness after a high temperature cycle.
  • non-aqueous electrolytes for power storage devices such as lithium secondary batteries mounted on devices that are likely to be used at high temperatures such as hybrid electric vehicles, plug-in hybrid electric vehicles, battery electric vehicles, tablet terminals and ultrabooks

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Abstract

La présente invention concerne une solution électrolytique non aqueuse dans laquelle un sel électrolytique est dissous dans une solution électrolytique non aqueuse, la solution électrolytique non aqueuse contenant un composé biphényle comprenant une structure d'ester d'acide phosphorique spécifique, le composé biphényle étant contenu dans la solution électrolytique non aqueuse en une quantité de 0,1 à 4,5 % en masse ; ou la solution électrolytique non aqueuse contenant un composé carbonate de phényle halogéné asymétrique spécifique, la quantité du composé carbonate de phényle halogéné contenu dans la solution électrolytique non aqueuse étant de 0,001 à 5 % en masse. Avec cette solution électrolytique non aqueuse, il est possible d'améliorer les propriétés électrochimiques sur une large plage de températures.
PCT/JP2015/081644 2014-11-11 2015-11-10 Solution électrolytique non aqueuse et dispositif de stockage d'électricité dans lequel cette solution électrolytique non aqueuse est utilisée Ceased WO2016076327A1 (fr)

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