CN114222748A - Thermal runaway inhibitor - Google Patents
Thermal runaway inhibitor Download PDFInfo
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- CN114222748A CN114222748A CN202080054058.8A CN202080054058A CN114222748A CN 114222748 A CN114222748 A CN 114222748A CN 202080054058 A CN202080054058 A CN 202080054058A CN 114222748 A CN114222748 A CN 114222748A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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
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- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- 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
Abstract
The invention provides a thermal runaway inhibitor, which is composed of phosphate ester compounds represented by general formula (1) described in the specification and is caused by internal short circuit of a nonaqueous electrolyte secondary battery; and a method for suppressing thermal runaway caused by an internal short circuit of a nonaqueous electrolyte electricity storage device, wherein the thermal runaway suppressor is incorporated in the nonaqueous electrolyte in an amount of 0.01 to 10 mass%.
Description
Technical Field
The present invention relates to a thermal runaway inhibitor caused by an internal short circuit in a nonaqueous electrolyte electricity storage device, and a method for inhibiting thermal runaway caused by an internal short circuit using the same.
Background
Nonaqueous electrolyte secondary batteries such as lithium ion secondary batteries are small and lightweight, have high energy density and high capacity, and can be repeatedly charged and discharged, and therefore are widely used as power sources for portable electronic devices such as portable computers, hand-held video cameras, and information terminals. In view of environmental problems, electric vehicles using nonaqueous electrolyte secondary batteries and hybrid vehicles using electric power as a part of motive power have been put to practical use.
The nonaqueous electrolyte secondary battery is composed of an electrode, a separator, a nonaqueous electrolyte, and the like. Various measures have been studied for the reason that a flammable organic solvent is used as a main solvent of the nonaqueous electrolyte, and when a large amount of energy is released due to an internal short circuit or the like, thermal runaway occurs, and there is a risk of ignition or rupture. As such countermeasures, the following methods are known: a method in which a porous membrane containing polyolefin as a main component is used as a separator (see, for example, patent documents 1 and 2); a method of providing a porous heat-resistant layer between a positive electrode and a negative electrode, in addition to a separator (see, for example, patent document 3); a method of coating the surface of an electrode active material with a metal oxide (for example, see patent document 4); a method in which a lithium-containing nickel oxide is used as a positive electrode active material (for example, see patent document 5); a method in which an olivine-type lithium phosphate compound is used as a positive electrode active material (see, for example, patent document 6); a method in which a lithium titanate compound having a spinel structure is used as a negative electrode active material (see, for example, patent document 7); a method in which a nonflammable fluorine-based solvent is used as a main solvent of a nonaqueous electrolyte (see, for example, patent documents 8 and 9); a method of using a solid electrolyte that does not use an organic solvent as a nonaqueous electrolyte (for example, see patent document 10), and the like.
In order to prevent an internal short circuit in a separator of a porous film containing polyolefin as a main component, it is necessary to provide the separator thick, and in the method of providing a porous heat-resistant layer, the battery becomes large according to the porous heat-resistant layer, and in the method of coating the surface of an electrode active material with a metal oxide, the content of the electrode active material contained in an electrode mixture layer of an electrode is relatively reduced, and the capacity of the battery becomes small, and the advantages of a small, lightweight, and high-capacity nonaqueous electrolyte secondary battery are lost. In both the method of using a lithium-containing nickel oxide or an olivine-type lithium phosphate compound as a positive electrode active material and the method of using a lithium titanate compound having a spinel structure as a negative electrode active material, a high energy density cannot be obtained. In addition, in the method using a fluorine-based solvent, the fluorine-based solvent is very expensive and needs to be used in a large amount, which leads to a significant increase in cost. In the method using a solid electrolyte, since a solid electrolyte material having no fluidity is used, the internal resistance becomes high, and the performance is lowered as compared with a non-aqueous electrolyte using an organic solvent.
On the other hand, phosphate ester compounds are known as flame retardants, and lithium ion secondary batteries having a nonaqueous electrolyte containing a phosphate ester compound are also known. However, although alkyl phosphate ester compounds have an effect of improving flame retardancy, the effect of suppressing thermal runaway caused by internal short circuits is insufficient (see, for example, patent documents 11 to 13), and the effect of suppressing thermal runaway when an aryl phosphate ester compound is overcharged is known (see, for example, patent document 14), but the effect of suppressing thermal runaway caused by internal short circuits is not known.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2016/152266
Patent document 2: international publication No. 2016/056288
Patent document 3: japanese patent laid-open publication No. 2005-174792
Patent document 4: japanese patent laid-open publication No. 2011-216300
Patent document 5: japanese laid-open patent publication No. 2002-015736
Patent document 6: japanese patent laid-open publication No. 2007-012441
Patent document 7: japanese laid-open patent publication No. 2008-159280
Patent document 8: international publication No. 2007/043526
Patent document 9: international publication No. 2008/007734
Patent document 10: japanese patent laid-open publication No. 2016-207567
Patent document 11: japanese laid-open patent publication No. 11-176471
Patent document 12: japanese patent laid-open No. 2008-204789
Patent document 13: japanese laid-open patent publication No. 2015-065130
Patent document 14: japanese patent laid-open publication No. 2005-347240
Disclosure of Invention
Problems to be solved by the invention
The problem of the present invention is to provide an additive for manufacturing a nonaqueous electrolyte electricity storage device which is not large-sized, does not increase the cost greatly, is less likely to cause thermal runaway even if an internal short circuit occurs, and has a low risk of ignition and rupture.
Means for solving the problems
The present inventors have intensively studied the above-mentioned problems, and as a result, they have found that even in a nonaqueous electrolyte power storage device having a nonaqueous electrolyte in which an organic solvent is used as a solvent, the incorporation of an aryl phosphate compound into the nonaqueous electrolyte makes it difficult to cause thermal runaway and prevents ignition or cracking due to internal short-circuiting. That is, the present invention is a thermal runaway inhibitor for a nonaqueous electrolyte power storage device comprising a phosphate compound represented by the following general formula (1), the nonaqueous electrolyte power storage device comprising: the nonaqueous electrolyte secondary battery includes a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and a nonaqueous electrolyte, and the thermal runaway is thermal runaway caused by an internal short circuit of the nonaqueous electrolyte secondary battery.
(in the formula, R1～R4Each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, X1Represents a group represented by the general formula (2) or the general formula (3), and a represents 0 or a number of 1 to 4. )
(in the formula, R5～R8Each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, X2Represents a direct bond, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a group represented by the following general formula (4), b represents a number of 0 or 1, and x represents a bond. )
(in the formula, R9～R10Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 2 carbon atoms or R9And R10A hydrocarbon group having 5 to 12 carbon atoms formed by crosslinking, which represents a bonding bond. )
(in the formula, R11～R14Each independently represents a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluoroalkyl group having 1 to 2 carbon atoms, and represents a bond. )
Effects of the invention
By using the thermal runaway inhibitor of the present invention, it is possible to provide a nonaqueous electrolyte electricity storage device which is small, lightweight, and high in capacity without increasing the size and cost, and which is less likely to cause thermal runaway and less likely to cause a risk of ignition and breakage even if an internal short circuit occurs.
Detailed Description
The present invention is a thermal runaway inhibitor for a nonaqueous electrolyte electricity storage device, characterized by being composed of a phosphate ester compound represented by the general formula (1). Further, the nonaqueous electrolyte electricity storage device includes: a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and a nonaqueous electrolyte, wherein thermal runaway is thermal runaway caused by an internal short circuit of a nonaqueous electrolyte electricity storage device. The phosphate ester compound represented by the general formula (1) may be referred to as the phosphate ester compound of the present invention.
In the general formula (1), R1～R4Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl. As R1～R4From the viewpoint of a large effect of suppressing thermal runaway, a hydrogen atom, a methyl group, and an ethyl group are preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is most preferable.
X1Represents a group represented by the following general formula (2) or general formula (3).
(in the formula, R5～R8Each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, X2Represents a direct bond, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a group represented by the following general formula (4), b represents a number of 0 or 1, and x represents a bond. )
(in the formula, R9～R10Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 2 carbon atoms or R9And R10A hydrocarbon group having 5 to 12 carbon atoms formed by crosslinking, which represents a bonding bond. )
(in the formula, R11～R14Each independently represents a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluoroalkyl group having 1 to 2 carbon atoms, and represents a bond. )
In the general formula (2), R5～R8Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include R in the general formula (1)1～R4The alkyl groups shown in (1) are exemplified. As R5～R8From the viewpoint of a large effect of suppressing thermal runaway, a hydrogen atom, a methyl group, and an ethyl group are preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is most preferable.
X2Represents a direct bond, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a group represented by the general formula (4), b represents a number of 0 or 1, and x represents a bond.
In the general formula (4), R9、R10Each independently represents a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 2 carbon atoms or R9And R10A hydrocarbon group having 5 to 12 carbon atoms formed by crosslinking. Examples of the hydrocarbon group having 1 to 10 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, sec-hexyl, heptyl, octyl, 2-methylhexyl, 2-ethylhexyl, nonyl, decyl, cyclohexyl, phenyl, benzyl, cyclohexyl, cyclopentyl, 2-norbornyl and the like. Examples of the fluoroalkyl group having 1 to 2 carbon atoms include: fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 1, 2, 2-tetrafluoroethyl, perfluoroethyl, and the like. As R9And R10Examples of the hydrocarbon group formed by crosslinking include X2To form cyclohexylidene [ the following formula (5) ]]3, 3, 5-trimethylcyclohexylidene [ formula (6) below ]]Octahydro-4, 7-methano-5H-inden-5-ylidene [ formula (7)]9H-fluoren-9-ylidene [ formula (8) below)]Such a hydrocarbon group.
(in formulae (5) to (8),. phi.
In the general formula (3), R11～R14Each independently represents a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluoroalkyl group having 1 to 2 carbon atoms, and represents a bond. Examples of the hydrocarbon group having 1 to 10 carbon atoms and the fluoroalkyl group having 1 to 2 carbon atoms include the hydrocarbon group and fluoroalkyl group exemplified in the general formula (2). As R11～R14From the viewpoint of a large effect of suppressing thermal runaway, a hydrogen atom, a methyl group, and an ethyl group are preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is most preferable.
As X2From the viewpoint of a large effect of suppressing thermal runaway, direct bonding, an oxygen atom, a sulfonyl group, and a group represented by the general formula (4) are preferable. At X2In the case where the group is not represented by the general formula (4), direct bonding and oxygen atom bonding are more preferable, and direct bonding is further preferable. At X2In the case of a group represented by the general formula (4), R9、R10Hydrogen atom, methyl group and ethyl group are preferable, and methyl group is more preferable.
In the general formula (1), a represents 0 or a number of 1 to 4. When a is a number of 1 to 4, a mixture of compounds having different numbers of repeating units a may be used, and in the case of a mixture, a represents an average number. a is preferably a number of 1 to 4, more preferably a number of 1 to 2, more preferably a number of 1.0 to 1.7, and further preferably a number of 1.1 to 1.6.
Preferable examples of the phosphate ester compound of the present invention include the following formulae (9) to (17).
(in formulae (9) to (17), a is the same as a in general formula (1))
Among the above compounds, compounds represented by formula (9), formula (10), formula (11), formula (12) and formula (16) are preferred.
The compound represented by formula (11) is preferably a compound represented by the following formula, and a is preferably 1.2.
As the compound represented by the formula (12), a compound in which a is 1.2 is preferable.
The compound represented by the formula (16) is preferably a compound in which a is 1.2.
The phosphate ester compound represented by the above general formula (1) can be obtained by a known method. For example, a compound in which a is 0 in the general formula (1) can be obtained by: phosphorus oxychloride (Phosphorus oxychloride) is reacted with a compound having one hydroxyl group on the benzene ring, such as phenol, cresol, or the like, under prescribed conditions. Further, the compound in which a in the general formula (1) is 1 to 4 can be obtained by: after an excessive amount of phosphorus oxychloride is reacted with a compound having two hydroxyl groups on the benzene ring, for example, Hydroquinone (Hydroquinone), resorcinol, bisphenol a, biphenyldiol F, or the like under a predetermined condition, unreacted phosphorus oxychloride is removed, and further, a compound having one hydroxyl group on the benzene ring is reacted. Further, the compound in the general formula (1) wherein a is 1 to 4 can be obtained by the so-called transesterification as follows: a compound having 0 as a in the general formula (1) is reacted with a compound having two hydroxyl groups on the benzene ring, while removing the resulting compound having one hydroxyl group on the benzene ring.
In the present invention, the phosphate ester compound of the present invention is blended as a thermal runaway inhibitor to a nonaqueous electrolyte. The content of the phosphate ester compound of the present invention in the nonaqueous electrolyte is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and most preferably 0.1 to 3% by mass, based on the total amount of the nonaqueous electrolyte. When the content of the phosphate compound of the present invention in the nonaqueous electrolyte is too small, a sufficient effect of suppressing thermal runaway cannot be obtained, and when the content of the phosphate compound of the present invention in the nonaqueous electrolyte is too large, an effect corresponding to an increase in the amount to be blended cannot be obtained. The phosphate ester compound of the present invention may be used alone, or two or more thereof may be used in combination. When two or more compounds are used in combination, at least one of the compounds is preferably a compound in which a is 0 in the general formula (1) and a compound in which a is 1 to 4 in the general formula (1).
The mechanism of the phosphate compound of the present invention for suppressing thermal runaway caused by an internal short circuit in a nonaqueous electrolyte storage device is not sufficiently understood, but it is presumed that at the initial stage of the internal short circuit, a part of the phosphate compound of the present invention is decomposed by a short-circuit current, and an insulating film is formed on the surface of an electrode. Such an insulating film may be formed of alkyl phosphate, but this is not sufficient, and it is presumed that the phosphate compound of the present invention forms a strong insulating film in the case of the compounds of formulae (9) to (17) in which the alkyl group is small or no alkyl group.
The thermal runaway caused by the internal short circuit is the following phenomenon: when the positive electrode and the negative electrode are electrically short-circuited and electricity flows from the positive electrode to the negative electrode at a time, abnormal joule heat is generated, and the generated heat becomes a trigger (trigger) and causes thermal runaway due to reaction between the electrolyte and the electrode, thermal decomposition of the electrolyte, thermal decomposition of the positive electrode, and the like. On the other hand, thermal runaway caused by overcharge is a phenomenon as follows: lithium ions are excessively extracted from the positive electrode due to overcharge, the crystal structure of the positive electrode material is destroyed, and thermal runaway is caused by heat generation due to a decrease in stability of the positive electrode, heat generation due to an increase in internal resistance of the battery, oxidative decomposition of the electrolyte solution, and the like. In this manner, thermal runaway caused by internal short circuit and thermal runaway caused by overcharge are caused by completely different phenomena.
Specific examples of the electric storage device include a nonaqueous electrolyte secondary battery (a lithium ion secondary battery or the like) and an electric double layer capacitor (a lithium ion capacitor or the like). The nonaqueous electrolytic solution of the present embodiment is particularly effective for applications to lithium ion secondary batteries and lithium ion capacitors.
Examples of the nonaqueous electrolyte power storage device to which the present invention is applicable include: a liquid electrolyte obtained by dissolving a supporting electrolyte in an organic solvent; a polymer gel electrolyte obtained by dissolving a supporting electrolyte in an organic solvent and gelling the supporting electrolyte with a polymer; pure polymer electrolytes which do not contain organic solvents and are formed by dispersing supporting electrolytes into polymers, and the like. Among these, in a nonaqueous electrolyte electricity storage device having a liquid electrolyte, thermal runaway is likely to occur due to an internal short circuit, and the risk of ignition and explosion is high, and therefore the inhibitor for thermal runaway of the present invention is preferably used for a nonaqueous electrolyte of a nonaqueous electrolyte electricity storage device having a liquid electrolyte.
As the supporting electrolyte used for the liquid electrolyte and the polymer gel electrolyte, a conventionally known supporting electrolyte can be used. In the following, a description will be given of a supporting electrolyte in the case where the nonaqueous electrolyte electric storage device is a lithium ion secondary battery or a lithium ion capacitor, but in the case of a sodium ion secondary battery or a sodium ion capacitor, a supporting electrolyte in which lithium atoms are replaced with sodium atoms is used. Examples of the supporting electrolyte used for the liquid electrolyte and the polymer gel electrolyte include: LiPF6、LiBF4、LiAsF6、LiCF3SO3、LiCF3CO2、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiN(SO2F)2、LiC(CF3SO2)3、LiB(CF3SO3)4、LiB(C2O4)2、LiBF2(C2O4)、LiSbF6、LiSiF5、LiSCN、LiClO4、LiCl、LiF、LiBr、LiI、LiAlF4、LiAlCl4、LiPO2F2And derivatives thereof, among them, those selected from the group consisting of LiPF are preferably used6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiN(SO2F)2、LiPO2F2And LiC (CF)3SO2)3And LiCF3SO3Derivative of (2), and LiC (CF)3SO2)3One of the group consisting of derivatives of (1)The above. The content of the supporting electrolyte in the liquid electrolyte and the polymer gel electrolyte is preferably 0.5mol/L to 7mol/L, and more preferably 0.8mol/L to 1.8 mol/L.
Examples of the supporting electrolyte for pure polymer electrolytes include: LiN (CF)3SO2)2、LiN(C2F5SO2)2、LiN(SO2F)2、LiC(CF3SO2)3、LiB(CF3SO3)4、LiB(C2O4)2。
As the organic solvent used in the present invention for preparing the liquid nonaqueous electrolyte, one kind or two or more kinds in combination of organic solvents generally used for nonaqueous electrolytes can be used. Specifically, for example, there are: saturated cyclic carbonate compounds, saturated cyclic ester compounds, sulfoxide compounds, sulfone compounds, amide compounds, saturated chain carbonate compounds, chain ether compounds, cyclic ether compounds, saturated chain ester compounds, and the like.
Among the organic solvents, a saturated cyclic carbonate compound, a saturated cyclic ester compound, a sulfoxide compound, a sulfone compound, and an amide compound are preferable because they have a high relative dielectric constant and thus function to increase the dielectric constant of the nonaqueous electrolyte. Examples of the saturated cyclic carbonate compound include: ethylene carbonate, 1, 2-propylene carbonate, 1, 3-propylene carbonate, 1, 2-butylene carbonate, 1, 3-butylene carbonate, 1-dimethylethylene carbonate, and the like. Examples of the saturated cyclic ester compound include: gamma-butyrolactone, gamma-valerolactone, gamma-caprolactone, delta-octalactone and the like. Examples of the sulfoxide compound include: dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, thiophene, etc. Examples of the sulfone compound include: dimethyl sulfone, diethyl sulfone, dipropyl sulfone, diphenyl sulfone, sulfolane (also referred to as tetramethylene sulfone), 3-methylsulfolane, 3, 4-dimethylsulfolane, 3, 4-diphenylmethylsulfolane, sulfolene, 3-methylsulfolane, 3-ethylsulfolene, 3-bromomethylsulfolane, etc., preferably sulfolane, tetramethylsulfolane. Examples of the amide compound include: n-methylpyrrolidone, dimethylformamide, dimethylacetamide, and the like.
Among the organic solvents, a saturated chain carbonate compound, a chain ether compound, a cyclic ether compound, and a saturated chain ester compound can reduce the viscosity of the nonaqueous electrolyte, can improve the mobility of electrolyte ions, and the like, and can make battery characteristics such as output density excellent. In addition, a saturated chain carbonate compound is particularly preferable from the viewpoint that the performance of the nonaqueous electrolyte at low temperature can be improved because of its low viscosity. Examples of the saturated chain carbonate compound include: dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl butyl carbonate, methyl-t-butyl carbonate, diisopropyl carbonate, t-butylpropyl carbonate, and the like. Examples of the chain ether compound or the cyclic ether compound include: dimethoxyethane, ethoxymethoxyethane, diethoxyethane, tetrahydrofuran, dioxolane, dioxane, 1, 2-bis (methoxycarbonyloxy) ethane, 1, 2-bis (ethoxycarbonyloxy) propane, ethylene glycol bis (trifluoroethyl) ether, propylene glycol bis (trifluoroethyl) ether, ethylene glycol bis (trifluoromethyl) ether, diethylene glycol bis (trifluoroethyl) ether and the like, and among them, dioxolane is preferable.
The saturated chain ester compound is preferably a monoester compound and a diester compound having 2 to 8 carbon atoms in total in the molecule, and specific examples of the compound include: methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl pivalate, ethyl pivalate, methyl malonate, ethyl malonate, methyl succinate, ethyl succinate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethylene glycol diacetyl, propylene glycol diacetyl, and the like, with preference given to methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, methyl propionate, and ethyl propionate.
In addition, as the organic solvent used for preparing the nonaqueous electrolyte, for example, acetonitrile, propionitrile, nitromethane, derivatives thereof, and various ionic liquids may also be used.
Examples of the polymer used for the polymer gel electrolyte include: polyethylene oxide, polypropylene oxide, polyvinyl chloride, polyacrylonitrile, polymethyl methacrylate, polyethylene, polyvinylidene fluoride, polyhexafluoropropylene, and the like. Examples of the polymer used for the pure polymer electrolyte include: polyethylene oxide, polypropylene oxide, polystyrene sulfonic acid. The mixing ratio in the gel electrolyte and the method of compounding are not particularly limited, and a mixing ratio known in the art and a known compounding method can be used.
The nonaqueous electrolyte may contain other known additives such as an electrode coating film forming agent, an antioxidant, a flame retardant, and an overcharge inhibitor in order to further improve the battery life and improve safety.
The positive electrode containing the positive electrode active material to which the nonaqueous electrolyte electricity storage device of the present invention is applied is an electrode in which an electrode mixture layer containing the positive electrode active material is formed on a current collector, and for example, a sheet-shaped electrode is formed by applying a material obtained by slurrying the positive electrode active material, a binder, and a conductive auxiliary material in an organic solvent or water to the current collector and drying the applied material.
As the positive electrode active material of the positive electrode, a known positive electrode active material can be used. In the following, a supporting electrolyte in the case where the nonaqueous electrolyte storage device is a lithium ion secondary battery or a lithium ion capacitor is described, but in the case of a sodium ion secondary battery or a sodium ion capacitor, a positive electrode active material in which lithium atoms are replaced with sodium atoms is used.
Examples of known positive electrode active materials for lithium ion secondary batteries and lithium ion capacitors include: lithium transition metal composite oxide, lithium-containing transition metal phosphate compound,Lithium-containing silicate compounds, lithium-containing transition metal sulfate compounds, sulfur-containing compounds, and the like. As the transition metal of the lithium transition metal composite oxide, vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper, and the like are preferable. Specific examples of the lithium transition metal composite oxide include: LiCoO2Lithium cobalt composite oxide; LiNiO2Lithium nickel composite oxide; LiMnO2、LiMn2O4、Li2MnO3Lithium manganese composite oxides, etc.; and composite oxides in which a part of transition metal atoms that are the main components of these lithium transition metal composite oxides is replaced with another metal such as aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, lithium, nickel, copper, zinc, magnesium, gallium, or zirconium. Examples of the lithium transition metal composite oxide in which a part of the transition metal atom as a main component is replaced with another metal include: li1.1Mn1.8Mg0.1O4、Li1.1Mn1.85Al0.05O4、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.5Mn0.5O2、LiNi0.80Co0.17Al0.03O2、LiNi0.80Co0.15Al0.05O2、Li(Ni1/3Co1/3Mn1/3)O2、LiNi0.6Co0.2Mn0.2O2、LiMn1.8Al0.2O4、LiNi0.5Mn1.5O4、Li2MnO3－LiMO2And (M ═ Co, Ni, Mn) and the like. As the transition metal of the lithium-containing transition metal phosphate compound, vanadium, titanium, manganese, iron, cobalt, nickel and the like are preferable, and specific examples thereof include: LiFePO4、LiMnXFe1-XPO4(x is more than 0 and less than 1) and other iron phosphate compounds; LiCoPO4And the like cobalt phosphate compounds; a part of transition metal atoms which are the main components of these lithium transition metal phosphate compounds is replaced with aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, lithium, nickel,Composite oxides of other metals such as copper, zinc, magnesium, gallium, zirconium, niobium, and the like; li3V2(PO4)3And vanadium phosphate compounds and the like. Examples of the lithium-containing silicate compound include Li2FeSiO4And the like. Examples of the lithium-containing transition metal sulfate compound include: LiFeSO4、LiFeSO4F, and the like. These may be used alone or in combination of two or more.
The inhibitor of thermal runaway of the present invention can be preferably used for a nonaqueous electrolytic storage device having a large charge-discharge capacity. Examples of the positive electrode active material having a large charge/discharge capacity include: LiCoO2、LiMn2O4、LiNi0.5Mn1.5O4、Li(Ni0.8Co0.15Al0.05)O2、LiNiXCoYMnZO2(X+Y+Z＝1，0≤X≤1，0≤Y≤1，0≤Z≤1)、LiNiO2、Li2MnO3－LiMO2(M ═ Co, Ni, Mn), the inhibitor of thermal runaway of the present invention can be preferably used for nonaqueous electrolyte storage devices having these positive electrode active materials.
Examples of the binder include: polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), ethylene-propylene-diene copolymer (EPDM), styrene-butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), styrene-isoprene copolymer, polymethyl methacrylate, polyacrylate, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose (CMCNa), Methyl Cellulose (MC), starch, polyvinyl pyrrolidone, Polyethylene (PE), polypropylene (PP), polyethylene oxide (PEO), Polyimide (PI), polyamide imide (PAI), Polyacrylonitrile (PAN), polyvinyl chloride (PVC), polyacrylic acid, polyurethane, and the like. The amount of the binder used is usually about 1 to 20 mass%, preferably 2 to 10 mass%, based on the positive electrode active material.
Examples of the conductive auxiliary material include: carbon Black, ketjen Black, acetylene Black, channel Black, furnace Black, Lamp Black (Lamp Black), thermal Black, carbon nanotubeCarbon materials such as Vapor Grown Carbon Fiber (VGCF), graphene, fullerene, and needle coke; metal powders such as aluminum powder, nickel powder, titanium powder, and the like; conductive metal oxides such as zinc oxide and titanium oxide; la2S3、Sm2S3、Ce2S3、TiS2And the like. The average particle diameter of the conductive auxiliary is preferably 0.0001 to 100. mu.m, and more preferably 0.01 to 50 μm.
As the solvent for slurrying, an organic solvent or water in which the binder is dissolved is used. Examples of the organic solvent include: n-methylpyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran, and the like. The amount of the solvent used is usually about 10 to 400 mass%, preferably 20 to 200 mass%, based on the positive electrode active material.
As the current collector of the positive electrode, aluminum, stainless steel, nickel-plated steel, or the like is generally used. Examples of the shape of the current collector include: foil, plate, net, etc., and foil is preferable. In the case of foil-like, the thickness of the foil is usually 1 μm to 100. mu.m.
The negative electrode containing the negative electrode active material to which the nonaqueous electrolyte electricity storage device of the present invention is applied is an electrode in which an electrode mixture layer containing the negative electrode active material is formed on a current collector, and for example, a negative electrode active material, a binder, and a conductive auxiliary material are formed into a slurry with an organic solvent or water, applied to the current collector, and dried to form a sheet-like electrode.
As the negative electrode active material of the negative electrode, a known negative electrode active material can be used. In the following, a supporting electrolyte in the case where the nonaqueous electrolyte storage device is a lithium ion secondary battery or a lithium ion capacitor is described, but in the case of a sodium ion secondary battery or a sodium ion capacitor, a negative electrode active material in which lithium atoms in a negative electrode active material having lithium atoms are replaced with sodium atoms is used.
Examples of known negative electrode active materials include: a carbonaceous material,LiVO, in addition to lithium, lithium alloy, silicon alloy, silicon oxide, tin alloy, tin oxide, phosphorus, germanium, indium, copper oxide, antimony sulfide, titanium oxide, iron oxide, manganese oxide, cobalt oxide, nickel oxide, lead oxide, ruthenium oxide, tungsten oxide, and zinc oxide2、Li2VO4、Li4Ti5O12Composite oxides such as titanium-niobium oxides, conductive polymers, sulfur-containing compounds, and the like. The carbonaceous material is not particularly limited, and includes: natural graphite, artificial graphite, fullerene, graphene, chopped graphite fiber, carbon nanotube, graphite whisker, highly oriented pyrolytic graphite, crystalline carbon such as kish graphite, hard graphitizable carbon, easy graphitizable carbon, petroleum coke, carbolite-based coke, carbonized petroleum pitch, carbonized carbolite-based pitch, carbonized phenolic resin/crystalline cellulose resin, and the like, and carbon materials obtained by partially carbonizing these, furnace black, acetylene black, pitch-based carbon fiber, polyacrylonitrile-based carbon fiber, and the like. Examples of the sulfur-containing compound include: sulfur-modified polyacrylonitrile, carbon polysulfides represented by the general formula (CSx) n (x is 0.9 to 1.5, and n is a number of 4 or more), and the like. When the positive electrode active material is a sulfur-containing compound, a negative electrode active material other than the sulfur-containing compound is used as the negative electrode active material.
Examples of the binder, the conductive auxiliary material, and the slurried solvent include those similar to those of the positive electrode. The amount of the binder used is usually about 1 to 30% by mass, preferably about 2 to 15% by mass, based on the negative electrode active material. The amount of the solvent used is usually about 10 to 400 mass%, preferably 20 to 200 mass%, based on the negative electrode active material.
As the current collector of the negative electrode, copper, nickel, stainless steel, nickel-plated steel, aluminum, or the like is generally used. Examples of the shape of the current collector include: foil, plate, net, etc., and foil is preferable. The thickness of the foil in the case of foil-like shape is usually 1 μm to 100. mu.m.
In the nonaqueous electrolyte electricity storage device to which the present invention is applied, a separator is used between the positive electrode and the negative electrode, and a generally used polymer microporous membrane or the like is preferable as the separator, and is not particularly limited. Examples of the film include films formed of polyethers such as polyethylene, polypropylene, polyvinylidene fluoride, polyvinylidene chloride, polyacrylonitrile, polyacrylamide, polytetrafluoroethylene, polysulfone, polyethersulfone, polycarbonate, polyamide, polyimide, polyethylene oxide, and polypropylene oxide, various celluloses such as carboxymethyl cellulose and hydroxypropyl cellulose, high molecular compounds mainly composed of poly (meth) acrylic acid and various esters thereof, derivatives thereof, copolymers thereof, and mixtures thereof, and these films may be covered with a ceramic material such as alumina and silica, magnesium oxide, an aramid resin, and polyvinylidene fluoride. When the nonaqueous solvent electrolyte is a pure polymer electrolyte, the separator may not be included.
The nonaqueous electrolyte electricity storage device to which the present invention is applied preferably applies a nonaqueous electrolyte secondary battery. The form of the nonaqueous electrolyte secondary battery may be any of the following forms: the present invention is preferably used for a stacked nonaqueous electrolyte secondary battery and a wound nonaqueous electrolyte secondary battery, in view of the high charge/discharge capacity of the stacked nonaqueous electrolyte secondary battery and the wound nonaqueous electrolyte secondary battery and the tendency of thermal runaway due to internal short-circuiting, such as a stacked battery in which a single cell, a positive electrode and a negative electrode are stacked in multiple layers with a separator interposed therebetween, a wound battery in which a long sheet-like separator, a positive electrode and a negative electrode are wound, and the like.
Examples
The present invention will be specifically described below with reference to examples and comparative examples, which do not limit the scope of the present invention. In the examples, "part" and "%" are by mass unless otherwise specified.
[ preparation of nonaqueous electrolyte ]
In a mixed solvent composed of 49.5 vol% of ethylene carbonate, 49.5 vol% of diethyl carbonate, and 1 vol% of vinylene carbonate, LiPF was added6Dissolved at a concentration of 1.0mol/L to prepare a nonaqueous solution of comparative example 1An electrolyte. Further, in the nonaqueous electrolyte of comparative example 1, the following phosphate ester compounds were dissolved at concentrations described in table 1 to prepare nonaqueous electrolytes of examples 1 to 9 and comparative examples 2 to 3.
A1
A2
A3
A4
A5
A6
[ Table 1]
| Phosphate ester compound | |
| Example 1 | A1(1.0 mass%) |
| Example 2 | A2(1.0 mass%) |
| Example 3 | A3(1.0 mass%) |
| Example 4 | A4(1.0 mass%) |
| Example 5 | A5(1.0 mass%) |
| Example 6 | A3(0.5 mass%) |
| Example 7 | A3(2.0 mass%) |
| Example 8 | A4(0.5 mass%) |
| Example 9 | A4(2.0 mass%) |
| Comparative example 2 | A6(1.0 mass%) |
| Comparative example 3 | A6(2.0 mass%) |
[ production of Positive electrode ]
To 90 parts by mass of N-methylpyrrolidone, 94.0 parts by mass of Li (Ni) as a positive electrode active material was mixed0.6Co0.2Mn0.2)O2(product name: NCM622 manufactured by Beijing Danengl materials Technology Co., Ltd.), 3.0 parts by mass of acetylene black (manufactured by DENKA) as a conductive aid, and 3.0 parts by mass of polyvinylidene fluoride (manufactured by KUREHA) as a binder, and the resultant was dispersed by a rotation/revolution stirrer to prepare a slurry. The slurry composition was continuously applied to each of both surfaces of a current collector of a roll-shaped aluminum foil (thickness: 20 μm) by a comma coater method, and dried at 90 ℃. The roll was cut to have a length of 50mm and a width of 90mm, the electrode mixture layers on both sides of one of the wide sides (short sides) were removed by 10mm from the end portions to expose the current collector, and the current collector was vacuum-dried at 150 ℃ for 2 hours to produce a positive electrode.
(production of negative electrode)
To 100 parts by mass of water were mixed 96.5 parts by mass of artificial graphite (manufactured by hitachi corporation) as an electrode active material, 0.5 part by mass of acetylene black (manufactured by DENKA) as a conductive aid, 2.0 parts by mass of styrene-butadiene rubber (aqueous dispersion, manufactured by japan ZEON) as a binder, and 1.0 part by mass of sodium carboxymethylcellulose (manufactured by Daicel FineChem), and the mixture was dispersed by using a rotation/revolution mixer to prepare a slurry. The slurry composition was continuously applied to each of both surfaces of a current collector of a roll-shaped copper foil (thickness: 10 μm) by a comma coater method, and dried at 90 ℃. The roll was cut to have a length of 55mm and a width of 95mm, the electrode mixture layers on both sides of one of the wide sides (short sides) were removed by 10mm from the end portions to expose the current collector, and the current collector was vacuum-dried at 150 ℃ for 2 hours to produce a negative electrode.
[ production of laminated Battery ]
A positive electrode and a negative electrode were laminated with a separator (trade name: Celgard 2325, manufactured by Celgard corporation) therebetween so that the battery capacity became 3Ah, and a positive electrode terminal and a negative electrode terminal were provided to the positive electrode and the negative electrode, respectively, to obtain a laminate. The obtained laminate and the nonaqueous electrolytes of examples 1 to 9 and comparative examples 1 to 3 were contained in an aluminum laminated film, and laminated batteries of examples 1 to 9 and comparative examples 1 to 3 were obtained.
[ charging method ]
In a 25 ℃ constant temperature bath, the exhaust treatment was performed by performing primary charging and discharging at a charging rate of 0.1C and a discharging rate of 0.1C with a charging end voltage of 4.2V and a discharging end voltage of 2.75V. Further, a charge-discharge cycle under the same conditions was performed five times, and the charge rate was 0.1C to 4.3V, which was used for the test.
[ spike test method ]
A battery having a surface temperature of 23 ℃ was fixed to a phenol resin plate having a hole of 10mm in diameter, and a round iron nail (N65) of 3mm in diameter and 65mm in length was inserted perpendicularly to the surface of the battery at a speed of 1mm/s into the center of the hole, and the nail was passed through the battery for 10mm, and held for 10 minutes, and then pulled out. The maximum surface temperature of the battery after the nail penetration into the battery was shown in table 2. The maximum surface temperature was measured by a thermocouple at a surface of the battery 10mm away from the nail portion, and the temperature at which the temperature increased to the maximum was defined as the maximum surface temperature.
[ Table 2]
| Maximum apparent temperature (. degree.C.) | |
| Example 1 | 62 |
| Example 2 | 66 |
| Example 3 | 33 |
| Example 4 | 29 |
| Example 5 | 38 |
| Example 6 | 45 |
| Example 7 | 30 |
| Example 8 | 33 |
| Example 9 | 28 |
| Comparative example 1 | 342 |
| Comparative example 2 | 167 |
| Comparative example 3 | 145 |
The rise in surface temperature in this test was caused by an internal short circuit of the battery. The batteries having a nonaqueous electrolyte containing the phosphate compound of the present invention exhibited a significantly lower maximum surface temperature and were less likely to suffer thermal runaway due to internal short circuits than comparative examples 1 and 2 to 3 containing no phosphate compound and alkyl phosphate.
Claims (6)
1. A thermal runaway inhibitor for a nonaqueous electrolyte electricity storage device, which is composed of a phosphate ester compound represented by the following general formula (1),
the nonaqueous electrolyte electricity storage device has: a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and a nonaqueous electrolyte, the thermal runaway being thermal runaway caused by an internal short circuit of a nonaqueous electrolyte storage device,
in the formula (1), R1～R4Each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, X1Represents a group represented by the general formula (2) or the general formula (3), a represents 0 or a number of 1 to 4,
in the formula (2), R5～R8Each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, X2Represents a direct bond, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a group represented by the following general formula (4), b represents a number of 0 or 1, and represents a bond,
in the formula (4), R9～R10Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 2 carbon atoms or R9And R10A hydrocarbon group having 5 to 12 carbon atoms formed by crosslinking, which represents a bonding bond,
in the formula (3), R11～R14Each independently represents a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluoroalkyl group having 1 to 2 carbon atoms, and represents a bond.
2. The thermal runaway inhibitor of claim 1,
a in the general formula (1) represents a number of 1 to 4.
3. A method of suppressing thermal runaway caused by an internal short circuit of a nonaqueous electrolyte electricity storage apparatus, comprising: the thermal runaway inhibitor according to claim 1 or 2, which is incorporated in the nonaqueous electrolyte in an amount of 0.01 to 10% by mass based on the total amount of the nonaqueous electrolyte.
4. The method of suppressing thermal runaway caused by an internal short circuit of a nonaqueous electrolyte electrical storage device according to claim 3,
the nonaqueous electrolyte is a nonaqueous electrolyte in which an organic solvent is used as a solvent.
5. Use of the thermal runaway inhibitor described in claim 1 or 2 for inhibiting thermal runaway caused by an internal short circuit of a nonaqueous electrolyte electrical storage device,
the thermal runaway inhibitor is added to the nonaqueous electrolyte in an amount of 0.01 to 10 mass% based on the total amount of the nonaqueous electrolyte.
6. The use according to claim 5, wherein,
the nonaqueous electrolyte is a nonaqueous electrolyte in which an organic solvent is used as a solvent.
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| JP2019003799A (en) * | 2017-06-14 | 2019-01-10 | 三菱ケミカル株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery |
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| JP4092757B2 (en) * | 1997-12-26 | 2008-05-28 | ソニー株式会社 | Non-aqueous electrolyte secondary battery |
| JP3394020B2 (en) | 2000-06-29 | 2003-04-07 | 株式会社東芝 | Lithium ion secondary battery |
| JP3953026B2 (en) | 2003-12-12 | 2007-08-01 | 松下電器産業株式会社 | Electrode plate for lithium ion secondary battery, lithium ion secondary battery and method for producing the same |
| KR100574328B1 (en) * | 2003-12-30 | 2006-04-26 | 제일모직주식회사 | Nonqueous Electrolyte for Battery |
| KR100670448B1 (en) | 2004-05-31 | 2007-01-16 | 삼성에스디아이 주식회사 | Electrolyte for lithium ion secondary battery and Lithium ion secondary battery comprising the same |
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| US8163422B2 (en) | 2006-07-13 | 2012-04-24 | Daikin Industries, Ltd. | Electrochemical device |
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