JP4190162B2 - Nonaqueous electrolyte, secondary battery using the same, and additive for electrolyte - Google Patents

Nonaqueous electrolyte, secondary battery using the same, and additive for electrolyte Download PDF

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JP4190162B2
JP4190162B2 JP2001151863A JP2001151863A JP4190162B2 JP 4190162 B2 JP4190162 B2 JP 4190162B2 JP 2001151863 A JP2001151863 A JP 2001151863A JP 2001151863 A JP2001151863 A JP 2001151863A JP 4190162 B2 JP4190162 B2 JP 4190162B2
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carbonate
electrolytic solution
electrolyte
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lithium
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JP2002329528A (en
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千穂 平野
剛史 林
昭男 檜原
達麗 石田
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三井化学株式会社
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Description

[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a nonaqueous electrolytic solution having excellent life characteristics, a secondary battery using the same, and an additive for electrolytic solution. Furthermore, the present invention relates to a non-aqueous electrolyte having excellent life characteristics, a high flash point and excellent safety, a secondary battery using the same, and an additive for electrolyte. More specifically, the present invention relates to a nonaqueous electrolytic solution suitable for a lithium secondary battery containing unsaturated sultone, a secondary battery using the same, and an additive for electrolytic solution.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
  A battery using a non-aqueous electrolyte is widely used as a power source for consumer electronic devices because of its high voltage and high energy density and high reliability such as storage.
[0003]
  As such a battery, there is a non-aqueous electrolyte secondary battery, the representative of which is a lithium battery. As an electrolytic solution used therefor, an aprotic organic solvent, LiBF4, LiPF6, LiClO4, LiAsF6, LiCF3SO3, Li2SiF6A solution in which Li electrolyte is mixed is used (Jean-Paul Gabano, “Lithium Battery”, ACADEMIC PRESS (1983)).
[0004]
  As representatives of aprotic organic solvents, carbonates are known, and use of various carbonate compounds such as ethylene carbonate, propylene carbonate, and dimethyl carbonate has been proposed (Japanese Patent Laid-Open Nos. Hei 4-184872, Hei 10-27625). Issue). Many other sulfur-based solvents have been proposed as other aprotic solvents that can be used. For example, cyclic sulfone (JP 57-187878, JP 61-16478), chain sulfone (JP 3-152879, JP 8-241732), sulfoxide (JP 57-141878). No., JP 61-16478, etc.), sultones (JP 63-102173), sulfites (JP 61-64080) and the like. In addition, the use of esters (Japanese Patent Laid-Open Nos. 4-14769 and 4-284374) and aromatic compounds (Japanese Patent Laid-Open No. 4-249870) has been proposed.
[0005]
  One of the mainstream lithium secondary batteries is a lithium ion secondary battery. This battery includes a negative electrode made of an active material capable of inserting and extracting lithium, a positive electrode made of a composite oxide of lithium and a transition metal, an electrolytic solution, and the like.
[0006]
  As the negative electrode active material for lithium ion secondary batteries, many carbon materials capable of occluding and releasing lithium are used. Particularly, highly crystalline carbon such as graphite has a flat discharge potential and a high true density. In addition, it has a feature such as good filling properties, and is adopted as a negative electrode active material for most of the lithium ion secondary batteries currently on the market.
[0007]
  In addition, the electrolyte includes a mixed solvent of a high dielectric constant carbonate solvent such as propylene carbonate and ethylene carbonate and a low viscosity carbonate solvent such as diethyl carbonate, methyl ethyl carbonate, and dimethyl carbonate, and LiBF.4, LiPF6, LiN (SO2CF3)2And LiN (SO2CF2CF3)2A solution in which a Li electrolyte such as is mixed is used.
[0008]
  However, when highly crystalline carbon such as graphite is used for the negative electrode, it is necessary to suppress the problem that the reductive decomposition reaction of the electrolytic solution occurs on the graphite negative electrode. For example, an electrolytic solution using propylene carbonate or 1,2-butylene carbonate as a high-dielectric-constant carbonate solvent undergoes severe reductive decomposition of the solvent with exfoliation of the graphite edge surface during the initial charge. The insertion reaction of lithium ions, which are active materials, into graphite is less likely to proceed. As a result, it is known that the initial charge / discharge efficiency is lowered and the energy density of the battery is lowered (J. Electrochem. Soc., 146 (5) 1664-1671 (1999), etc.).
[0009]
  As an attempt to solve this problem, as a non-aqueous solvent having a high dielectric constant used in an electrolytic solution, ethylene carbonate that is solid at room temperature but hardly undergoes a reductive decomposition reaction continuously, or ethylene carbonate and propylene are used. A proposal using a mixed solvent of carbonate is known (J. Electrochem. Soc., 146 (5) 1664-1671 (1999)). In addition, even when ethylene carbonate is used, it is known that a reductive decomposition reaction of a small amount of electrolyte continuously occurs on the negative electrode surface (J. Electrochem. Soc., 147 (10) 3628-3632 (2000) J. Electrochem. Soc., 146 (11) 4014-4018 (1999), J. Power Sources 81-82 (1999) 8-12) It is conceivable that the capacity of the battery decreases when the battery is stored at.
[0010]
  Therefore, as an attempt to further suppress the reductive decomposition reaction of the solvent on the negative electrode, it has been reported many times that a compound that suppresses the reductive decomposition of the electrolytic solution is added to the electrolytic solution.
[0011]
  For example, by containing vinylene carbonate, the storage characteristics and cycle characteristics of the battery are improved (JP-A-5-13088, JP-A-6-52887, JP-A-7-122296, JP-A-9-347778). It has been reported that propylene carbonate which undergoes reductive decomposition on the edge surface of the graphite negative electrode can be used (10th Lithium Battery International Conference, Abstract No.286, Japanese Patent Application No. 10-150420).
[0012]
  As another example, the addition of sulfur acids has been reported. For example, ethylene sulfate (J. Electrochem. Soc. 146 (2) 470-472 (1999), 10th Lithium Battery International Conference, Abstract No. 289, Japanese Patent Laid-Open No. 11-73990) and SO3(J. Electrochem. Soc., 143, L195 (1996)) makes it possible to use propylene carbonate as a graphite negative electrode, and sultones (JP-A-11-162511, JP-A-11-339850, JP-A-2000- No. 3724, JP-A 2000-3725, JP-A 2000-123868, JP-A 2000-77098), sulfonic acid esters (JP-A 9-245834, JP-A 10-189041, JP-A 2000-133304). ) Has been proposed as an additive to improve cycle characteristics.
[0013]
  In addition, vinylene carbonate has a structure in which a carbon-carbon unsaturated bond is introduced into ethylene carbonate, which is a common solvent for graphite negative electrodes. Therefore, the carbon-carbon unsaturated bond is added to the above-mentioned general solvents and additives. Many attempts have been made to improve the content of the composition.
[0014]
  For example, a cyclic carbonate having a vinyl group (Japanese Patent Laid-Open No. 2000-40526), an acid anhydride containing a double bond (Japanese Patent Laid-Open No. 7-122297), and a sulfone containing a double bond (Japanese Patent Laid-Open No. 11-329494) , JP 2000-294278), esters in which a triple bond is introduced, benzenes, sulfones (JP 2000-195545), and esters containing a double bond (JP 11-273725, special (Kaihei 11-273724, JP-A-11-273723, JP-A-2000-182666).
[0015]
  Additives containing these carbon-carbon unsaturated bonds showed certain effects by making it possible to use propylene carbonate in the graphite negative electrode, but they are equivalent to vinylene carbonate in improving high-temperature storage characteristics and cycle characteristics. The above effects have not yet been achieved.
[0016]
  For example, in the study of the present inventor, the electrolytic solution to which the above-described sulfur-based compound containing a carbon-carbon unsaturated bond is added increases self-discharge due to electrolysis, particularly when the battery is stored at a high temperature, The desired effect is not manifested.
[0017]
  As described above, various types of electrolytic solutions have been studied, but no satisfactory one has been obtained yet, including vinylene carbonate. Reduction of the electrolytic solution that occurs when high-temperature storage and charge / discharge cycles are repeated There is a need for an electrolytic solution that further suppresses the decomposition reaction and further improves the deterioration of the load characteristics of the battery and the reduction of the battery capacity.
[0018]
  Therefore, the present inventor has intensively studied to solve the above problems, and has reached the present invention. According to the present invention, reductive decomposition of the electrolyte during high temperature storage is greatly suppressed, and as a result, self-discharge is small, deterioration of load characteristics and resistance is greatly suppressed, and a battery with a small amount of gas generation in the battery is obtained. I found out that I can.
[0019]
[Problems to be solved by the invention]
  In order to meet the above-mentioned demands, the present invention suppresses the decomposition reaction of the solvent on the negative electrode, and suppresses battery capacity reduction, gas generation, and battery load characteristics even when stored at high temperatures. An object of the present invention is to provide a non-aqueous electrolyte. It is another object of the present invention to provide a non-aqueous electrolyte having excellent life characteristics, high flash point and excellent safety. It is another object of the present invention to provide a non-aqueous electrolyte that gives the battery excellent load characteristics and low temperature characteristics. An object of this invention is to provide the secondary battery containing this non-aqueous electrolyte. Furthermore, an object of this invention is to provide the additive for electrolyte solutions which provides such a function to electrolyte solution.
[0020]
[Means for Solving the Problems]
  The present inventionA nonaqueous electrolytic solution containing an unsaturated sultone, a nonaqueous solvent and an electrolyte, wherein the unsaturated sultone is a compound represented by the following general formula (1), and the amount of unsaturated sultone added is a nonaqueous electrolytic solution Non-aqueous electrolyte which is 0.001-10 mass% with respect to the wholeI will provide a.
[Formula 4]
Where R1~ R4Is a hydrocarbon group that may contain hydrogen, fluorine, or fluorine having 1 to 12 carbon atoms, and n is an integer of 0 to 3.
[0021]
  A nonaqueous electrolytic solution in which the nonaqueous solvent is a cyclic aprotic solvent and / or a chain aprotic solvent is a preferred embodiment of the present invention.
[0022]
  A non-aqueous electrolyte in which the non-aqueous solvent is γ-butyrolactone or a mixture of γ-butyrolactone and at least one selected from ethylene carbonate, propylene carbonate, butylene carbonate, sulfolane, and methyl sulfolane is preferred in the present invention. It is an aspect.
[0023]
  A nonaqueous electrolytic solution further containing a vinylene carbonate derivative represented by the following general formula (3) is a preferred embodiment of the present invention.
[Chemical formula 5]
(R5, R6Is hydrogen, a methyl group, an ethyl group, or a propyl group. )
[0024]
  The non-aqueous electrolyte solution in which the electrolyte is a lithium salt is a preferred embodiment of the present invention.
[0025]
  The present invention also provides a nonaqueous solvent containing unsaturated sultone and γ-butyrolactone, LiPF6A nonaqueous electrolytic solution containing an electrolyte containing is provided.
[0026]
  Furthermore, the present invention relates to a metal lithium, a lithium-containing alloy, a metal or alloy that can be alloyed with lithium, an oxide that can be doped / undoped with lithium ions, and a lithium-ion doped / undoped material as a negative electrode active material. A transition metal oxide, a transition metal sulfide, a negative electrode including at least one selected from possible transition metal nitrides, carbon materials capable of doping and dedoping lithium ions, or mixtures thereof; Provided is a lithium secondary battery comprising a positive electrode including at least one selected from a composite oxide of lithium and a transition metal, a conductive polymer material, and a carbon material, and the non-aqueous electrolyte.
[0027]
  Furthermore, the present invention providesAboveProvided is an electrolyte additive comprising an unsaturated sultone.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
  The non-aqueous electrolyte according to the present invention, the non-aqueous electrolyte secondary battery using the non-aqueous electrolyte, and the additive for the electrolyte will be specifically described.
  The nonaqueous electrolytic solution of the present invention is a nonaqueous electrolytic solution containing unsaturated sultone. A preferred embodiment of the present invention is a nonaqueous electrolytic solution containing unsaturated sultone, a nonaqueous solvent and an electrolyte. The present invention also provides a non-aqueous electrolyte secondary battery using the non-aqueous electrolyte, and the present invention also provides an electrolyte additive comprising an unsaturated sultone having a specific structure.
[0029]
Unsaturated sultone
  The unsaturated sultone of the present invention is a sulfonic acid ester having a carbon-carbon unsaturated bond in the ring. Preferable examples of the unsaturated sultone of the present invention include unsaturated sultone having a specific structure represented by the following general formula (1).
[Chemical 6]
  Where R1~ R4Is a hydrocarbon group that may contain hydrogen, fluorine, or fluorine having 1 to 12 carbon atoms, and n is an integer of 0 to 3.
[0030]
  As n, all of n = 0 to 3 are effective, but n = 1 or 2 is preferable, and n = 1 is more preferable.
[0031]
  Specific examples of the hydrocarbon group which may contain fluorine having 1 to 12 carbon atoms include methyl group, ethyl group, vinyl group, ethynyl group, propyl group, isopropyl group, 1-propenyl group, 2-propenyl group, 1 -Propynyl, 2-propynyl, butyl, sec-butyl, t-butyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-2-propenyl, 1-methylenepropyl Group, 1-methyl-2-propenyl group, 1,2-dimethylvinyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl Group, 1-methyl-2-methylpropyl group, 2,2-dimethylpropyl group, phenyl group, methylphenyl group, ethylphenyl group, vinylphenyl group, ethynylphenyl group, hexyl group, cyclohexyl group, heptyl group, octyl group , Nonyl group, de Group, undecyl group, dodecyl group, difluoromethyl group, monofluoromethyl group, trifluoromethyl group, trifluoroethyl group, difluoroethyl group, pentafluoroethyl group, pentafluoropropyl group, tetrafluoropropyl group, perfluoro Butyl group, perfluoropentyl group, perfluorohexyl group, perfluorocyclohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, perfluoroundecyl group, perfluorododecyl group, fluoro Examples include a phenyl group, a difluorophenyl group, a trifluorophenyl group, a perfluorophenyl group, a trifluoromethylphenyl group, a naphthyl group, and a biphenyl group.
[0032]
  R1~ R4The number of carbon atoms is preferably from 1 to 12, but is preferably 4 or less, more preferably 2 or less, from the viewpoint of solubility in the electrolytic solution. Most preferred R1~ R4Is that they are both hydrogen.
[0033]
  Specific examples of the unsaturated sultone of the present invention represented by the above general formula (1) of the present invention include the following compounds.
[0034]
[Chemical 7]
[0035]
[Chemical 8]
[0036]
  Among these, the most preferred compound is 1,3-propene sultone represented by the following formula (2).
[Chemical 9]
[0037]
  This compound can be synthesized by a method described in the following literature.
Angew.Chem./70.Jahrg.1958/Nr.16, Ger.Pat. 1146870 (1963) (CA5911259 (1963)), Can.J.Chem.48, 3704 (1970), Synlett, 1411 (1988), Chem. Commun. 611 (1997), Tetrahedron55, 2245 (1999)
[0038]
  The electrolyte solution to which the unsaturated sultone of the present invention is added has a high effect of suppressing the reductive decomposition reaction of the electrolyte solution on the negative electrode, suppresses battery capacity reduction during high-temperature storage tests and cycle tests, and helps to decompose the electrolyte solution. The accompanying gas generation is suppressed. In addition, although the action is unknown, it suppresses the increase in the interface impedance of the positive electrode during the high temperature storage test and the cycle test, thereby suppressing the deterioration of the load characteristics. The unsaturated sultone of the present invention is effective as an additive for an electrolytic solution, and the additive for an electrolytic solution comprising the unsaturated sultone of the present invention can impart excellent characteristics to the electrolytic solution.
[0039]
  If the added amount of the unsaturated sultone of the present invention is too small, the effect may be hardly exhibited, and if it is too much, the interface impedance of the negative electrode may be increased. Therefore, the addition amount (content in the electrolyte solution) of the unsaturated sultone of the present invention to the electrolyte solution is 0.0001 with respect to the entire electrolyte solution.mass% -30mass% Is preferred, 0.001mass% -10mass% Is more preferable, 0.1mass% -7mass% Is more preferable, 0.2mass% ~ 5mass% Is particularly preferred.
[0040]
  Since the unsaturated sultone of the present invention is presumed to exhibit an effect by forming a passive film that prevents reductive decomposition of the electrolyte on the negative electrode surface, the addition amount is the surface area of the negative electrode active material of the battery and the electrolyte contained in the battery It may be determined from the amount. When the addition amount is too small, a sufficient passive film is not formed, and when the addition amount is too large, the interface impedance of the negative electrode active material may be excessively increased.
[0041]
  From this viewpoint, the unsaturated sultone of the present invention is 0.1 mg / m 2 per BET surface area of the negative electrode active material.2~ 100mg / m2Is preferred, 0.5 mg / m2~ 50mg / m2Is more preferable, 1 mg / m2~ 20mg / m2Is more preferable, 2 mg / m2-10 mg / m2Is particularly preferred.
[0042]
  In this case, the amount of the unsaturated sultone of the present invention added to the electrolytic solution is determined in consideration of the electrolytic solution and negative electrode active material amount ratio used in the battery, and the BET surface area of the negative electrode active material.
[0043]
  The amount ratio of the electrolytic solution and the negative electrode active material, the BET surface area of the negative electrode seems to be different depending on the battery, so it is not possible to set a preferable range of addition amount per electrolytic solution, but in general, as described above, 0.0001 to the total electrolytemass% -30mass% Is preferred, 0.001mass% -10mass% Is more preferable, 0.1mass% -7mass% Is more preferable, 0.2mass% ~ 5mass% Is particularly preferred.
[0044]
Non-aqueous solvent
  The non-aqueous solvent used in the present invention can be selected as appropriate, and in particular, it preferably comprises a cyclic aprotic solvent and / or a chain aprotic solvent.
[0045]
  Examples of the cyclic aprotic solvent include cyclic carbonates such as ethylene carbonate, cyclic carboxylic acid esters such as γ-butyrolactone, cyclic sulfones such as sulfolane, and cyclic ethers such as dioxolane. Examples of the solvent include a chain carbonate such as dimethyl carbonate, a chain carboxylate such as methyl propionate, a chain ether such as dimethoxyethane, and a chain phosphate such as trimethyl phosphate. .
  These aprotic solvents may be used alone or in combination of two or more.
[0046]
  In the case where the load characteristics and low temperature characteristics of the battery are particularly intended to be improved, it is desirable that the non-aqueous solvent is a combination of a cyclic aprotic solvent and a chain aprotic solvent. Furthermore, in view of the electrochemical stability of the electrolytic solution, it is most preferable to apply a cyclic carbonate to the cyclic aprotic solvent and a chain carbonate to the chain aprotic solvent.
[0047]
  Also, the conductivity of the electrolyte solution related to the charge / discharge characteristics of the battery can be increased by a combination of a cyclic carboxylic acid ester and a cyclic carbonate and / or a chain carbonate.
[0048]
  Specific examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate and the like. In particular, ethylene carbonate and propylene carbonate having a high dielectric constant are preferably used. In the case of a battery using graphite as the negative electrode active material, ethylene carbonate is particularly preferable. Moreover, you may use these cyclic carbonates in mixture of 2 or more types.
[0049]
  Specific examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, dipropyl carbonate, methyl butyl carbonate, dibutyl carbonate, ethyl propyl carbonate, methyl trifluoroethyl carbonate, and the like. It is done. In particular, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate having low viscosity are preferably used. These chain carbonates may be used as a mixture of two or more.
[0050]
  Specific examples of cyclic carboxylic acid esters include γ-butyrolactone, γ-valerolactone, δ-valerolactone, or alkyl-substituted products such as methyl γ-butyrolactone, ethyl γ-valerolactone, and ethyl δ-valerolactone. be able to.
[0051]
  Specific combinations of cyclic carbonate and chain carbonate include ethylene carbonate and dimethyl carbonate, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate, propylene carbonate and dimethyl carbonate, propylene carbonate and methyl ethyl carbonate, propylene carbonate and diethyl Carbonate, ethylene carbonate and propylene carbonate and dimethyl carbonate, ethylene carbonate and propylene carbonate and methyl ethyl carbonate, ethylene carbonate and propylene carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl Carbonate, ethylene carbonate and methyl ethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate and diethyl carbonate, ethylene carbonate and propylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and propylene carbonate, dimethyl carbonate and diethyl carbonate, Examples thereof include ethylene carbonate, propylene carbonate, methyl ethyl carbonate and diethyl carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate.
[0052]
  The mixing ratio of cyclic carbonate and chain carbonate ismassExpressed as a ratio, the cyclic carbonate: chain carbonate is 5:95 to 80:20, more preferably 10:90 to 70:30, and particularly preferably 15:85 to 55:45. By setting such a ratio, the increase in the viscosity of the electrolyte can be suppressed and the degree of dissociation of the electrolyte can be increased, so that the conductivity of the electrolyte related to the charge / discharge characteristics of the battery can be increased. The solubility of can be further increased. Therefore, since it can be set as the electrolyte solution excellent in the electrical conductivity in normal temperature or low temperature, the load characteristic of the battery from normal temperature to low temperature can be improved.
[0053]
  Specific examples of combinations of cyclic carboxylic acid esters and cyclic carbonates and / or chain carbonates include γ-butyrolactone and ethylene carbonate, γ-butyrolactone and ethylene carbonate and dimethyl carbonate, and γ-butyrolactone and ethylene carbonate and methylethyl. Carbonate, γ-butyrolactone and ethylene carbonate and diethyl carbonate, γ-butyrolactone and propylene carbonate, γ-butyrolactone and propylene carbonate and dimethyl carbonate, γ-butyrolactone and propylene carbonate and methyl ethyl carbonate, γ-butyrolactone and propylene carbonate and diethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, γ-butyrolactone, Tylene carbonate and propylene carbonate and dimethyl carbonate, γ-butyrolactone and ethylene carbonate, propylene carbonate and methyl ethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate and diethyl carbonate, γ-butyrolactone, ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, γ-butyrolactone, ethylene carbonate, dimethyl carbonate and diethyl carbonate, γ-butyrolactone, ethylene carbonate, methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone and ethylene carbonate And professional Ren carbonate, dimethyl carbonate and methyl ethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate, γ-butyrolactone, ethylene carbonate, propylene carbonate, methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone and ethylene carbonate Propylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate, γ-butyrolactone and sulfolane, γ-butyrolactone and ethylene carbonate and sulfolane, γ-butyrolactone and propylene carbonate and sulfolane, γ-butyrolactone, ethylene carbonate, propylene carbonate and sulfolane, γ -Butyrolactone and sul Such as orchids and dimethyl carbonate.
[0054]
  The mixing ratio of the cyclic carboxylic acid ester in the non-aqueous solvent ismassExpressed as a ratio, it is 100 to 10%, more preferably 90 to 20%, and particularly preferably 80 to 30%. By setting it as such a ratio, the electroconductivity of the electrolyte solution relating to the charge / discharge characteristics of the battery can be increased.
[0055]
  In order to improve the flash point of the solvent in order to improve the safety of the battery, it is preferable to use a cyclic aprotic solvent as the non-aqueous solvent. A cyclic aprotic solvent may be used alone, or a plurality of kinds may be mixed and used. In addition, a cyclic aprotic solvent and a chain aprotic solvent may be used as a mixture. In this case, a chain aprotic solvent is used as a mixture. The mixing amount ofmassThe ratio is preferably less than about 20%.
[0056]
  Cyclic carboxylic acid esters such as γ-butyrolactone have a low vapor pressure, a low viscosity, and a high dielectric constant. For this reason, the viscosity of the electrolytic solution can be lowered without lowering the flash point of the electrolytic solution and the degree of dissociation of the electrolyte. For this reason, since it has the feature that the conductivity of the electrolytic solution, which is an index related to the discharge characteristics of the battery, can be increased without increasing the flammability of the electrolytic solution, when aiming to improve the flash point of the solvent, It is preferable to use a cyclic carboxylic acid ester as the cyclic aprotic solvent.
[0057]
  A preferable non-aqueous solvent for improving the flash point of the solvent may be a cyclic carboxylic acid ester alone, but a preferable mixture of a cyclic carboxylic acid ester and another cyclic aprotic solvent is preferable.
[0058]
  Examples of preferred combinations of a mixture of a cyclic carboxylic acid ester and another cyclic aprotic solvent include γ-butyrolactone and ethylene carbonate, γ-butyrolactone and propylene carbonate, γ-butyrolactone, ethylene carbonate and propylene carbonate, and γ-butyrolactone. And ethylene carbonate and sulfolane.
[0059]
  Other preferred specific examples when using a cyclic aprotic solvent when aiming to improve the flash point of the solvent for improving the safety of the battery include ethylene carbonate, propylene carbonate, sulfolane, N -1 type chosen from methyl oxazolidinone or a mixture thereof can be mentioned. Specific examples of the mixture include ethylene carbonate and propylene carbonate, ethylene carbonate and sulfolane, ethylene carbonate and propylene carbonate and sulfolane, and ethylene carbonate and N-methyloxazolidinone.
[0060]
  For the purpose of improving the flash point of the solvent for improving the safety of the battery, chain aprotic solvents that can be used in combination include chain carbonates, chain carboxylates, chain phosphorus Acid esters are exemplified, and chain carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diheptyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl butyl carbonate, and methyl heptyl carbonate are particularly preferable.
[0061]
  The nonaqueous electrolytic solution according to the present invention may contain a solvent other than the above as the nonaqueous solvent. Specific examples of other solvents include amides such as dimethylformamide, chain carbamates such as methyl-N, N-dimethylcarbamate, cyclic amides such as N-methylpyrrolidone, and N, N-dimethylimidazolidinone. Examples thereof include boron-containing compounds such as cyclic urea, trimethyl borate, triethyl borate, tributyl borate, trioctyl borate, trimethylsilyl borate, and polyethylene glycol derivatives represented by the following general formula. HO (CH2CH2O)aH, HO {CH2CH (CH3) O}bH, CH3O (CH2CH2O)cH, CH3O {CH2CH (CH3) O}dH, CH3O (CH2CH2O)eCH3, CH3O {CH2CH (CH3) O}fCH3, C9H19PhO (CH2CH2O)g{CH (CH3) O}hCH3(Ph is a phenyl group), CH3O {CH2CH (CH3) O}iCO {OCH (CH3) CH2}jOCH3(In the above formula, a to f are integers of 5 to 250, g to j are integers of 2 to 249, 5 ≦ g + h ≦ 250, and 5 ≦ i + j ≦ 250.)
[0062]
Other additives
  In the present invention, in addition to the unsaturated sultone of the present invention, by adding other additives together, it is possible to impart further excellent characteristics to the electrolytic solution.
[0063]
  As another additive that may be added in the present invention, selecting one having an action of suppressing electrolysis on the negative electrode by itself can further suppress the electrolysis on the negative electrode and further reduce the self-discharge of the battery. Can be suppressed. As a result, the effect that the load characteristics, high temperature storage characteristics, and cycle characteristics of the battery are improved is obtained.
[0064]
  As a compound having an action of suppressing electrolysis on the negative electrode, a vinylene carbonate derivative represented by the following general formula (3)
[Chemical Formula 10]
(R5, R6Is hydrogen, a methyl group, an ethyl group, or a propyl group. );
[0065]
Carboxylic anhydrides such as maleic anhydride, norbornene dicarboxylic anhydride, diglycolic acid, ethynyl phthalic anhydride, vinyl phthalic anhydride, sulfobenzoic anhydride; benzene disulfonic anhydride, dibenzene sulfonic anhydride, Phenylsulfonic acids such as benzenesulfonic acid methyl ester, o-, m-, p-benzenedisulfonic acid dimethyl ester, o-, m-, p-benzenedisulfonic acid dilithium salt; 1,3-propane sultone, 1,4- Examples include sultone comprising a saturated hydrocarbon substituent such as butane sultone.
[0066]
  Of these compounds, the vinylene carbonate derivative represented by the general formula (3) is most preferable.
[0067]
  Specific examples of the vinylene carbonate derivative represented by the general formula (3) include vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, propyl ethylene carbonate, dimethyl vinylene carbonate, diethyl vinylene carbonate, and dipropyl vinylene carbonate. The Of these, vinylene carbonate is most preferred.
[0068]
  When the above other additives are contained in the electrolyte together with the unsaturated sultone of the present invention, the ratio of the unsaturated sultone of the present invention to the other additive ismassThe ratio is preferably 1: 100 to 100: 1, more preferably 1:20 to 20: 1, and particularly preferably 1:10 to 20: 1. In particular, when the other additive is vinylene carbonate, the above ratio is preferable, and the most preferable ratio is 1: 5 to 20: 1. In addition, when the unsaturated sultone of the present invention and the above-mentioned other additives are included in the electrolytic solution, the total amount is 30 with respect to the entire electrolytic solution.mass% Or less is preferable.
[0069]
Non-aqueous electrolyte
  The nonaqueous electrolytic solution of the present invention is a nonaqueous electrolytic solution containing the unsaturated sultone of the present invention. More preferably, it comprises the unsaturated sultone of the present invention, a non-aqueous solvent, and an electrolyte. Any electrolyte can be used as long as it is normally used as an electrolyte for a non-aqueous electrolyte.
[0070]
  Specific examples of electrolytes include (C2H5)4NPF6, (C2H5)4NBF4, (C2H5)4NClO4, (C2H5)4NAsF6, (C2H5)4N2SiF6, (C2H5)4NOSO2CkF(2k + 1) (K = integer from 1 to 8), (C2H5)4NPFn(CkF(2k + 1))(6-n) Tetraalkylammonium salts such as (n = 1 to 5, k = 1 to 8), LiPF6, LiBF4, LiClO4, LiAsF6, Li2SiF6, LiOSO2CkF(2k + 1) (K = integer from 1 to 8), LiPFn(CkF(2k + 1))(6-n) And lithium salts such as (n = 1 to 5, k = 1 to 8). Moreover, the lithium salt shown by the following general formula can also be used. LiC (SO2R7) (SO2R8) (SO2R9), LiN (SO2OR10) (SO2OR11), LiN (SO2R12) (SO2OR13) (Where R7~ R13May be the same as or different from each other and are perfluoroalkyl groups having 1 to 8 carbon atoms. These lithium salts may be used alone or in combination of two or more.
[0071]
  Of these, lithium salts are particularly desirable, and LiPF6, LiBF4, LiOSO2CkF(2k + 1) (K = integer from 1 to 8), LiClO4, LiAsF6, LiN (SO2CkF(2k + 1))2 (K = integer from 1 to 8), LiPFn(CkF(2k + 1))(6-n)(N = 1 to 5, k = 1 to 8) is preferable.
[0072]
  In the electrolyte solution of the present invention, when a cyclic carboxylic acid ester such as γ-butyrolactone is used in combination as a nonaqueous solvent, LiPF is particularly used.6It is desirable to contain. LiPF6Since the degree of dissociation is high, the conductivity of the electrolytic solution can be increased, and the reductive decomposition reaction of the electrolytic solution on the negative electrode can be suppressed.
[0073]
  In the electrolytic solution of the present invention, LiPF6Can be used alone or LiPF6And other lithium salts are recommended. LiPF6As the electrolyte used in addition to the above, any electrolyte can be used as long as it is normally used as an electrolyte for a non-aqueous electrolyte. Specifically, among the specific examples of the lithium salt described above, LiPF6Other lithium salts can be exemplified.
[0074]
  LiPF6As a specific example of a combination of lithium and other lithium salt, LiPF6And LiBF4, LiPF6And LiN (SO2CkF(2k + 1))2 (K = integer from 1 to 8), LiPF6And LiBF4And LiN (SO2CkF(2k + 1))2(K = integer of 1 to 8).
[0075]
  LiPF in the lithium salt6The ratio is 100-1mass%, Preferably 100 to 10mass%, More preferably 100-50mass% Is desirable.
[0076]
  Such an electrolyte is preferably contained in the non-aqueous electrolyte at a concentration of 0.1 to 3 mol / liter, preferably 0.5 to 2 mol / liter.
[0077]
  The non-aqueous electrolyte in the present invention preferably contains the unsaturated sultone of the present invention, a non-aqueous solvent and an electrolyte as essential components, but if necessary, other additives and other solvents mentioned above are added. May be.
  In addition to the other additives described above, hydrogen fluoride, water, oxygen, nitrogen, and the like can be present in the electrolytic solution of the present invention.
[0078]
  In the case of using hydrogen fluoride as an additive, the method of adding to the electrolytic solution includes blowing a predetermined amount of hydrogen fluoride gas directly into the electrolytic solution. The lithium salt used in the present invention is LiPF.6And LiBF4In the case of a lithium salt containing fluorine such as, water may be added to the electrolytic solution using the reaction of water and the electrolyte shown in the following (formula 1), and may be generated in the electrolytic solution.
    LiMFn + H2O → LiPF(N-2)O + 2HF (Formula 1)
(However, M = P, B, etc., when M is P, n = 6, when M is B, n = 4)
[0079]
  The method of adding water to the electrolytic solution may be to add water directly to the electrolytic solution, or to add water into the battery electrode in advance and inject the electrolytic solution into the battery, and then electrolyze from the electrode. Water may be supplied into the liquid.
[0080]
  When water is added to the electrolyte and HF is indirectly generated in the electrolyte, two molecules of HF are generated almost quantitatively from one molecule of water, so the amount of water added matches the desired concentration of HF added. Calculate and add. Specifically, 0.45 times the desired HF amount (massRatio) of water.
[0081]
  As a compound that generates HF by utilizing the reaction between the electrolyte and water, a protic compound having strong acidity can be used in addition to water. Specific examples of such a compound include methanol, ethanol, ethylene glycol, propylene glycol, acetic acid, acrylic acid, maleic acid, 1,4-dicarboxy-2-butene, and the like. The amount added as hydrogen fluoride is 0.0001 to 0.7 with respect to the entire electrolyte.mass% Is preferred, 0.001 to 0.3mass% Is more preferable, 0.001-0.2mass% Is more preferable, 0.001 to 0.1mass% Is particularly preferred.
[0082]
  The non-aqueous electrolyte according to the present invention as described above is not only suitable as a non-aqueous electrolyte for a lithium secondary battery, but also a non-aqueous electrolyte for a primary battery and a non-aqueous electrolyte for an electrochemical capacitor. It can also be used as an electrolytic solution for electric double layer capacitors and aluminum electrolytic capacitors.
[0083]
Secondary battery
  The non-aqueous electrolyte secondary battery according to the present invention basically includes a negative electrode, a positive electrode, and the non-aqueous electrolyte, and usually includes a separator between the negative electrode and the positive electrode. ing.
[0084]
  The negative electrode active material constituting the negative electrode includes metal lithium, lithium-containing alloy, metal or alloy that can be alloyed with lithium, oxide that can be doped / undoped with lithium ion, and lithium ion doped / dedope. Any of the possible transition metal nitrides, carbon materials that can be doped / undoped with lithium ions, or mixtures thereof can be used.
[0085]
  Examples of metals or alloys that can be alloyed with lithium include silicon, silicon alloys, tin, and tin alloys. Examples of oxides that can be doped / undoped with lithium ions include tin oxide, silicon oxide, and transition metal oxides that can be doped / undoped with lithium ions.
[0086]
  Among these, carbon materials that can be doped / undoped with lithium ions are preferable. Such a carbon material may be carbon black, activated carbon, artificial graphite, natural graphite, or amorphous carbon, and may be in the form of a fiber, a sphere, a potato, or a flake.
[0087]
  Specific examples of the amorphous carbon material include hard carbon, coke, mesocarbon microbeads (MCMB) fired at 1500 ° C. or less, and mesophase pitch carbon fiber (MCF). Graphite materials include natural graphite, There is artificial graphite, and as the artificial graphite, graphitized MCMB, graphitized MCF and the like are used. In addition, as the graphite material, a material containing boron can be used, and the graphite material can be coated with a metal such as gold, platinum, silver, copper, or Sn, or can be coated with amorphous carbon or amorphous. A mixture of carbon and graphite can also be used. These carbon materials may be used alone or in combination of two or more.
[0088]
  As a carbon material, interplanar spacing d of (002) plane measured by X-ray analysis in particular.(002)Is preferably a carbon material having a true density of 1.70 g / cm.3The above-described graphite or a highly crystalline carbon material having properties close thereto is preferable. When such a carbon material is used, the energy density of the battery can be increased.
[0089]
  As the positive electrode active material constituting the positive electrode, FeS2, MoS2, TiS2, MnO2, V2O5Transition metal oxides or transition metal sulfides such as LiCoO2, LiMnO2, LiMn2O4, LiNiO2, LiNixCo(1-x)O2, LiNixCoyMn(1-xy)O2Examples include composite oxides composed of lithium and transition metals such as polyaniline, polythiophene, polypyrrole, polyacetylene, polyacene, conductive polymer materials such as dimercaptothiadiazole / polyaniline composites, and carbon materials such as fluorinated carbon and activated carbon. It is done.
[0090]
  Among these, a composite oxide composed of lithium and a transition metal is particularly preferable. The positive electrode active material may be used alone or in combination of two or more. Since the positive electrode active material usually has insufficient conductivity, it is used with a conductive auxiliary agent to constitute the positive electrode. Examples of the conductive aid include carbon materials such as carbon black, amorphous whiskers, and graphite.
[0091]
  The separator is a film that electrically insulates the positive electrode and the negative electrode and transmits lithium ions, and examples thereof include a porous film and a polymer electrolyte. A microporous polymer film is preferably used as the porous film, and examples of the material include polyolefin, polyimide, polyvinylidene fluoride, and polyester. In particular, a porous polyolefin film is preferable, and specifically, a porous polyethylene film, a porous polypropylene film, or a multilayer film of a porous polyethylene film and polypropylene can be exemplified. On the porous polyolefin film, other resin excellent in thermal stability may be coated.
[0092]
  Examples of the polymer electrolyte include a polymer in which a lithium salt is dissolved, a polymer swollen with an electrolytic solution, and the like. The electrolytic solution of the present invention may be used for the purpose of obtaining a polymer electrolyte by swelling a polymer.
[0093]
  Such a nonaqueous electrolyte secondary battery can be formed in a cylindrical shape, a coin shape, a square shape, a film shape, or any other shape. However, the basic structure of the battery is the same regardless of the shape, and the design can be changed according to the purpose. Next, the structures of the cylindrical and coin-type batteries will be described. The negative electrode active material, the positive electrode active material, and the separator constituting each battery are commonly used.
[0094]
  For example, in the case of a cylindrical non-aqueous electrolyte secondary battery, a negative electrode obtained by applying a negative electrode active material to a negative electrode current collector such as a copper foil, and a positive electrode active material applied to a positive electrode current collector such as an Al foil The positive electrode formed is wound through a separator into which a non-aqueous electrolyte is injected, and is housed in a battery can in a state where insulating plates are placed above and below the wound body.
[0095]
  The non-aqueous electrolyte secondary battery according to the present invention can also be applied to a coin-type non-aqueous electrolyte secondary battery. In a coin-type battery, a disc-shaped negative electrode, a separator into which a non-aqueous electrolyte is injected, a disc-shaped positive electrode, and a spacer plate made of stainless steel or aluminum, if necessary, are stacked in this order on the coin-type battery can. It is stored.
[0096]
【Example】
  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
[0097]
(Examples 1-6 and Reference Example 1)
1. Fabrication of coin-type battery
<Preparation of non-aqueous electrolyte>
  Ethylene carbonate (EC) and methyl ethyl carbonate (MEC) are converted into EC: MEC = 4: 6 (massRatio) and then the electrolyte LiPF6Was dissolved in a non-aqueous solvent to prepare a non-aqueous electrolyte so that the electrolyte concentration was 1.0 mol / liter. Next, for this non-aqueous solvent, 1,3-propene sultone 0.5 as an additive, respectively.mass% (Example 1), 1.0mass% (Example 2), 1.5mass% (Example 3), 2.0mass% (Example 4), 2.5mass% (Example 5) 3.0mass% (Example 6) was added to obtain a nonaqueous electrolytic solution of the present invention. Moreover, the case where the addition of the additive was omitted was referred to as Reference Example 1 (blank).
[0098]
<Production of negative electrode>
  Natural graphite (LF-18A made by Chuetsu Graphite) 87massPart and binder of polyvinylidene fluoride (PVDF) 13massParts were mixed and dispersed in N-methylpyrrolidinone as a solvent to prepare a natural graphite mixture slurry. Next, this negative electrode mixture slurry was applied to a negative electrode current collector made of a strip-shaped copper foil having a thickness of 18 μm and dried.
  This was compression molded and punched into a 14 mm disk shape to obtain a coin-shaped natural graphite electrode. The thickness of this natural graphite electrode mixture is 110 μm,massWas 20 mg per area of a circle with a diameter of 14 mm.
[0099]
<LiCoO2Production of electrodes>
  LiCoO2(Honjo FMC Energy Systems Co., Ltd. HLC-21) 90massPart and graphite 6 of conductive agentmassPart and acetylene black 1massPart and binder of polyvinylidene fluoride 3massParts were mixed and dispersed in N-methylpyrrolidone as a solvent, and LiCoO2A mixture slurry was prepared. This LiCoO2The mixture slurry was applied to an aluminum foil having a thickness of 20 μm and dried.
This is compression molded and punched out into a 13.5 mm disk, coin-shaped LiCoO2An electrode was obtained. This LiCoO2The thickness of the mixture is 90 μm,massWas 40 mg per area of a 13.5 mm diameter circle.
[0100]
<Production of battery>
  Natural graphite electrode with a diameter of 14 mm, LiCoO with a diameter of 13.5 mm2A separator made of an electrode and a microporous polypropylene film having a thickness of 25 μm and a diameter of 16 mm is placed in a 2032 size battery can made of stainless steel, a natural graphite electrode, a separator, LiCoO2Laminated in the order of electrodes. Thereafter, 0.03 ml of the non-aqueous electrolyte prepared above was injected into the separator, and an aluminum plate (thickness 1.2 mm, diameter 16 mm, and a spring was accommodated. Finally, via a polypropylene gasket, By crimping the battery can lid, a coin-type battery having a diameter of 20 mm and a height of 3.2 mm was produced while maintaining airtightness in the battery.
[0101]
3. Evaluation of battery characteristics
<Evaluation of high-temperature storage characteristics by battery>
  Using the coin-type battery manufactured as described above, this battery was charged under the condition of a constant current of 0.3 mA and a constant voltage of 4.2 V until the current value at a constant voltage of 4.2 V was 0.05 mA, Thereafter, discharging was performed under the condition of a constant current of 1 mA and a constant voltage of 3.0 V until the current value at a constant voltage of 3.0 V was 0.05 mA. Next, this battery was charged under the condition of a 1 mA constant current 3.85 V constant voltage until the current value at the 3.85 V constant voltage became 0.05 mA.
  Thereafter, the battery was stored (“aging”) in a 45 ° C. constant temperature bath for 7 days.
[0102]
  After aging, with a constant current / constant voltage condition of 1 mA and a termination condition of 0.05 mA at a constant voltage, charge / discharge of 4.2 V to 3.0 V is performed once (“low load discharge capacity”). ) Was measured. At this time, the resistance of the battery (“resistance after aging”) was determined from the change in battery voltage 2 minutes after the start of discharge.
  Next, after charging to 4.2 V under the same conditions, discharge at a constant current of 10 mA, and discharging is performed under the condition that the discharge is terminated when the battery voltage reaches 3.0 V (“high load discharge capacity”). ) Was measured. In Examples 20 to 22 and Reference Example 3, measurement was performed at 5 mA instead of 10 mA for constant current discharge. Then, the ratio of the high load discharge capacity to the low load discharge capacity at this time was determined, and this was used as the “load characteristic index after aging”.
[0103]
  After the battery was once discharged to 3.0 V, the capacity (“charge capacity”) when charged again to 4.2 V was measured, and then stored at 60 ° C. for 4 days (“high temperature storage”).
[0104]
  The capacity ("remaining capacity") when discharged to 3.0 V after high temperature storage was measured. In addition, “low load discharge capacity” and “high load discharge capacity” were measured by the same method as at the time of aging, and “load characteristic index after high temperature storage” was obtained. Further, “resistance after high temperature storage” corresponding to “resistance after aging” was measured.
[0105]
The results of the above examples were analyzed from the following indices.
  The ratio of the “load characteristic index after high temperature storage” to the “load characteristic index after aging” was defined as “load characteristic change rate”.
Load characteristic change rate = (“Load characteristic index after high-temperature storage” / “Load characteristic index after aging”) × 100 (%)
  The ratio of “resistance after high temperature storage” to “resistance after aging” was defined as “resistance change rate”.
  Resistance change rate = (“resistance after high temperature storage” / “resistance before high temperature storage (after aging)”) × 100 (%)
[0106]
  Further, as an index representing the self-discharge property of the battery, that is, the electrolysis property of the electrolytic solution, the difference between the charge capacity before aging after high temperature storage and the remaining capacity after high temperature storage (charge capacity-remaining capacity) was obtained. The ratio of the difference of the electrolyte with respect to the difference of the electrolyte (reference example 1, blank) when no additive was added was determined as “self-discharge ratio”.
  Self-discharge ratio = {(electrolyte charge capacity−remaining capacity) / (blank charge capacity−blank remaining capacity)} × 100 (%)
  Table 1 shows the measurement results of the evaluated battery characteristics.
[0107]
(Comparative Examples 1 to 13)
  In Example 1, 0.5% of 1,3-propene sultone was used as an additive in <Preparation of Nonaqueous Electrolyte>.massA coin-type battery was prepared in the same manner except that the additive shown in Table 1 was added in the addition amount shown in the same table, and its battery characteristics were measured.
The results are shown in Table 1.
[0108]
[Table 1]
[0109]
  From the above results, it can be seen that the electrolyte solution to which the 1,3-propene sultone of the present invention is added has excellent effects with respect to all of the self-discharge ratio, the load characteristics, and the resistance deterioration suppression with respect to the comparative example. .
[0110]
(Examples 7 to 15)
  In Example 1, in addition to 1,3-propene sultone as an additive in <Preparation of Nonaqueous Electrolyte>, vinylene carbonate was added and each was added in the same amount as shown in Table 2. A coin-type battery was produced and its battery characteristics were measured.
The results are shown in Table 2.
[0111]
[Table 2]
[0112]
  From the above results, the 1,3-propene sultone of the present invention shows an excellent effect even when used alone, but when compared with a constant addition amount to the electrolyte, when used in combination with vinylene carbonate, the self-discharge rate ratio It can be seen that the load characteristic and resistance deterioration suppressing effect can be maintained at a high level.
[0113]
(Reference Example 2)
  A laminated battery was produced and the amount of gas generated in the battery during the high temperature storage test was measured.
1. Fabrication of laminated battery
<Preparation of non-aqueous electrolyte>
  The nonaqueous electrolytic solution prepared in Reference Example 1 was used as the nonaqueous electrolytic solution.
[0114]
<Production of negative electrode>
  Natural graphite (LF-18A made by Chuetsu Graphite) 87massPart and binder of polyvinylidene fluoride (PVDF) 13massParts were mixed and dispersed in N-methylpyrrolidinone as a solvent to prepare a natural graphite mixture slurry. Next, this negative electrode mixture slurry was applied to a negative electrode current collector made of a strip-shaped copper foil having a thickness of 18 μm and dried. The natural graphite electrode mixture had a thickness of 110 μm. This was punched out to 85 mm × 50 mm, and a copper lead wire was attached.
[0115]
<LiCoO2Production of electrodes>
  LiCoO2(Honjo FMC Energy Systems Co., Ltd. HLC-21) 90massPart and graphite 6 of conductive agentmassPart and acetylene black 1massPart and binder of polyvinylidene fluoride 3massParts were mixed and dispersed in N-methylpyrrolidone as a solvent, and LiCoO2A mixture slurry was prepared. This LiCoO2The mixture slurry was applied to an aluminum foil having a thickness of 20 μm and dried. This was punched into 76 mm × 46 mm, and a platinum lead wire was attached.
[0116]
<Production of laminated battery>
  Natural graphite electrode with dimensions of 85mm x 50mm, LiCoO with dimensions of 76mm x 46mm2The electrodes were made to face each other through a separator made of a microporous polypropylene film having a width of 55 mm and a length of 110 mm. This electrode group is accommodated in a cylindrical bag made of an aluminum laminate film (manufactured by Showa Laminate) so that both the positive and negative lead wires are drawn from one open portion, and the lead wires are drawn first. The other side was heat sealed and closed.
  Next, after 1.4 ml of the non-aqueous electrolyte prepared as described above was injected into the electrode group and impregnated, the remaining open portion was heat-sealed to seal the electrode group in a bag, thereby obtaining a laminated battery.
[0117]
2. Measurement of gas generation during high-temperature storage with laminate battery
  Using the laminated battery produced as described above, this battery was charged under the condition of a 10 mA constant current of 4.2 V constant voltage until the current value at a constant voltage of 4.2 V was 0.05 mA, and then a constant current of 10 mA was used. The discharge was performed under the condition that the current was discharged and the discharge was terminated when the battery voltage reached 3.0V. Next, this battery was charged under the condition of a 10 mA constant current 3.85 V constant voltage until the current value at the 3.85 V constant voltage became 0.05 mA.
[0118]
  Thereafter, this battery was aged for 7 days in a 45 ° C. constant temperature bath.
After aging, the battery was discharged at a constant current of 10 mA, and the discharge was terminated when the battery voltage reached 3.0V. Next, this battery was charged under the condition of a constant current of 10 mA and a constant voltage of 4.2 V until the current value at a constant voltage of 4.2 V was 0.05 mA. This battery was stored at 85 ° C. for 3 days at a high temperature.
[0119]
  Immediately after preparation of the laminated battery and after storage at high temperature, the volume of the battery was measured, and the difference was taken as the gas generation amount. The results are shown in Table 3.
[0120]
(Example 16)
  A laminated battery was produced in the same manner as in Reference Example 2 except that the nonaqueous electrolyte prepared in Example 10 was used as the nonaqueous electrolyte, and the amount of gas generated during high-temperature storage was measured. The results are shown in Table 3.
[0121]
(Example 17)
  A laminated battery was produced in the same manner as in Reference Example 2 except that the nonaqueous electrolyte prepared in Example 1 was used as the nonaqueous electrolyte, and the amount of gas generated during high-temperature storage was measured. The results are shown in Table 3.
[0122]
(Example 18)
  A laminated battery was produced in the same manner as in Reference Example 2 except that the nonaqueous electrolyte prepared in Example 11 was used as the nonaqueous electrolyte, and the amount of gas generated during high-temperature storage was measured. The results are shown in Table 3.
[0123]
(Example 19)
  A laminated battery was produced in the same manner as in Reference Example 2 except that the nonaqueous electrolyte prepared in Example 3 was used as the nonaqueous electrolyte, and the amount of gas generated during high-temperature storage was measured. The results are shown in Table 3.
[0124]
(Comparative Example 14)
  As a non-aqueous electrolyte, 1,3-propene sultone 1.5 as an additive in <Preparation of non-aqueous electrolyte> in Example 3 was used.mass%, Instead of 1,3-propane sultone 1.5massA non-aqueous electrolyte prepared in the same manner except that% was added, a laminate battery was produced in the same manner as in Reference Example 2, and the amount of gas generated during high-temperature storage was measured.
The results are shown in Table 3.
[0125]
[Table 3]
[0126]
(Examples 20 to 22)
  In Example 1, ethylene carbonate (EC), γ-butyrolactone (γ-BL), and dibutyl carbonate (DBC) as nonaqueous solvents in <Preparation of Nonaqueous Electrolytic Solution>, EC: γ-BL: DBC = 30: 65: 5 (massRatio) and then as the electrolyte, LiPF6Was prepared so that the electrolyte concentration was 1 mol / liter, and then 1,3-propene sultone 1 was added as an additive to the non-aqueous solvent.mass% (Example 20), 1,3-propene sultone 2mass% (Example 21), 1,3-propene sultone 2mass% And vinylene carbonate 2massA coin-type battery was prepared in the same manner except that a non-aqueous electrolyte solution was obtained by adding a mixture of 20% (Example 22), and the battery characteristics were measured. The case where the addition of the additive was omitted was designated as Reference Example 3. The results are shown in Table 4.
[0127]
[Table 4]
[0128]
【The invention's effect】
  By using the electrolytic solution to which the unsaturated sultone of the present invention is added, non-aqueous electrolysis in which self-discharge is small, load characteristics and resistance deterioration are greatly suppressed, and gas generation in the battery is greatly reduced. A liquid secondary battery can be obtained.
  Moreover, the nonaqueous electrolyte secondary battery excellent also in the low temperature characteristic and load characteristic can be obtained with the composition specific nonaqueous solvent of the present invention.

Claims (23)

  1. A nonaqueous electrolytic solution containing an unsaturated sultone , a nonaqueous solvent and an electrolyte , wherein the unsaturated sultone is a compound represented by the following general formula (1), and the amount of unsaturated sultone added is a nonaqueous electrolytic solution A non-aqueous electrolyte solution of 0.001 to 10% by mass with respect to the whole.
    Here, R 1 to R 4 are hydrogen, fluorine, or a hydrocarbon group that may contain fluorine having 1 to 12 carbon atoms, and n is an integer of 0 to 3.
  2. Nonaqueous electrolytic solution according to claim 1, wherein the R 1 to R 4 are both hydrogen in the formula (1).
  3. Non-aqueous electrolyte according to claim 1 or 2, characterized in that said that n is 1 in the general formula (1).
  4. The non-aqueous electrolyte according to claim 1, wherein the unsaturated sultone is 1,3-propene sultone represented by the following formula (2).
  5. The nonaqueous electrolytic solution according to claim 1, wherein the nonaqueous solvent contains a cyclic aprotic solvent and / or a chain aprotic solvent.
  6. The nonaqueous electrolytic solution according to claim 5 , wherein the cyclic aprotic solvent is a cyclic carbonate, a cyclic carboxylic acid ester, a cyclic sulfone, or a mixture thereof.
  7. The non-aqueous electrolyte according to claim 6 , wherein the cyclic aprotic solvent is ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, sulfolane, or a mixture thereof.
  8. Claim aprotic solvent annular, characterized in that it is a γ- butyrolactone or γ- butyrolactone and ethylene carbonate, propylene carbonate, a mixture of the butylene carbonate, at least one selected from sulfolane and methyl sulfolane, 6 The non-aqueous electrolyte described in 1.
  9. The non-aqueous electrolytic solution according to claim 5 , wherein the chain aprotic solvent is a chain carbonate, a chain ester, or a mixture thereof.
  10. The non-aqueous electrolyte according to claim 9 , wherein the chain aprotic solvent is dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, or a mixture thereof.
  11. Mass ratio of the aprotic solvent of a cyclic aprotic solvent and a chain in the nonaqueous solvent is 15: 85-55: Non according to any one of claims 5-10, which is a 45 Water electrolyte.
  12. The nonaqueous electrolytic solution according to any one of claims 1 to 11 , further comprising a vinylene carbonate derivative represented by the following general formula (3).
    (R 5 and R 6 are hydrogen, a methyl group, an ethyl group, or a propyl group.)
  13. The non-aqueous electrolyte according to claim 12, wherein an addition ratio of the unsaturated sultone to the vinylene carbonate derivative represented by the general formula (3) is 1: 100 to 100: 1 by mass ratio.
  14. The nonaqueous electrolytic solution according to any one of claims 1 to 13 , wherein the electrolyte is a lithium salt.
  15. Lithium salt is LiPF 6, LiBF 4 , LiOSO 2 C k F (2k + 1) (k = 1 to 8 ) , LiClO 4 , LiAsF 6 , LiN (SO 2 C k F (2k + 1) ) 2 (k = 1 to 8) integer), LiPF n (C k F (2k + 1)) (6-n) (n = 1~5, claim, characterized in that k = at least one selected from an integer from 1 to 8) 14 The non-aqueous electrolyte described.
  16.   A nonaqueous electrolytic solution comprising a nonaqueous solvent containing unsaturated sultone and γ-butyrolactone and an electrolyte containing LiPF6.
  17. Lithium ion, lithium-containing alloy, metal or alloy that can be alloyed with lithium, oxides that can be doped / undoped with lithium ions, transition metal nitrides that can be doped / undoped with lithium ions , A negative electrode including at least one selected from a carbon material capable of doping and dedoping lithium ions, or a mixture thereof, and a transition metal oxide, transition metal sulfide, and a composite of lithium and transition metal as a positive electrode active material A lithium secondary battery comprising a positive electrode including at least one selected from an oxide, a conductive polymer material, and a carbon material, and the nonaqueous electrolytic solution according to any one of claims 1 to 16 .
  18. The lithium secondary battery according to claim 17 , wherein the negative electrode active material is a carbon material capable of being doped / undoped with lithium ions.
  19. Doping and dedoping of lithium ions as the negative electrode active material of carbon materials capable interplanar spacing in was measured by X-ray analysis (002) plane distance d (002) is characterized in the following der Turkey 0.340nm The lithium secondary battery according to claim 18 .
  20. The additive for lithium secondary battery electrolyte solution which consists of unsaturated sultone which is a compound represented by the said General formula (1) .
  21. The additive for electrolytic solution according to claim 20, wherein R 1 to R 4 in the general formula (1) are hydrogen.
  22. The additive for electrolytic solution according to claim 20 or 21 , wherein n is 1 in the general formula (1).
  23. The additive for electrolytic solution according to claim 20 , wherein the unsaturated sultone is 1,3-propene sultone represented by the formula (2).
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