JP4187959B2 - Non-aqueous electrolyte and secondary battery using the same - Google Patents

Non-aqueous electrolyte and secondary battery using the same Download PDF

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JP4187959B2
JP4187959B2 JP2001326630A JP2001326630A JP4187959B2 JP 4187959 B2 JP4187959 B2 JP 4187959B2 JP 2001326630 A JP2001326630 A JP 2001326630A JP 2001326630 A JP2001326630 A JP 2001326630A JP 4187959 B2 JP4187959 B2 JP 4187959B2
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carbonate
borate
non
electrolytic solution
lithium
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JP2003132946A (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 non-aqueous electrolyte excellent in charge / discharge characteristics and a secondary battery using the same. More specifically, the present invention relates to a nonaqueous electrolytic solution suitable for a lithium secondary battery containing a borate ester, and a secondary battery using the same.
[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 nonaqueous electrolyte secondary battery, and a typical example thereof is a lithium ion secondary battery. Non-aqueous electrolytes are widely used as electrolyte materials for lithium ion secondary batteries, and carbonate compounds having a high dielectric constant are known as non-aqueous solvents used therefor. More specifically, as a non-aqueous electrolyte, LiBF is mixed with a mixed solvent of a carbonate compound solvent having a high dielectric constant such as propylene carbonate or ethylene carbonate and a carbonate solvent having a low viscosity such as dimethyl carbonate or diethyl carbonate.4, LiPF6, LiClO4, LiAsF6, LiCF3SO3, LI2SiF6A solution in which an electrolyte such as the above is mixed has been proposed.
[0004]
  On the other hand, research on electrodes has been conducted with the aim of increasing the capacity of batteries, and carbon materials capable of inserting and extracting lithium are used as negative electrodes of lithium ion secondary batteries. In particular, highly crystalline carbon such as graphite has features such as a flat discharge potential, and is therefore adopted as a negative electrode material in many of the lithium ion secondary batteries currently on the market.
[0005]
  However, when highly crystalline carbon such as graphite is used for the negative electrode, if non-aqueous solvent for the electrolyte is propylene carbonate or 1,2-butylene carbonate, which is a high dielectric constant having a low freezing point, As a result, reductive decomposition reaction of lithium ion, which is the active material, becomes difficult to proceed into the graphite, resulting in a decrease in the initial charge / discharge efficiency and the Li ion conductivity of the electrolyte solution due to the decomposition product of the electrolyte solution. Or the load characteristics of the battery are reduced due to an increase in electrode interface resistance.
[0006]
  Therefore, as a non-aqueous solvent having a high dielectric constant used for the electrolyte, ethylene carbonate, which is solid at room temperature but hardly undergoes reductive decomposition reaction, can be used instead of propylene carbonate or mixed. Although attempts have been made to suppress the reductive decomposition reaction of non-aqueous solvents by doing so, it is not always sufficient. In addition, even when amorphous carbon is used for the negative electrode, a slight reductive decomposition reaction of the solvent occurs, and the battery load is reduced due to a decrease in Li ion conductivity of the electrolytic solution due to the decomposition product of the electrolytic solution and an increase in electrode interface resistance. Degradation of characteristics occurs.
[0007]
  For this reason, in order to further suppress the reductive decomposition reaction, it has been proposed to add various additives. (JP-A-5-13088, JP-A-6-52887, JP-A-63-102173, JP-A-11-162511, JP-A-11-3728)
[0008]
  Further, as an attempt to improve the load characteristics of the battery, mixing a low-viscosity chain solvent (Japanese Patent Laid-Open No. 10-27625) has been proposed in order to improve the ionic conductivity of the electrolytic solution.
[0009]
[Problems to be solved by the invention]
  An object of the present invention is to provide a nonaqueous electrolytic solution that suppresses an increase in interfacial resistance of an electrode, gives excellent load characteristics and low temperature characteristics to a battery, and gives excellent life characteristics.
  It is another object of the present invention to provide a secondary battery having excellent life characteristics using this non-aqueous electrolyte.
[0010]
[Means for Solving the Problems]
  The present inventionTrimethyl borate, triethyl borate, tripropyl borate, tributyl borate, tripentyl borate, diethyl methyl borate, tri (methoxyethyl) borate, dimethyl hydroxyborate, dimethyl monolithium borate and monomethyl diborate Alkyl borate esters selected from lithium salts and tri (trifluoroethyl) borate, methyl di (trifluoroethyl) borate, tri (trichloroethyl) borate, tri (tetrafluoroethyl) borate, tri (monofluoroborate) Fluoroethyl), tri (pentafluoropropyl) borate, tri (hexafluoropropyl) borate, tri (2-methyl-1,1,1,3,3,3-hexafluoropropyl) borate, triborate (2-Phenyl-1,1,1,3,3,3-hexafluoro Boric acid ester selected from the group consisting of halogen-containing boric acid ester selected from tripropyl (trifluoroethoxyethyl) borate and methyl di (trifluoroethoxyethyl) borate, 1,3-propane sultone, A sulfonyl group-containing compound selected from the group consisting of sultone selected from 4-butane sultone, 1,3-propene sultone, 1,4-butene sultone and 1,5-pentene sultone, and dimethyl benzenedisulfonate, Including non-aqueous solvent and electrolyteLithium secondary batteryProvide non-aqueous electrolyte.
[0011]
  The non-aqueous electrolyte is furtherSelected from vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, propyl ethylene carbonate, dimethyl vinylene carbonate, diethyl vinylene carbonate, dipropyl vinylene carbonate, fluoro vinylene carbonate and trifluoromethyl vinylene carbonateThe non-aqueous electrolyte containing a vinylene carbonate derivative is a preferred embodiment of the present invention..
[0012]
in frontThe above-mentioned non-aqueous electrolytic solution in which the non-aqueous solvent is a solvent comprising a cyclic aprotic solvent and / or a chain aprotic solvent is a preferred embodiment of the present invention.
[0013]
  The non-aqueous electrolyte solution in which the cyclic aprotic solvent is at least one solvent selected from cyclic carbonates and cyclic esters is a preferred embodiment of the present invention.
[0014]
  The non-aqueous electrolyte solution in which the chain aprotic solvent is at least one solvent selected from a chain carbonate and a chain ester is a preferred embodiment of the present invention.
[0015]
  The electrolyte is 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)The nonaqueous electrolytic solution which is at least one selected from (n = 1 to 5, k = 1 to 8) is a preferred embodiment of the present invention.
[0016]
  The present invention also includes the above non-aqueous electrolyte.lithiumA secondary battery is provided.
[0017]
  Furthermore, the present invention includes metallic lithium as a negative electrode active material, a lithium-containing alloy, a carbon material that can be doped / undoped with lithium ions, a tin oxide that can be doped / undoped with lithium ions, and a doped / undoped lithium ion. Transitions with possible negative electrode containing titanium oxide, niobium oxide or vanadium oxide, or silicon or tin that can be doped / undoped with lithium ion, and transition metal oxide, transition metal sulfide, lithium as positive electrode active material Provided is a lithium secondary battery comprising a positive electrode including any one of a metal complex oxide, a conductive polymer material, a carbon material, or a mixture thereof, and the non-aqueous electrolyte.
[0018]
  The lithium ion secondary battery in which the intercalation distance (d002) on the (002) plane measured by X-ray analysis is 0.340 nm or less is the carbon material that can be doped / undoped with lithium ions. This is a preferred embodiment of the invention.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
  The nonaqueous electrolyte solution according to the present invention and the nonaqueous electrolyte secondary battery using the nonaqueous electrolyte solution will be specifically described.
[0020]
  The nonaqueous electrolytic solution according to the present invention is a nonaqueous electrolytic solution containing a boric acid ester, a nonaqueous solvent, and an electrolyte.
  When the boric acid ester is contained in the electrolytic solution of the present invention, an increase in electrode interface resistance during initial charging is suppressed, and thus a desirable nonaqueous electrolytic solution is obtained. A non-aqueous electrolyte secondary battery using this non-aqueous electrolyte exhibits excellent load characteristics.
[0021]
                              Borate ester
  The borate esters used in the present invention are:Trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, tripentyl borate, diethyl methyl borate, tri (methoxyethyl) borate, dimethyl hydroxyborate, dimethyl monolithium borate and monomethyl diborate Alkyl borate esters selected from lithium salts and tri (trifluoroethyl) borate, methyl di (trifluoroethyl) borate, tri (trichloroethyl) borate, tri (tetrafluoroethyl) borate, tri (monofluoroborate) Fluoroethyl), tri (pentafluoropropyl) borate, tri (hexafluoropropyl) borate, tri (2-methyl-1,1,1,3,3,3-hexafluoropropyl) borate, triborate (2-Phenyl-1,1,1,3,3,3-hexafluoro Propyl), tri borate (trifluoroethoxy ethyl) and halogen-containing borate ester comprising a boric acid ester selected from the group selected from boric acid methyl di (trifluoroethoxy ethyl)Is.
[0022]
BookThe non-aqueous electrolyte of the inventionRecordIn addition to oxalate, non-aqueous solvent and electrolyte,Sultone selected from the group consisting of 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone, 1,4-butene sultone and 1,5-pentene sultone, and a sulfonyl group selected from the group consisting of dimethyl benzenedisulfonate ContainsCompounds can be included.
  Non-aqueous electrolyteContains sulfonyl groupWhen the compound is contained, an effect of suppressing an increase in interface resistance at the time of initial charge is enhanced. In addition, it is desirable not only during initial charging, but also because the increase in interface resistance after repeated use and storage at high temperatures is suppressed..
[0023]
  Contains sulfonyl groupThe amount of the compound added to the non-aqueous electrolyte is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight.
[0024]
                        Vinylene carbonate derivative
  The nonaqueous electrolytic solution of the present invention may further contain a vinylene carbonate derivative represented by the following general formula (3).
[0025]
  When the nonaqueous electrolytic solution of the present invention contains a vinylene carbonate derivative represented by the following general formula (3), in addition to further enhancing the effect of suppressing an increase in interface resistance during initial charging, a cycle test or The maintenance rate of the battery capacity during the high temperature storage test is improved.
[0026]
[Chemical 1]
[0027]
  Where R7And R8May be the same or different and are hydrogen or an organic group having 1 to 10 carbon atoms.
  Preferable examples of the organic group include a hydrocarbon group and a hetero atom-containing hydrocarbon group.
[0028]
  Examples of the hydrocarbon group include a saturated hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group, a double bond-containing hydrocarbon group such as a vinyl group and an allyl group, an ethynyl group, and a propargyl group. Examples thereof include unsaturated hydrocarbon groups such as a triple bond-containing hydrocarbon group.
[0029]
  Examples of the hetero atom of the hetero atom-containing hydrocarbon group include oxygen, nitrogen, sulfur, phosphorus and boron. Preferred examples of heteroatom-containing hydrocarbon groups include oxygen-containing hydrocarbon groups containing ether bonds, ester bonds, carbonate bonds, etc., such as methoxyethyl groups and methoxycarbonylethyl groups, and nitrogen-containing hydrocarbon groups containing amino groups, etc. Can be mentioned.
[0030]
  The organic group may be substituted with a halogen atom. Examples of the halogen element include fluorine, chlorine, bromine and the like, with fluorine being preferred. Examples of the organic group substituted with a halogen atom include a halogenated hydrocarbon group such as a trifluoroethyl group, a hydrocarbon group substituted with a halogen-containing group, and a halogenated heteroatom-containing hydrocarbon group. In particular, a halogenated hydrocarbon group is preferable.
[0031]
  As the organic group, a hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group having 1 to 10 carbon atoms is preferable.
[0032]
  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, dipropyl vinylene carbonate, fluoro vinylene carbonate, Examples thereof include trifluoromethyl vinylene carbonate. Of these, vinylene carbonate is preferred.
[0033]
  The amount of vinylene carbonate derivative added to the electrolytic solution is preferably 0.05 to 5% by weight with respect to the entire non-aqueous electrolytic solution.
[0034]
  The non-aqueous electrolyte containing the boric acid ester represented by the general formula (1), the compound represented by the general formula (2) and the vinylene carbonate derivative represented by the general formula (3) is a non-aqueous electrolyte of the present invention. This is a preferred embodiment of the electrolytic solution.
  A nonaqueous electrolytic solution containing the boric acid ester represented by the general formula (1) and the vinylene carbonate derivative represented by the general formula (3) is also a preferred embodiment of the nonaqueous electrolytic solution of the present invention.
[0035]
  Among these, a boric acid ester represented by the general formula (1), a non-aqueous electrolyte containing a compound represented by the general formula (2), and a vinylene carbonate derivative represented by the general formula (3) are included. A non-aqueous electrolyte is a more preferred embodiment.
[0036]
                                Non-aqueous solvent
  The nonaqueous electrolytic solution of the present invention has a configuration in which the compound described so far is contained in a solution obtained by dissolving an electrolyte in a nonaqueous solvent.
[0037]
  In the present invention, the non-aqueous solvent is preferably composed of a cyclic aprotic solvent and / or a chain aprotic solvent.
  Examples of the cyclic aprotic solvent include a cyclic carbonate such as ethylene carbonate, a cyclic ester such as γ-butyrolactone, and a cyclic ether such as dioxolane. The chain aprotic solvent includes a chain such as dimethyl carbonate. Examples thereof include chain carbonates, chain carboxylic acid esters such as methyl propionate, chain ethers such as dimethoxyethane, and chain phosphate esters such as trimethyl phosphate.
[0038]
  In the case where the load characteristics and low temperature characteristics of the battery are particularly intended to be improved, the non-aqueous solvent is preferably a combination of a cyclic aprotic solvent and a chain aprotic solvent. Furthermore, it is preferable to apply a cyclic carbonate to the cyclic aprotic solvent and a chain carbonate to the chain aprotic solvent from the electrochemical stability of the electrolytic solution.
[0039]
  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. Among them, 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 preferable. Two or more of these cyclic carbonates may be used as a mixture.
[0040]
  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. Can be. Among them, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate having a low viscosity are preferably used. These chain carbonates may be used as a mixture of two or more.
[0041]
  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.
[0042]
  The mixing ratio of the cyclic carbonate and the chain carbonate is expressed by weight ratio, and the cyclic carbonate: chain carbonate is 5:95 to 80:20, more preferably 10:90 to 70:30, and particularly preferably 15:85. ~ 55: 45.
[0043]
  By setting such a ratio, an increase in the viscosity of the electrolytic solution can be suppressed and the degree of dissociation of the electrolyte can be increased, so that the conductivity of the electrolytic solution related to the charge / discharge characteristics of the battery can be increased, and the solubility of the electrolyte Can be further enhanced. As a result, an electrolytic solution having excellent electrical conductivity from room temperature to low temperature can be obtained, so that the load characteristics of the battery from room temperature to low temperature can be improved.
[0044]
  In addition, to improve the flash point of the solvent to improve battery safety, use a cyclic aprotic solvent alone as the non-aqueous solvent, or mix a chain of aprotic solvents. It is desirable to limit the amount to less than 20% by weight with respect to the total non-aqueous solvent.
[0045]
  As the cyclic aprotic solvent in this case, it is particularly desirable to mix one kind or a mixture selected from ethylene carbonate, propylene carbonate, γ-butyrolactone, and methyloxazolinone. Specific examples of the solvent combination include ethylene carbonate and sulfolane, ethylene carbonate and γ-butyrolactone, ethylene carbonate and propylene carbonate, ethylene carbonate, propylene carbonate, and gamma butyrolactone.
[0046]
  When the amount of the chain aprotic solvent mixed is 20% or less by weight with respect to the total amount of the nonaqueous solvent, the chain aprotic solvent may be a chain carbonate, a chain carboxylate ester, a chain In particular, chain phosphates 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 preferable.
[0047]
  In the non-aqueous electrolyte solution according to the present invention, as the non-aqueous solvent, a solvent other than the above may be included. Specifically, as the other solvent, an amide such as dimethylformamide, methyl-N, N And chain carbamates such as -dimethylcarbamate, cyclic amides such as N-methylpyrrolidone, cyclic ureas such as N, N-dimethylimidazolidinone, and ethylene 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 {O (CH3) CHCH2}jOCH3(In the formula, a to f are integers of 5 to 250, g to j are integers of 2 to 249, 5 ≦ g + h ≦ 250, 5 ≦ i + j ≦ 250.)
                                Non-aqueous electrolyte
  The non-aqueous electrolyte solution of the present invention dissolves an electrolyte in a non-aqueous solvent and further contains the aforementioned compounds. Any electrolyte can be used as long as it is normally used as an electrolyte for a non-aqueous electrolyte.
[0048]
  As a specific example of the electrolyte, LiPF6, LiBF4, LiClO4, LiAsF6, Li2SiF6, LiC4F9SO3, LiC8F17SO3And lithium salts. Moreover, the lithium salt shown by the following general formula can also be used. LiOSO2R8, LiN (SO2R9) (SO2R10), LiC (SO2R11) (SO2R12) (SO2R13), LiN (SO2OR14) (SO2OR15) (Where R8~ R15May be the same as or different from each other, and are perfluoroalkyl groups having 1 to 6 carbon atoms). These lithium salts may be used alone or in combination of two or more.
[0049]
  Of these, in particular, LiPF6, LiBF4, LiOSO2R8, LiN (SO2R9) (SO2R10), LiC (SO2R11) (SO2R12) (SO2R13), LiN (SO2OR14) (SO2OR15) Is preferred.
[0050]
  Such an electrolyte is desirably contained in the non-aqueous electrolyte at a concentration of 0.1 to 3 mol / liter, preferably 0.5 to 2 mol / liter.
[0051]
  The non-aqueous electrolyte in the present invention contains the aforementioned compounds, a non-aqueous solvent and an electrolyte as essential components, but other additives may be added as necessary.
[0052]
  Other additives include carboxylic anhydrides such as maleic anhydride, norbornene dicarboxylic anhydride, diglycolic acid; unsaturated hydrocarbons such as vinyl ethylene carbonate, divinyl ethylene carbonate, methylene-1,2-ethylene carbonate Substituted cyclic carbonates; hydrogen fluoride and the like.
[0053]
  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, etc., water may be added to the electrolytic solution using the reaction of an active proton compound such as water and an electrolyte shown below, and may be generated in the electrolytic solution. .
[0054]
  LiMFn + H2O → LiPF(N-2)O + 2HF
(However, M represents P, B, etc., n = 6 when M = P, and n = 4 when M = B.)
[0055]
  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, it is preferable to add 0.45 times (weight ratio) water as desired.
[0056]
  Specific examples of other protic compounds include trifluoroacetic acid, methanol, ethanol, ethylene glycol, propylene glycol and the like.
[0057]
  The addition amount as hydrogen fluoride is 0.0001 to 0.7 wt%, preferably 0.001 to 0.3 wt%, more preferably 0.001 to 0.1 wt%.
[0058]
  The non-aqueous electrolyte according to the present invention is not only suitable as a non-aqueous electrolyte for a lithium ion secondary battery, but can also be used as a non-aqueous electrolyte for a primary battery.
[0059]
                                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.
[0060]
  Examples of the negative electrode active material constituting the negative electrode include metallic lithium, lithium alloy, carbon material capable of doping / dedoing lithium ions, tin oxide, niobium oxide or oxidation capable of doping / dedoping lithium ions. Vanadium, titanium oxide that can be doped / undoped with lithium ions, or silicon or tin that can be doped / undoped with lithium ions can be used. Among these, a carbon material that can dope / dedope lithium ions is preferable. Such a carbon material may be graphite or amorphous carbon, and activated carbon, carbon fiber, carbon black, mesocarbon microbeads, natural graphite and the like are used.
[0061]
  As the negative electrode active material, a carbon material having a (002) plane distance (d002) of 0.340 nm or less measured by X-ray analysis is particularly preferable, and the density is 1.70 g / cm.3The above-described graphite or a highly crystalline carbon material having properties close thereto is desirable. When such a carbon material is used, the energy density of the battery can be increased.
[0062]
  As the positive electrode active material constituting the positive electrode, MoS2TiS2, MnO2, V2O5Transition metal oxides or transition metal sulfides such as LiCoO2LiMnO2, LiMn2O4, LiNiO2, LiNixCo(1-x)O2, LiNixMnyCo(1-xy)O2Examples thereof include composite oxides composed of lithium and a transition metal such as polyaniline, polythiophene, polypyrrole, polyacetylene, polyacene, and dimercaptothiadiazole / polyaniline composite. Among these, a composite oxide composed of lithium and a transition metal is particularly preferable. When the negative electrode is lithium metal or a lithium alloy, a carbon material can also be used as the positive electrode. As the positive electrode, a mixture of lithium and transition metal composite oxide and a carbon material can be used.
[0063]
  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. As the porous film, a microporous polymer film is preferably used, and examples of the material include polyolefin, polyimide, and polyvinylidene fluoride. 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. 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.
[0064]
  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.
[0065]
  For example, in the case of a cylindrical non-aqueous electrolyte secondary battery, a negative electrode formed by applying a negative electrode active material to a negative electrode current collector and a positive electrode formed by applying a positive electrode active material to a positive electrode current collector are It winds through the separator which inject | poured the water electrolyte solution, and is accommodated in the battery can in the state which mounted the insulating board on the upper and lower sides of the wound body.
[0066]
  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 disk-shaped negative electrode, a separator, a disk-shaped positive electrode, and a stainless steel or aluminum plate are stored in a coin-type battery can in a state of being laminated in this order.
[0067]
【Example】
  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not restrict | limited at all by these Examples.
[0068]
(Example 17, Reference Examples 1-3)
1. Battery fabrication
<Preparation of non-aqueous electrolyte>
  Ethylene carbonate (EC) and methyl ethyl carbonate (MEC) are mixed in a ratio of EC: MEC = 4: 6 (weight ratio), 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, the additives shown in Table 1 were added to the non-aqueous electrolyte solution (100% by weight) at the ratio shown in Table 1.
[0069]
<Production of negative electrode>
  87 parts by weight of natural graphite (LF-18A made by Chuetsu Graphite) and 13 parts by weight of polyvinylidene fluoride (PVDF) as a binder 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, dried, compression-molded, punched into a 14 mm disk, and coin-shaped natural graphite. An electrode was obtained. The natural graphite electrode mixture had a thickness of 110 μm and a weight of 20 mg per area of a circle having a diameter of 14 mm.
[0070]
<LiCoO2Production of electrodes>
  LiCoO290 parts by weight (HLC-21 manufactured by Honjo FMC Energy Systems Co., Ltd.), 6 parts by weight of graphite as a conductive agent and 1 part by weight of acetylene black and 3 parts by weight of polyvinylidene fluoride as a binder were mixed. Dispersed in methylpyrrolidone and LiCoO2A mixture slurry was prepared.
  This LiCoO2The mixture slurry was applied to an aluminum foil with a thickness of 20 μm, dried, compression molded, and punched out to a diameter of 13 mm, and LiCoO2An electrode was produced.
This LiCoO2The thickness of the mixture was 90 μm, and the weight was 35 mg per area of a circle having a diameter of 13 mm.
[0071]
<Production of battery>
  Natural graphite electrode with a diameter of 14 mm, LiCoO with a diameter of 13 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 was poured into the separator, and an aluminum plate (thickness 1.2 mm, diameter 16 mm, and spring was accommodated. Finally, the battery can lid was passed through a polypropylene gasket. By crimping, a coin-type battery having a diameter of 20 mm and a height of 3.2 mm was produced while maintaining the airtightness in the battery.
[0072]
2. Evaluation of battery characteristics
<Measurement of initial battery characteristics>
(1) Measurement of initial low-load discharge capacity
  Using the coin-type battery produced as described above, this battery was charged under the condition of a constant current of 0.5 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 a condition of a constant current of 0.5 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. The discharge capacity of the coin-type battery at this time is referred to as “initial low-load discharge capacity”. The initial low load discharge capacity was around 4.5 mAh in any of the batteries.
[0073]
(2) Measurement of initial medium load discharge capacity
  Next, this battery was charged under the condition of a constant current of 3 mA and a constant voltage of 4.2 V until the current value at a constant voltage of 4.2 V reached 0.05 mA, and then the battery voltage was 3.0 V at a current of 5 mA. Discharged until The discharge capacity of the coin-type battery at this time is referred to as “initial medium load discharge capacity”.
[0074]
<Measurement of electrode interface resistance>
  After charging the coin-type battery to 4.2 V, the impedance at 0.2 Hz and 2500 Hz was measured, and the impedance value obtained by subtracting the impedance value at 2500 Hz from the impedance value at 0.2 Hz was defined as “electrode interface resistance”. .
[0075]
<Measurement of battery storage characteristics>
(1) Measurement of discharge capacity
  The battery was once discharged to 3 V, and charged under the condition of a 3 mA constant current of 4.1 V constant voltage until the current value at the time of 4.1 V constant voltage was 0.05 mA. The charge amount at this time was defined as “charge capacity before storage”.
  This battery was stored at 50 ° C. for 1 week, and then discharged under a condition of a constant current of 0.5 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. The discharge amount at this time was defined as “discharge capacity after storage”.
  The difference between “discharge capacity after storage” and “charge capacity before storage” was defined as “high-temperature storage self-discharge capacity” (“discharge capacity after storage” − “charge capacity before storage” = “high-temperature storage self-discharge capacity”).
[0076]
(2) Measurement of medium load discharge capacity after storage
  Next, this battery was charged under the condition of a constant current of 3 mA and a constant voltage of 4.2 V until the current value at a constant voltage of 4.2 V reached 0.05 mA, and then the battery voltage was 3.0 V at a current of 5 mA. Discharged until The discharge capacity of the coin-type battery at this time is referred to as “medium-load discharge capacity after storage”.
[0077]
  Example 17, Reference Examples 1-3The evaluation results of the battery characteristics are shown in Table 2.
[0078]
(Comparative Example 1)
  In <Preparation of Nonaqueous Electrolyte> in Example 1, a nonaqueous electrolyte was prepared in the same manner except that the addition of the additive was omitted. Using the obtained nonaqueous electrolyte, Example 1 and Similarly, batteries were prepared and battery characteristics were evaluated.
  The “electrode interface resistance” and “high temperature storage self-discharge capacity” measured in Comparative Example 1 are defined as “electrode interface resistance in blank” and “high temperature storage self-discharge capacity in blank”, respectively.
  The evaluation results of the battery characteristics are shown in Table 2.
[0079]
  The battery characteristics shown in Table 2 were evaluated using the following indices from the experimental results in Examples 1 to 10 and Comparative Example 1. In both cases, the unit is%.
“Electrode interface resistance ratio” = {“electrode interface resistance of battery using test electrolyte” / “electrode interface resistance in blank”} × 100
“Initial load characteristic index” = {“Initial load discharge capacity” / “Initial low load discharge capacity”} × 100
“Load characteristic maintenance ratio” = {“Medium load discharge capacity after storage” / “Initial medium load discharge capacity”} × 100
“Self-discharge ratio” = {“High-temperature storage self-discharge capacity of test electrolyte” / “High-temperature storage self-discharge capacity in blank”} × 100
[0080]
[Table 1]
[0081]
[Table 2]
[0082]
  From Table 2, Examples 1 to7It was found that even when any of these electrolytes was used, the initial interface resistance was smaller than that of the blank (Comparative Example 1), and a battery exhibiting excellent load characteristics was obtained.
[0083]
  From Table 2With the electrolyte of the present invention, highIt can be seen that a battery with little deterioration in load characteristics after storage at a high temperature can be obtained. It can be seen that when the electrolytic solution further contains a vinylene carbonate derivative represented by the general formula (3), deterioration of load characteristics and self-discharge after high-temperature storage are suppressed, and a battery exhibiting superior characteristics can be obtained.
[0084]
【The invention's effect】
  The present invention provides a non-aqueous electrolyte that is particularly suitable as an electrolyte for a lithium ion secondary battery.
  By using the non-aqueous electrolyte of the present invention, it is possible to obtain a non-aqueous electrolyte secondary battery with low initial electrode interface resistance and excellent load characteristics in initial characteristics or characteristics after storage at high temperature. it can.

Claims (14)

  1. Trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, tripentyl borate, diethyl methyl borate, tri (methoxyethyl) borate, dimethyl hydroxyborate, dimethyl monolithium borate and monomethyl diborate Alkyl borate esters selected from lithium salts and tri (trifluoroethyl) borate, methyl di (trifluoroethyl) borate, tri (trichloroethyl) borate, tri (tetrafluoroethyl) borate, tri (monofluoroborate) Fluoroethyl), tri (pentafluoropropyl) borate, tri (hexafluoropropyl) borate, tri (2-methyl-1,1,1,3,3,3-hexafluoropropyl) borate, triborate (2-Phenyl-1,1,1,3,3,3-hexafluoro Boric acid ester selected from the group consisting of halogen-containing boric acid ester selected from tripropyl (trifluoroethoxyethyl) borate and methyl di (trifluoroethoxyethyl) borate, 1,3-propane sultone, A sulfonyl group-containing compound selected from the group consisting of sultone selected from 4-butane sultone, 1,3-propene sultone, 1,4-butene sultone and 1,5-pentene sultone, and dimethyl benzenedisulfonate , a non-aqueous solvent, and an electrolyte A non-aqueous electrolyte for a lithium secondary battery .
  2. Further , it contains a vinylene carbonate derivative selected from vinylene carbonate, methyl vinylene carbonate, ethyl vinylene carbonate, propyl ethylene carbonate, dimethyl vinylene carbonate, diethyl vinylene carbonate, dipropyl vinylene carbonate, fluoro vinylene carbonate and trifluoromethyl vinylene carbonate. The nonaqueous electrolytic solution according to claim 1 .
  3. The nonaqueous electrolytic solution according to claim 1 or 2, wherein the nonaqueous solvent comprises a cyclic aprotic solvent and / or a chain aprotic solvent.
  4. The nonaqueous electrolytic solution according to claim 3 , wherein the cyclic aprotic solvent is at least one solvent selected from cyclic carbonates and cyclic esters.
  5. The nonaqueous electrolytic solution according to claim 4 , wherein the cyclic aprotic solvent is at least one solvent selected from ethylene carbonate, propylene carbonate, butylene carbonate, and γ-butyrolactone.
  6. 6. The nonaqueous electrolytic solution according to claim 2 , wherein the chain aprotic solvent is at least one solvent selected from a chain carbonate and a chain ester.
  7. Chain aprotic solvent, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, claim 6, characterized in that at least one solvent selected from methyl propionate and propyl acetate Non-aqueous electrolyte.
  8. The electrolyte 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), LiPF n (C k F (2k + 1) ) (6-n) (n = 1 to 5, k = 1 to 8) Item 8. The nonaqueous electrolytic solution according to any one of Items 1 to 7 .
  9. The nonaqueous electrolytic solution according to any one of claims 1 to 8, wherein the boric acid ester is contained in an amount of 0.5 to 1 wt% with respect to the entire nonaqueous electrolytic solution.
  10. Before SL sulfonyl group-containing reduction compound is a non-aqueous electrolyte according to any one of claims 1 to 9, characterized in that it contains 0.05 to 5 wt% with respect to the total non-aqueous electrolyte.
  11. Non-aqueous electrolyte according to any one of claims 1 to 10 before millet two alkylene carbonate derivative, with respect to the entire non-aqueous electrolyte characterized in that it contains 0.05 to 5 wt%.
  12. Lithium secondary battery comprising the nonaqueous electrolytic solution according to any one of claims 1 to 11.
  13. As a negative electrode active material, metallic lithium, lithium-containing alloy, carbon material that can be doped / undoped with lithium ions, tin oxide that can be doped / undoped with lithium ions, titanium oxide that can be doped / undoped with lithium ions, A negative electrode containing either niobium oxide or vanadium oxide, or silicon or tin capable of being doped / undoped with lithium ions, and transition metal oxides, transition metal sulfides, and composite oxides of lithium and transition metals as positive electrode active materials A lithium secondary battery comprising: a positive electrode including any one of a conductive polymer material, a carbon material, or a mixture thereof; and the nonaqueous electrolytic solution according to any one of claims 1 to 11 .
  14. Doping and dedoping of the lithium ions is a carbon material capable, surface separation distance in was measured by X-ray analysis (002) plane (d002) is, according to claim 13, characterized in that at most 0.340nm Lithium ion secondary battery.
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