WO2016027588A1 - Organic electrolyte and organic electrolyte storage battery - Google Patents
Organic electrolyte and organic electrolyte storage battery Download PDFInfo
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- WO2016027588A1 WO2016027588A1 PCT/JP2015/069994 JP2015069994W WO2016027588A1 WO 2016027588 A1 WO2016027588 A1 WO 2016027588A1 JP 2015069994 W JP2015069994 W JP 2015069994W WO 2016027588 A1 WO2016027588 A1 WO 2016027588A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to an organic electrolyte and an organic electrolyte storage battery using the same.
- Patent Document 1 a compound having a cyclohexyl group improves the initial storage capacity
- Non-Patent Document 1 formation of lithium dendrite on an alloy electrode is suppressed when a saturated hydrocarbon such as decalin is added to an electrolyte in an energization experiment using a lithium-indium alloy electrode. It has been reported. This report suggests the effect of suppressing deterioration in a secondary battery using a lithium metal negative electrode, but it is not clear whether it can be applied to an actual storage battery because the details of the experiment may not be clear. .
- the object of the present invention is to improve the long-term durability of an organic electrolyte storage battery.
- the present inventors have found that the durability is improved by including a compound containing a cyclohexyl group in the organic electrolyte. It has been found that durability can be further improved by adjusting the type and blending amount of the viscosity solvent, and the present invention has been completed.
- the present invention provides an organic electrolyte comprising an organic solvent comprising a high dielectric constant solvent and a low viscosity solvent, and a compound represented by any of the following formulas (1) to (4), wherein the low viscosity solvent is diethyl
- the organic electrolyte is characterized in that it is carbonate and / or ethyl methyl carbonate, and the proportion of the low-viscosity solvent in the organic solvent is 70% by volume or more.
- R 1 to R 11 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen.
- R 12 to R 13 are a hydrogen atom, a methyl group, an ethyl group or a methyl group containing a halogen, an ethyl group or a halogen; and R 14 is an unsubstituted or substituted cyclohexyl group.
- the number of substituents is 11 at the maximum, and each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms including halogen, or halogen.
- R 1 to R 11 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen.
- R 12 is an alkyl group or halogen, and R 12 is a linear alkylene group having 3 or 4 carbon atoms, and a part of hydrogen may be substituted with halogen and / or a methyl group or a methyl group containing a halogen.
- R 13 is an unsubstituted or substituted cyclohexyl group, having a maximum of 11 substituents, each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a carbon number containing halogen 1 to 4 linear or branched alkyl groups, or halogen.)
- R 1 to R 14 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen.
- R 1 to R 16 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen.
- the present invention also relates to an organic electrolyte storage battery using the organic electrolyte.
- the durability of the storage battery can be improved by using the organic electrolyte of the present invention. Therefore, when the storage battery using the organic electrolyte of the present invention is mounted on an electric vehicle, it is possible to suppress deterioration due to repeated charge and discharge over a long period of time and extend the use period of the electric vehicle. Further, due to its high durability, charging with a relatively high voltage is possible.
- the organic electrolyte of the present invention contains a compound represented by any of the following formulas (1) to (4).
- R 1 to R 11 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen.
- R 12 to R 13 are a hydrogen atom, a methyl group, an ethyl group or a methyl group containing a halogen, an ethyl group or a halogen, and R 14 is an unsubstituted or substituted cyclohexyl group.
- the maximum number of substituents is 11, and each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms including halogen, or halogen. is there.
- R 1 to R 11 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen.
- R 12 is a straight-chain alkylene group having 3 or 4 carbon atoms, and a part of hydrogen may be substituted with halogen and / or a methyl group or a methyl group containing a halogen.
- R 13 is an unsubstituted or substituted cyclohexyl group, having a maximum of 11 substituents, each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a carbon number containing halogen 1 to 4 linear or branched alkyl groups, or halogen.
- R 1 to R 14 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen. Group, or halogen.
- R 1 to R 16 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen. Group, or halogen.
- Specific examples of the compound represented by any one of the formulas (1) to (4) include cyclohexyl (3,4-dimethylcyclohexyl) methane, 1-cyclohexyl-1- (3,4-dimethylcyclohexyl) ethane.
- 1,1-dicyclohexylethane 1-cyclohexyl-1- (2,5-dimethylcyclohexyl) ethane, 1-cyclohexyl-1- (2,3-dimethylcyclohexyl) ethane, 1-cyclohexyl-1 -(2,4-dimethylcyclohexyl) ethane, 1-cyclohexyl-1- (4-ethylcyclohexyl) ethane, 1,3-dicyclohexylpropane, 1,4-dicyclohexylbutane, 1,3-dicyclohexylbutane, trans-hydrindane Cis-hydrindane is preferred, and 1,1-dicyclohexylethane, 1-cyclohexyl-1- (2,5-dimethylcyclohexyl) ethane, trans-hydrindane, and cis-hydrindane are particularly preferred.
- the compounding ratio of the compound represented by any one of formulas (1) to (4) is preferably 0.05% by weight or more, and more preferably 0.1% by weight or more in the organic electrolyte. On the other hand, it is preferably 10% by weight or less, and more preferably 5% by weight or less. If the compounding ratio of the compound represented by the formula (1) is less than 0.05% by weight, the effect of the present invention may not be obtained. If it is more than 10% by weight, the solubility of the electrolyte salt may decrease, When the viscosity of the system electrolyte increases, the performance of the storage battery may be deteriorated.
- the purity of the compound represented by any one of formulas (1) to (4) is preferably 95% or more, more preferably 96% or more, and even more preferably 97% or more. If the purity is lower than 95%, impurities that inhibit the effect of the present invention may be contained, and the original effect may not be obtained.
- the organic electrolyte of the present invention is mainly composed of a compound represented by any one of formulas (1) to (4), an organic solvent and an electrolyte salt, and a high dielectric constant solvent and a low viscosity solvent are used as the organic solvent. It is done.
- the content of the high dielectric constant solvent in the organic solvent is preferably 5 to 30% by volume, more preferably 10 to 25% by volume, and particularly preferably 15 to 25% by volume.
- the content of the low-viscosity solvent in the organic electrolyte is preferably 70 to 95% by volume, more preferably 75 to 90% by volume, and particularly preferably 75 to 85% by volume.
- Examples of the high dielectric constant solvent include, in addition to ethylene carbonate and propylene carbonate, butylene carbonate, ⁇ -butyllactone, ⁇ -valerolactone, tetrahydrofuran, 1,4-dioxane, N-methyl-2-pyrrolidone, N— And methyl-2-oxazolidinone, sulfolane, 2-methylsulfolane and the like.
- diethyl carbonate and / or ethyl methyl carbonate are used as the low viscosity solvent.
- diethyl carbonate is particularly preferable.
- Low viscosity solvents include dimethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, methyl butyl carbonate, dibutyl carbonate, dimethoxyethane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate,
- Various solvents such as isobutyl acetate, methyl propionate, ethyl propionate, methyl formate, ethyl formate, methyl butyrate and methyl isobutyrate are known.
- diethyl carbonate and / or ethyl methyl are used as the low-viscosity solvents.
- organic solvent containing 70% by volume or more of carbonate and combining with the compound represented by the formula (1) By using an organic solvent containing 70% by volume or more of carbonate and combining with the compound represented by the formula (1), the durability of the storage battery can be improved. Electric vehicle equipped with storage battery using the electrolyte, it is possible to suppress the deterioration due to long-term repeated charging and discharging.
- lithium hexafluorophosphate LiPF 6
- lithium tetrafluoroborate LiBF 4
- lithium hexafluoroarsenate LiAsF 6
- lithium hexafluoro antimonate LiSbF 6
- Inorganic lithium salts such as lithium perchlorate (LiClO 4 ) and lithium tetrachloroaluminate (LiAlCl 4 ), and lithium trifluoromethanesulfonate (CF 3 SO 3 Li)
- lithium bis (trifluoromethanesulfone) imide [(CF 3 SO 2 ) 2 NLi]
- lithium bis (pentafluoroethanesulfone) imide [(C 2 F 5 SO 2 ) 2 NLi]
- lithium tris (trifluoromethanesulfone) methide [(CF 3 SO 2 ) 3 CLi]
- One electrolyte salt may be used alone, or a plurality of electrolyte salts may be mixed and used.
- the electrolyte salt is usually contained in the organic electrolyte at a concentration of 0.5 to 3 mol / liter, preferably 0.8 to 2 mol / liter, more preferably 1.0 to 1.6 mol / liter. It is desirable.
- the electrolyte may contain an electrode protective material such as vinylene carbonate, fluoroethylene carbonate, vinyl ethylene carbonate, 1,3-propane sultone, ethylene sulfite, and the like.
- an electrode protective material such as vinylene carbonate, fluoroethylene carbonate, vinyl ethylene carbonate, 1,3-propane sultone, ethylene sulfite, and the like.
- the present invention also provides an organic electrolyte storage battery using the above-described organic electrolyte of the present invention.
- any material that can occlude and release lithium can be used as the positive electrode active material.
- the lithium-containing composite oxide LiMO 2 (M is one kind selected from metals such as Mn, Fe, Co, Ni, or a mixture of two or more kinds, and some of them are other cations such as Mg, Al, Ti, etc.
- Olivine type materials represented by LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , LiFePO 4 , LiMnPO 4, etc. can also be used.
- lithium-rich materials such as Li 2 MnO 3 and Li 2 MSiO 4 (M is a metal) can also be used.
- the positive electrode preferably contains lithium and a transition metal, and particularly preferably contains a layered oxide containing cobalt.
- a carbon-based negative electrode material containing artificial graphite or natural graphite is used for the negative electrode.
- the negative electrode active material a negative electrode active material into which lithium can be inserted or reacts with lithium is used.
- graphite is mainly used, but a carbon material such as amorphous carbon, or a material that forms an alloy with Li, such as Li metal, Si, Sn, Al, Si oxide, Si and Si.
- Si composite oxides containing other metal elements than the above, Sn oxides, Sn composite oxides containing other metal elements other than Sn and Sn, Li 4 Ti 5 O 12, and the like may be mixed and used.
- the separator should just be formed from the electrically insulating porous body, for example, polymer films, such as polyolefin, such as polyethylene and a polypropylene, polyester, polyethylene terephthalate, a polyimide, or a fiber nonwoven fabric.
- the material may be used alone or in combination.
- the separator may be a single layer or a multilayer (composite film).
- an electrolyte that is gelled by containing a polymer compound that swells with an organic solvent and becomes a holding body that holds the organic electrolyte may be used. This is because by including a polymer compound that swells with an organic solvent, high ionic conductivity can be obtained, excellent charge / discharge efficiency can be obtained, and battery leakage can be prevented.
- the organic electrolyte contains a polymer compound, the content of the polymer compound is preferably in the range of 0.1% by mass to 10% by mass.
- the mass ratio of the organic electrolyte to the polymer compound is preferably in the range of 50: 1 to 10: 1. By setting it within this range, higher charge / discharge efficiency can be obtained.
- polymer compound examples include polyvinyl formal, polyethylene oxide, and ether-based polymer compounds such as crosslinked products containing polyethylene oxide, ester-based polymer compounds such as polymethacrylate, acrylate-based polymer compounds, and polyvinylidene fluoride,
- a vinylidene fluoride polymer such as a copolymer of vinylidene fluoride and hexafluoropropylene may be used.
- a high molecular compound may be used individually by 1 type, and multiple types may be mixed and used for it.
- it is desirable to use a fluorine-based polymer compound such as polyvinylidene fluoride.
- the higher the voltage (charging voltage) when charging a battery the more power can be charged into the battery, and the output during discharging can be improved.
- the charging voltage is high, the electrode material and the like are liable to be deteriorated, and there are problems in terms of reduction in repeatability, safety and economy. Therefore, the current charging voltage of the organic electrolyte storage battery is generally 4.10 to 4.20V.
- a higher charging voltage can be adopted. Specifically, it can be used at a charging voltage higher than 4.20V, preferably 4.25V or higher, more preferably 4.35V or higher, and still more preferably 4.45V or higher.
- the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
- the coin type organic electrolyte storage battery will be described with reference to FIG. 1, but the type of the organic electrolyte storage battery of the present invention is not limited to the coin type.
- the button type, the pouch type, the corner type, etc. The present invention can also be applied to organic electrolyte storage batteries such as a mold or a cylinder having a spiral structure.
- the size of the organic electrolyte storage battery is also arbitrary, and may be large, small, or thin.
- FIG. 1 is a schematic cross-sectional view showing the structure of a coin-type organic electrolyte storage battery.
- a positive electrode 12 and a negative electrode 14 are laminated via a separator 15.
- Each of the positive electrode 12, the negative electrode 14, and the separator 15 has a disk shape, and is accommodated in a space defined by the metal exterior component 11 and the exterior component 13.
- the interiors of the exterior parts 11 and 13 are filled with an organic electrolyte, and the peripheral parts of the exterior parts 11 and 13 are sealed by caulking through a seal gasket 17.
- a metal spring 18 and a spacer 19 are disposed between the exterior component 13 and the negative electrode 14.
- the positive electrode was produced as follows. Active material: LiNi 1/3 Mn 1/3 Co 1/3 O 2 90 weight percent, conductive additive: acetylene black 5 weight percent, binder: polyvinylidene fluoride 5 weight percent in a mixture of N-methylpyrrolidone (hereinafter And abbreviated as NMP) and kneaded to prepare a slurry.
- NMP N-methylpyrrolidone
- the prepared slurry was dropped onto an aluminum current collector, formed into a film using a film applicator with a micrometer and an automatic coating machine, and dried in an oven at 100 ° C. in a nitrogen atmosphere.
- the produced positive electrode was punched into a circle having a diameter of 15 mm, and then pressed.
- the amount of the positive electrode active material was about 16 mg.
- the negative electrode was produced as follows. NMP was added to a mixture of active material: 94% by weight of artificial graphite, conductive auxiliary agent: 1% by weight of acetylene black, binder: 5% by weight of polyvinylidene fluoride, and kneaded to prepare a slurry. The prepared slurry was dropped on a copper current collector, formed into a film using a film applicator with a micrometer and an automatic coating machine, and dried in an oven at 110 ° C. in a nitrogen atmosphere. The produced negative electrode was punched into a circle having a diameter of 15 mm, and then pressed. The amount of the negative electrode active material was about 10 mg.
- a coin-type storage battery was produced using a positive electrode produced by the above-described method, a negative electrode made of a polypropylene separator having a thickness of 25 micrometers punched out in a circular shape, and various organic electrolytes.
- the organic solvent a high dielectric constant solvent and a low viscosity solvent were used, and LiPF 6 was dissolved at a rate of 1 mol / liter in a solvent in which these were mixed at a predetermined volume ratio. The purity of all the compounds was 97% or more.
- Ethylene carbonate (hereinafter abbreviated as EC) is used as the high dielectric constant solvent, and diethyl carbonate (hereinafter abbreviated as DEC), ethyl methyl carbonate (hereinafter abbreviated as EMC), or dimethyl carbonate (hereinafter referred to as DMC) as the low viscosity solvent. (Abbreviated) was used.
- DEC diethyl carbonate
- EMC ethyl methyl carbonate
- DMC dimethyl carbonate
- Example 1 An organic electrolyte was prepared as shown in Table 1 below, and a coin-type storage battery was produced as described above.
- Example 2 As shown in Table 4 below, an organic electrolyte in which the ratio of the high dielectric constant solvent and the low viscosity solvent was changed was prepared, and a coin-type storage battery was produced in the same manner as in Example 1.
- the coin-type storage battery and pouch-type storage battery produced by the above-described method were installed in a room temperature incubator, and a charge / discharge test was performed.
- the battery was charged at a constant current of 0.840 mA for 8 hours at a constant voltage of 4.45 V, and then discharged to 3.00 V at a constant current of 0.840 mA.
- the discharge capacity at this time is defined as the initial storage capacity.
- the battery was charged with a constant current of 1.68 mA and a constant voltage of 4.45 V for 4 hours, left in a constant temperature bath at 60 ° C. in a charged state, and stored at a high temperature for 3 weeks.
- the battery After storage, the battery was discharged to 3.00 V at a current of 1.68 mA, charged at a constant current of 1.68 mA for 4 hours at a constant voltage of 4.45 V, and then discharged again to 3.00 V at a current of 1.68 mA. .
- the discharge capacity at this time is defined as the storage capacity after storage.
- Table 6 shows the initial storage capacity and the storage capacity after storage of each battery. Since the battery of Comparative 1-4 deteriorated during the initial charge / discharge, a storage test was not performed.
- the organic electrolyte of the present invention has the effect of increasing the storage capacity of the storage battery after high-temperature storage, and when the storage battery using the organic electrolyte of the present invention is mounted on an electric vehicle, the durability of the battery is improved. It is possible to improve the long-term reliability of the automobile.
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Abstract
Provided is an organic electrolyte which is capable of improving the initial storage capacity of an organic electrolyte storage battery, said initial storage capacity affecting the mileage of an electric vehicle. This organic electrolyte contains: an organic solvent that is composed of a high dielectric constant solvent and a low viscosity solvent; and a compound such as 1,1-dicyclohexyl ethane, a derivative thereof and hydrindane. This organic electrolyte is characterized in that: the low viscosity solvent is diethyl carbonate and/or ethylmethyl carbonate; and the ratio of the low viscosity solvent in the organic solvent is 70% by volume or more.
Description
本発明は、有機系電解質およびそれを用いた有機系電解質蓄電池に関する。
The present invention relates to an organic electrolyte and an organic electrolyte storage battery using the same.
近年、地球環境との調和を目指した社会構築に向け、化石燃料利用によるＣＯ２排出を抑制する試みが多くされている。なかでも自動車等、運輸部門におけるＣＯ２排出に関しては、政府により規制がなされ、自動車会社各社によるハイブリッド電気自動車（ＨＥＶ）、プラグインハイブリッド電気自動車（ＰＨＥＶ）、蓄電池駆動式電気自動車（ＢＥＶ）の開発、製品化が加速されている。これら電気自動車のエネルギー源として、安定的に長期間繰返して充放電可能な大型蓄電池の開発が盛んに行われている。有機系電解質蓄電池は、ニッケル水素電池を含む他の蓄電池に比べ、その動作電圧が高く、高出力、高エネルギー密度を達成しやすい有力な電池であり、電気自動車のエネルギー源として益々重要性が増している。このため種々の開発が進められてきており、例えば、電気自動車の走行可能距離を左右する初期蓄電容量を向上させるための化合物等が検討されている。発明者らも種々の化合物を検討した結果、シクロヘキシル基を有する化合物が初期蓄電容量を向上させることを見出している（特許文献１）。
一方、自動車用途においては、初期蓄電容量とともに約１０年間程度の長期間にわたる使用が可能であること、すなわち高い耐久性が求められている。例えば、非特許文献１においては、リチウム―インジウム合金電極を用いた通電実験により、デカリン等の飽和炭化水素を電解質に添加した場合において、合金電極上へのリチウムデンドライトの形成が抑制されることが報告されている。本報告は、リチウム金属負極を用いた二次電池での劣化抑制効果を示唆するものであるが、詳細な実験内容が不明であることもあり、実際の蓄電池へ適応可能かどうかは明らかではない。 In recent years, many attempts have been made to suppress CO 2 emissions due to the use of fossil fuels for the construction of a society aiming at harmony with the global environment. Among them, an automobile or the like, with respect to CO 2 emissions in the transport sector, regulated by the government have been made, the development of a hybrid electric vehicle according to car companies each company (HEV), plug-in hybrid electric vehicles (PHEV), battery-driven electric vehicle (BEV) , Commercialization has been accelerated. As energy sources for these electric vehicles, large-scale storage batteries that can be charged and discharged repeatedly for a long period of time have been actively developed. Organic electrolyte storage batteries have a higher operating voltage than other storage batteries, including nickel metal hydride batteries, and are powerful batteries that can easily achieve high output and high energy density. They are becoming increasingly important as energy sources for electric vehicles. ing. For this reason, various developments have been promoted. For example, a compound for improving the initial storage capacity that affects the travelable distance of an electric vehicle has been studied. As a result of studying various compounds, the inventors have found that a compound having a cyclohexyl group improves the initial storage capacity (Patent Document 1).
On the other hand, in automotive applications, it is required that the battery can be used for a long period of about 10 years together with the initial storage capacity, that is, high durability. For example, in Non-Patent Document 1, formation of lithium dendrite on an alloy electrode is suppressed when a saturated hydrocarbon such as decalin is added to an electrolyte in an energization experiment using a lithium-indium alloy electrode. It has been reported. This report suggests the effect of suppressing deterioration in a secondary battery using a lithium metal negative electrode, but it is not clear whether it can be applied to an actual storage battery because the details of the experiment may not be clear. .
一方、自動車用途においては、初期蓄電容量とともに約１０年間程度の長期間にわたる使用が可能であること、すなわち高い耐久性が求められている。例えば、非特許文献１においては、リチウム―インジウム合金電極を用いた通電実験により、デカリン等の飽和炭化水素を電解質に添加した場合において、合金電極上へのリチウムデンドライトの形成が抑制されることが報告されている。本報告は、リチウム金属負極を用いた二次電池での劣化抑制効果を示唆するものであるが、詳細な実験内容が不明であることもあり、実際の蓄電池へ適応可能かどうかは明らかではない。 In recent years, many attempts have been made to suppress CO 2 emissions due to the use of fossil fuels for the construction of a society aiming at harmony with the global environment. Among them, an automobile or the like, with respect to CO 2 emissions in the transport sector, regulated by the government have been made, the development of a hybrid electric vehicle according to car companies each company (HEV), plug-in hybrid electric vehicles (PHEV), battery-driven electric vehicle (BEV) , Commercialization has been accelerated. As energy sources for these electric vehicles, large-scale storage batteries that can be charged and discharged repeatedly for a long period of time have been actively developed. Organic electrolyte storage batteries have a higher operating voltage than other storage batteries, including nickel metal hydride batteries, and are powerful batteries that can easily achieve high output and high energy density. They are becoming increasingly important as energy sources for electric vehicles. ing. For this reason, various developments have been promoted. For example, a compound for improving the initial storage capacity that affects the travelable distance of an electric vehicle has been studied. As a result of studying various compounds, the inventors have found that a compound having a cyclohexyl group improves the initial storage capacity (Patent Document 1).
On the other hand, in automotive applications, it is required that the battery can be used for a long period of about 10 years together with the initial storage capacity, that is, high durability. For example, in Non-Patent Document 1, formation of lithium dendrite on an alloy electrode is suppressed when a saturated hydrocarbon such as decalin is added to an electrolyte in an energization experiment using a lithium-indium alloy electrode. It has been reported. This report suggests the effect of suppressing deterioration in a secondary battery using a lithium metal negative electrode, but it is not clear whether it can be applied to an actual storage battery because the details of the experiment may not be clear. .
本発明は有機系電解質蓄電池の長期耐久性を向上させることを目的とする。
The object of the present invention is to improve the long-term durability of an organic electrolyte storage battery.
本発明者らは、前記課題について鋭意検討を行った結果、シクロヘキシル基を含有する化合物を有機系電解質に含有させることにより、耐久性が向上することを見出したが、有機系電解質に含まれる低粘度溶媒の種類、および配合量を調整することにより、耐久性をさらに向上させることができることを見出し、本発明を完成するに至った。
As a result of intensive studies on the above problems, the present inventors have found that the durability is improved by including a compound containing a cyclohexyl group in the organic electrolyte. It has been found that durability can be further improved by adjusting the type and blending amount of the viscosity solvent, and the present invention has been completed.
すなわち、本発明は、高誘電率溶媒および低粘度溶媒からなる有機溶媒、並びに下記式（１）～（４）のいずれかで示される化合物を含有する有機電解質であって、低粘度溶媒がジエチルカーボネートおよび／またはエチルメチルカーボネートであり、有機溶媒中の低粘度溶媒の割合が７０容量％以上であることを特徴とする有機系電解質に関する。
（式（１）において、Ｒ１～Ｒ１１は、それぞれ独立して、水素原子、炭素数１～４の直鎖もしくは分岐のアルキル基、ハロゲンを含む炭素数１～４の直鎖もしくは分岐のアルキル基、またはハロゲンであり、Ｒ１２～Ｒ１３は水素原子、メチル基、エチル基もしくはハロゲンを含むメチル基、エチル基またはハロゲンであり、Ｒ１４は無置換または置換基の付いたシクロヘキシル基であって、置換基数は最大で１１であり、それぞれ独立して、炭素数１～４の直鎖もしくは分岐のアルキル基、ハロゲンを含む炭素数１～４の直鎖もしくは分岐のアルキル基、またはハロゲンである。）
（式（２）において、Ｒ１～Ｒ１１は、それぞれ独立して、水素原子、炭素数１～４の直鎖もしくは分岐のアルキル基、ハロゲンを含む炭素数１～４の直鎖もしくは分岐のアルキル基、またはハロゲンであり、Ｒ１２は炭素数３もしくは４の直鎖のアルキレン基であり、水素の一部がハロゲンおよび／またはメチル基もしくはハロゲンを含むメチル基で置換されていてもよい。Ｒ１３は無置換または置換基の付いたシクロヘキシル基であって、置換基数は最大で１１であり、それぞれ独立して、炭素数１～４の直鎖もしくは分岐のアルキル基、ハロゲンを含む炭素数１～４の直鎖もしくは分岐のアルキル基、またはハロゲンである。）
（式（３）において、Ｒ１～Ｒ１４は、それぞれ独立して、水素原子、炭素数１～４の直鎖もしくは分岐のアルキル基、ハロゲンを含む炭素数１～４の直鎖もしくは分岐のアルキル基、またはハロゲンである。）
（式（４）において、Ｒ１～Ｒ１６は、それぞれ独立して、水素原子、炭素数１～４の直鎖もしくは分岐のアルキル基、ハロゲンを含む炭素数１～４の直鎖もしくは分岐のアルキル基、またはハロゲンである。）
That is, the present invention provides an organic electrolyte comprising an organic solvent comprising a high dielectric constant solvent and a low viscosity solvent, and a compound represented by any of the following formulas (1) to (4), wherein the low viscosity solvent is diethyl The organic electrolyte is characterized in that it is carbonate and / or ethyl methyl carbonate, and the proportion of the low-viscosity solvent in the organic solvent is 70% by volume or more.
(In Formula (1), R 1 to R 11 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen. An alkyl group or a halogen; R 12 to R 13 are a hydrogen atom, a methyl group, an ethyl group or a methyl group containing a halogen, an ethyl group or a halogen; and R 14 is an unsubstituted or substituted cyclohexyl group. The number of substituents is 11 at the maximum, and each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms including halogen, or halogen. .)
(In Formula (2), R 1 to R 11 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen. R 12 is an alkyl group or halogen, and R 12 is a linear alkylene group having 3 or 4 carbon atoms, and a part of hydrogen may be substituted with halogen and / or a methyl group or a methyl group containing a halogen. R 13 is an unsubstituted or substituted cyclohexyl group, having a maximum of 11 substituents, each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a carbon number containing halogen 1 to 4 linear or branched alkyl groups, or halogen.)
(In the formula (3), R 1 to R 14 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen. An alkyl group or a halogen.)
(In the formula (4), R 1 to R 16 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen. An alkyl group or a halogen.)
また本発明は、前記有機系電解質を用いた有機系電解質蓄電池に関する。
The present invention also relates to an organic electrolyte storage battery using the organic electrolyte.
本発明の有機系電解質を用いることにより、蓄電池の耐久性を向上させることができる。したがって、本発明の有機系電解質を用いた蓄電池を電気自動車に搭載した場合には、長期にわたる繰り返し充放電による劣化を抑制し、電気自動車の使用期間を延ばすことが可能となる。またその高い耐久性ゆえ比較的高い電圧による充電が可能となる。
The durability of the storage battery can be improved by using the organic electrolyte of the present invention. Therefore, when the storage battery using the organic electrolyte of the present invention is mounted on an electric vehicle, it is possible to suppress deterioration due to repeated charge and discharge over a long period of time and extend the use period of the electric vehicle. Further, due to its high durability, charging with a relatively high voltage is possible.
以下、本発明について詳述する。
Hereinafter, the present invention will be described in detail.
本発明の有機系電解質は、下記式（１）～（４）のいずれかで示される化合物を含有する。
The organic electrolyte of the present invention contains a compound represented by any of the following formulas (1) to (4).
式（１）において、Ｒ１～Ｒ１１は、それぞれ独立して、水素原子、炭素数１～４の直鎖もしくは分岐のアルキル基、ハロゲンを含む炭素数１～４の直鎖もしくは分岐のアルキル基、またはハロゲンであり、Ｒ１２～Ｒ１３は水素原子、メチル基、エチル基もしくはハロゲンを含むメチル基、エチル基またはハロゲンであり、Ｒ１４は無置換または置換基の付いたシクロヘキシル基であって、置換基数は最大で１１であり、それぞれ独立して、炭素数１～４の直鎖もしくは分岐のアルキル基、ハロゲンを含む炭素数１～４の直鎖もしくは分岐のアルキル基、またはハロゲンである。
In the formula (1), R 1 to R 11 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen. R 12 to R 13 are a hydrogen atom, a methyl group, an ethyl group or a methyl group containing a halogen, an ethyl group or a halogen, and R 14 is an unsubstituted or substituted cyclohexyl group. The maximum number of substituents is 11, and each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms including halogen, or halogen. is there.
式（２）において、Ｒ１～Ｒ１１は、それぞれ独立して、水素原子、炭素数１～４の直鎖もしくは分岐のアルキル基、ハロゲンを含む炭素数１～４の直鎖もしくは分岐のアルキル基、またはハロゲンであり、Ｒ１２は炭素数３もしくは４の直鎖のアルキレン基であり、水素の一部がハロゲンおよび／またはメチル基もしくはハロゲンを含むメチル基で置換されていてもよい。Ｒ１３は無置換または置換基の付いたシクロヘキシル基であって、置換基数は最大で１１であり、それぞれ独立して、炭素数１～４の直鎖もしくは分岐のアルキル基、ハロゲンを含む炭素数１～４の直鎖もしくは分岐のアルキル基、またはハロゲンである。
In the formula (2), R 1 to R 11 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen. R 12 is a straight-chain alkylene group having 3 or 4 carbon atoms, and a part of hydrogen may be substituted with halogen and / or a methyl group or a methyl group containing a halogen. R 13 is an unsubstituted or substituted cyclohexyl group, having a maximum of 11 substituents, each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a carbon number containing halogen 1 to 4 linear or branched alkyl groups, or halogen.
式（３）において、Ｒ１～Ｒ１４は、それぞれ独立して、水素原子、炭素数１～４の直鎖もしくは分岐のアルキル基、ハロゲンを含む炭素数１～４の直鎖もしくは分岐のアルキル基、またはハロゲンである。
In the formula (3), R 1 to R 14 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen. Group, or halogen.
式（４）において、Ｒ１～Ｒ１６は、それぞれ独立して、水素原子、炭素数１～４の直鎖もしくは分岐のアルキル基、ハロゲンを含む炭素数１～４の直鎖もしくは分岐のアルキル基、またはハロゲンである。
In the formula (4), R 1 to R 16 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms including halogen. Group, or halogen.
かかる式（１）～（４）のいずれかで示される化合物としては、具体的には、シクロヘキシル（３、４－ジメチルシクロヘキシル）メタン、１－シクロヘキシル－１－（３、４－ジメチルシクロヘキシル）エタン、２－（３、４－ジメチルシクロヘキシル）－２－シクロヘキシルプロパン、シクロヘキシル（２、４－ジメチルシクロヘキシル）メタン、１－シクロヘキシル－１－（２、４－ジメチルシクロヘキシル）エタン、２－（２、４－ジメチルシクロヘキシル）－２－シクロヘキシルプロパン、シクロヘキシル（２、５－ジメチルシクロヘキシル）メタン、１－シクロヘキシル－１－（２、５－ジメチルシクロヘキシル）エタン、２－（２、５－ジメチルシクロヘキシル）－２－シクロヘキシルプロパン、シクロヘキシル（２－エチルシクロヘキシル）メタン、１－シクロヘキシル－１－（２－エチルシクロヘキシル）エタン、２－シクロヘキシル－２－（２－エチルシクロヘキシル）プロパン、シクロヘキシル（３－エチルシクロヘキシル）メタン、１－シクロヘキシル－１－（３－エチルシクロヘキシル）エタン、２－シクロヘキシル－２－（３－エチルシクロヘキシル）プロパン、シクロヘキシル（４－エチルシクロヘキシル）メタン、１－シクロヘキシル－１－（４－エチルシクロヘキシル）エタン、２－シクロヘキシル－２－（４－エチルシクロヘキシル）プロパン、シクロヘキシル（２－メチルシクロヘキシル）メタン、１－シクロヘキシル－１－（２－メチルシクロヘキシル）エタン、シクロヘキシル（３－メチルシクロヘキシル）メタン、１－シクロヘキシル－１－（３－メチルシクロヘキシル）エタン、２－シクロヘキシル－２－（３－メチルシクロヘキシル）プロパン、シクロヘキシル（４－メチルシクロヘキシル）メタン、１－シクロヘキシル－１－（４－メチルシクロヘキシル）エタン、（２－メチルシクロヘキシル）（４－メチルシクロヘキシル）メタン、１－（２－メチルシクロヘキシル）－１－（４－メチルシクロヘキシル）エタン、２－（２－メチルシクロヘキシル）－２－（４－メチルシクロヘキシル）プロパン、（２－メチルシクロヘキシル）（３－メチルシクロヘキシル）メタン、１－（２－メチルシクロヘキシル）－１－（３－メチルシクロヘキシル）エタン、２－（２－メチルシクロヘキシル）－２－（３－メチルシクロヘキシル）プロパン、（４－メチルシクロヘキシル）（３－メチルシクロヘキシル）メタン、１－（４－メチルシクロヘキシル）－１－（３－メチルシクロヘキシル）エタン、２－（４－メチルシクロヘキシル）－２－（３－メチルシクロヘキシル）プロパン、シクロヘキシル（４－イソブチルフェニル）メタン、シクロヘキシル（４－イソブチルシクロヘキシル）メタン、１－シクロヘキシル－１－（４－イソブチルシクロヘキシル）エタン、２－シクロヘキシル－２－（４－イソブチルシクロヘキシル）プロパン、シクロヘキシル（２－イソブチルシクロヘキシル）メタン、１－シクロヘキシル－１－（２－イソブチルシクロヘキシル）エタン、２－シクロヘキシル－２－（２－イソブチルシクロヘキシル）プロパン、シクロヘキシル（３－イソブチルシクロヘキシル）メタン、１－シクロヘキシル－１－（３－イソブチルシクロヘキシル）エタン、２－シクロヘキシル－２－（３－イソブチルシクロヘキシル）プロパン、シクロヘキシル（４－イソプロピルフェニル）メタン、シクロヘキシル（４－イソプロピルシクロヘキシル）メタン、１－シクロヘキシル－１－（４－イソプロピルシクロヘキシル）エタン、２－シクロヘキシル－２－（４－イソプロピルシクロヘキシル）プロパン、シクロヘキシル（２－イソプロピルシクロヘキシル）メタン、１－シクロヘキシル－１－（２－イソプロピルシクロヘキシル）エタン、２－シクロヘキシル－２－（２－イソプロピルシクロヘキシル）プロパン、２－シクロヘキシル－２－（２－イソプロピルシクロヘキシル）プロパン、シクロヘキシル（３－イソプロピルシクロヘキシル）メタン、１－シクロヘキシル－１－（３－イソプロピルシクロヘキシル）エタン、２－シクロヘキシル－２－（３－イソプロピルシクロヘキシル）プロパン、２、２－ジシクロヘキシルブタン、１，３－ジシクロヘキシルブタン、１、４－ジシクロヘキシルブタン、１、１－ジシクロヘキシル－２－メチルプロパン、ジシクロヘキシルメタン、１、１－ジシクロヘキシルエタン、２、２－ジシクロヘキシルプロパン、ビス（４－メチルシクロヘキシル）メタン、１、１－ビス（４－メチルシクロヘキシル）エタン、１、１－ビス（２－メチルシクロヘキシル）エタン、１、１－ビス（３－メチルシクロヘキシル）エタン、１、１－ビス（４－エチルシクロヘキシル）エタン、１、１－ビス（２－エチルシクロヘキシル）エタン、１、１－ビス（３－エチルシクロヘキシル）エタン、１、１－ビス（４－（イソプロピルシクロヘキシル））エタン、１、１－ビス（２－（イソプロピルシクロヘキシル））エタン、１、１－ビス（３－（イソプロピルシクロヘキシル））エタン、１、１－ビス（３、４－ジメチルシクロヘキシル）エタン、１、１－ビス（３、５－ジメチルシクロヘキシル）エタン、１、１－ビス（２、５－ジメチルシクロヘキシル）エタン、１、１－ビス（３、４、５－トリメチルシクロヘキシル）エタン、１、１－ビス（３－フルオロシクロヘキシル）エタン、１、１－ビス（２、５－ジフルオロシクロヘキシル）エタン、１、１－ビス（３、５－ジフルオロシクロヘキシル）エタン、１、１－ビス（２、４－ジフルオロシクロヘキシル）エタン、１、１－ビス（３、４、５－トリフルオロシクロヘキシル）エタン、ビス（４－メチルシクロヘキシル）メタン、ビス（２－メチルシクロヘキシル）メタン、ビス（３－メチルシクロヘキシル）メタン、ビス（４－エチルシクロヘキシル）メタン、ビス（２－エチルシクロヘキシル）メタン、ビス（３－エチルシクロヘキシル）メタン、ビス（４－イソプロピルシクロヘキシル））メタン、ビス（２－イソプロピルシクロヘキシル））メタン、ビス（３－イソプロピルシクロヘキシル））メタン、ビス（３、４－ジメチルシクロヘキシル）メタン、ビス（３、５－ジメチルシクロヘキシル）メタン、ビス（２、５－ジメチルシクロヘキシル）メタン、ビス（３、４、５－トリメチルシクロヘキシル）メタン、ビス（３－フルオロシクロヘキシル）メタン、ビス（２、５－ジフルオロシクロヘキシル）メタン、ビス（３、４－ジフルオロシクロヘキシル）メタン、ビス（３、５－ジフルオロシクロヘキシル）メタン、ビス（３、４、５－トリフルオロシクロヘキシル）メタン、２，２－ビス（４－メチルシクロヘキシル）プロパン、２、２－ビス（２－メチルシクロヘキシル）プロパン、２、２－ビス（３－メチルシクロヘキシル）プロパン、２、２－ビス（４－エチルシクロヘキシル）プロパン、２、２－ビス（２－エチルシクロヘキシル）プロパン、２、２－ビス（３－エチルシクロヘキシル）プロパン、２、２－ビス（４－イソプロピルフェニル）プロパン、２、２－ビス（２－イソプロピルフェニル）プロパン、２、２－ビス（３－イソプロピルフェニル）プロパン、２、２－ビス（３、４－ジメチルシクロヘキシル）プロパン、２、２－ビス（３、５－ジメチルシクロヘキシル）プロパン、２、２－ビス（２、５－ジメチルシクロヘキシル）プロパン、２、２－ビス（３、４、５－トリメチルシクロヘキシル）プロパン、２、２－ビス（３－フルオロシクロヘキシル）プロパン、２、２－ビス（２、５－ジフルオロシクロヘキシル）プロパン、２、２－ビス（３、４－ジフルオロシクロヘキシル）プロパン、２、２－ビス（３、５－ジフルオロシクロヘキシル）プロパン、トランス－ヒドリンダン、シス－ヒドリンダンなどが挙げられる。これらは１種を単独で使用しても２種以上を併用しても良い。
Specific examples of the compound represented by any one of the formulas (1) to (4) include cyclohexyl (3,4-dimethylcyclohexyl) methane, 1-cyclohexyl-1- (3,4-dimethylcyclohexyl) ethane. 2- (3,4-dimethylcyclohexyl) -2-cyclohexylpropane, cyclohexyl (2,4-dimethylcyclohexyl) methane, 1-cyclohexyl-1- (2,4-dimethylcyclohexyl) ethane, 2- (2,4 -Dimethylcyclohexyl) -2-cyclohexylpropane, cyclohexyl (2,5-dimethylcyclohexyl) methane, 1-cyclohexyl-1- (2,5-dimethylcyclohexyl) ethane, 2- (2,5-dimethylcyclohexyl) -2- Cyclohexylpropane, cyclohexyl (2-ethyl) Cyclohexyl) methane, 1-cyclohexyl-1- (2-ethylcyclohexyl) ethane, 2-cyclohexyl-2- (2-ethylcyclohexyl) propane, cyclohexyl (3-ethylcyclohexyl) methane, 1-cyclohexyl-1- (3- Ethylcyclohexyl) ethane, 2-cyclohexyl-2- (3-ethylcyclohexyl) propane, cyclohexyl (4-ethylcyclohexyl) methane, 1-cyclohexyl-1- (4-ethylcyclohexyl) ethane, 2-cyclohexyl-2- (4 -Ethylcyclohexyl) propane, cyclohexyl (2-methylcyclohexyl) methane, 1-cyclohexyl-1- (2-methylcyclohexyl) ethane, cyclohexyl (3-methylcyclohexyl) methane, 1-cyclohexyl 1- (3-methylcyclohexyl) ethane, 2-cyclohexyl-2- (3-methylcyclohexyl) propane, cyclohexyl (4-methylcyclohexyl) methane, 1-cyclohexyl-1- (4-methylcyclohexyl) ethane, 2-methylcyclohexyl) (4-methylcyclohexyl) methane, 1- (2-methylcyclohexyl) -1- (4-methylcyclohexyl) ethane, 2- (2-methylcyclohexyl) -2- (4-methylcyclohexyl) propane , (2-methylcyclohexyl) (3-methylcyclohexyl) methane, 1- (2-methylcyclohexyl) -1- (3-methylcyclohexyl) ethane, 2- (2-methylcyclohexyl) -2- (3-methylcyclohexyl) ) Propane, (4-methylcyclohex Syl) (3-methylcyclohexyl) methane, 1- (4-methylcyclohexyl) -1- (3-methylcyclohexyl) ethane, 2- (4-methylcyclohexyl) -2- (3-methylcyclohexyl) propane, cyclohexyl ( 4-isobutylphenyl) methane, cyclohexyl (4-isobutylcyclohexyl) methane, 1-cyclohexyl-1- (4-isobutylcyclohexyl) ethane, 2-cyclohexyl-2- (4-isobutylcyclohexyl) propane, cyclohexyl (2-isobutylcyclohexyl) ) Methane, 1-cyclohexyl-1- (2-isobutylcyclohexyl) ethane, 2-cyclohexyl-2- (2-isobutylcyclohexyl) propane, cyclohexyl (3-isobutylcyclohexyl) methane, 1- Cyclohexyl-1- (3-isobutylcyclohexyl) ethane, 2-cyclohexyl-2- (3-isobutylcyclohexyl) propane, cyclohexyl (4-isopropylphenyl) methane, cyclohexyl (4-isopropylcyclohexyl) methane, 1-cyclohexyl-1- (4-Isopropylcyclohexyl) ethane, 2-cyclohexyl-2- (4-isopropylcyclohexyl) propane, cyclohexyl (2-isopropylcyclohexyl) methane, 1-cyclohexyl-1- (2-isopropylcyclohexyl) ethane, 2-cyclohexyl-2 -(2-Isopropylcyclohexyl) propane, 2-cyclohexyl-2- (2-isopropylcyclohexyl) propane, cyclohexyl (3-isopropylcyclohexyl) ) Methane, 1-cyclohexyl-1- (3-isopropylcyclohexyl) ethane, 2-cyclohexyl-2- (3-isopropylcyclohexyl) propane, 2,2-dicyclohexylbutane, 1,3-dicyclohexylbutane, 1,4- Dicyclohexylbutane, 1,1-dicyclohexyl-2-methylpropane, dicyclohexylmethane, 1,1-dicyclohexylethane, 2,2-dicyclohexylpropane, bis (4-methylcyclohexyl) methane, 1,1-bis (4-methylcyclohexyl) ) Ethane, 1,1-bis (2-methylcyclohexyl) ethane, 1,1-bis (3-methylcyclohexyl) ethane, 1,1-bis (4-ethylcyclohexyl) ethane, 1,1-bis (2- Ethylcyclohexyl) ethane, 1,1- Bis (3-ethylcyclohexyl) ethane, 1,1-bis (4- (isopropylcyclohexyl)) ethane, 1,1-bis (2- (isopropylcyclohexyl)) ethane, 1,1-bis (3- (isopropylcyclohexyl) )) Ethane, 1,1-bis (3,4-dimethylcyclohexyl) ethane, 1,1-bis (3,5-dimethylcyclohexyl) ethane, 1,1-bis (2,5-dimethylcyclohexyl) ethane, 1-bis (3,4,5-trimethylcyclohexyl) ethane, 1,1-bis (3-fluorocyclohexyl) ethane, 1,1-bis (2,5-difluorocyclohexyl) ethane, 1,1-bis ( 3,5-difluorocyclohexyl) ethane, 1,1-bis (2,4-difluorocyclohexyl) ethane, 1,1-bis 3,4,5-trifluorocyclohexyl) ethane, bis (4-methylcyclohexyl) methane, bis (2-methylcyclohexyl) methane, bis (3-methylcyclohexyl) methane, bis (4-ethylcyclohexyl) methane, bis ( 2-ethylcyclohexyl) methane, bis (3-ethylcyclohexyl) methane, bis (4-isopropylcyclohexyl)) methane, bis (2-isopropylcyclohexyl)) methane, bis (3-isopropylcyclohexyl)) methane, bis (3, 4-dimethylcyclohexyl) methane, bis (3,5-dimethylcyclohexyl) methane, bis (2,5-dimethylcyclohexyl) methane, bis (3,4,5-trimethylcyclohexyl) methane, bis (3-fluorocyclohexyl) methane , (2,5-difluorocyclohexyl) methane, bis (3,4-difluorocyclohexyl) methane, bis (3,5-difluorocyclohexyl) methane, bis (3,4,5-trifluorocyclohexyl) methane, 2,2 -Bis (4-methylcyclohexyl) propane, 2,2-bis (2-methylcyclohexyl) propane, 2,2-bis (3-methylcyclohexyl) propane, 2,2-bis (4-ethylcyclohexyl) propane, 2, 2-bis (2-ethylcyclohexyl) propane, 2,2-bis (3-ethylcyclohexyl) propane, 2,2-bis (4-isopropylphenyl) propane, 2,2-bis (2-isopropylphenyl) propane 2,2-bis (3-isopropylphenyl) propane, 2,2-bis (3,4) -Dimethylcyclohexyl) propane, 2,2-bis (3,5-dimethylcyclohexyl) propane, 2,2-bis (2,5-dimethylcyclohexyl) propane, 2,2-bis (3,4,5-trimethylcyclohexyl) ) Propane, 2,2-bis (3-fluorocyclohexyl) propane, 2,2-bis (2,5-difluorocyclohexyl) propane, 2,2-bis (3,4-difluorocyclohexyl) propane, 2,2- Bis (3,5-difluorocyclohexyl) propane, trans-hydrindane, cis-hydrindane and the like can be mentioned. These may be used alone or in combination of two or more.
これらの中でも、１，１－ジシクロヘキシルエタン、１－シクロヘキシル－１－（２，５－ジメチルシクロヘキル）エタン、１－シクロヘキシル－１－（２，３－ジメチルシクロヘキル）エタン、１－シクロヘキシル－１－（２，４－ジメチルシクロヘキル）エタン、１－シクロヘキシル－１－（４－エチルシクロヘキシル）エタン、１，３－ジシクロヘキシルプロパン、１，４－ジシクロヘキシルブタン、１，３－ジシクロヘキシルブタン、トランス－ヒドリンダン、シス－ヒドリンダンが好ましく、１，１－ジシクロヘキシルエタン、１－シクロヘキシル－１－（２，５－ジメチルシクロヘキル）エタン、トランス－ヒドリンダン、シス－ヒドリンダンが特に好ましい。
Among these, 1,1-dicyclohexylethane, 1-cyclohexyl-1- (2,5-dimethylcyclohexyl) ethane, 1-cyclohexyl-1- (2,3-dimethylcyclohexyl) ethane, 1-cyclohexyl-1 -(2,4-dimethylcyclohexyl) ethane, 1-cyclohexyl-1- (4-ethylcyclohexyl) ethane, 1,3-dicyclohexylpropane, 1,4-dicyclohexylbutane, 1,3-dicyclohexylbutane, trans-hydrindane Cis-hydrindane is preferred, and 1,1-dicyclohexylethane, 1-cyclohexyl-1- (2,5-dimethylcyclohexyl) ethane, trans-hydrindane, and cis-hydrindane are particularly preferred.
式（１）～（４）のいずれかで示される化合物の配合割合は、有機系電解質中に０．０５重量％以上が好ましく、０．１重量％以上がより好ましい。一方、１０重量％以下が好ましく、５重量％以下がより好ましい。式（１）で示される化合物の配合割合が０．０５重量％より少ないと、本発明による効果が得られない可能性があり、１０重量％より多いと電解質塩の溶解度が低下したり、有機系電解質の粘度が増加することにより、蓄電池の性能が悪化する可能性がある。
The compounding ratio of the compound represented by any one of formulas (1) to (4) is preferably 0.05% by weight or more, and more preferably 0.1% by weight or more in the organic electrolyte. On the other hand, it is preferably 10% by weight or less, and more preferably 5% by weight or less. If the compounding ratio of the compound represented by the formula (1) is less than 0.05% by weight, the effect of the present invention may not be obtained. If it is more than 10% by weight, the solubility of the electrolyte salt may decrease, When the viscosity of the system electrolyte increases, the performance of the storage battery may be deteriorated.
なお、式（１）～（４）のいずれかで示される化合物の純度は、９５％以上であることが好ましく、９６％以上がより好ましく、９７％以上がさらに好ましい。純度が９５％より低い場合には、本発明の効果を阻害する不純物が含まれる可能性があり、本来の効果が得られないおそれがある。
The purity of the compound represented by any one of formulas (1) to (4) is preferably 95% or more, more preferably 96% or more, and even more preferably 97% or more. If the purity is lower than 95%, impurities that inhibit the effect of the present invention may be contained, and the original effect may not be obtained.
本発明の有機系電解質は、主として、式（１）～（４）のいずれかで示される化合物、有機溶媒および電解質塩から構成され、該有機溶媒としては高誘電率溶媒および低粘度溶媒が用いられる。
The organic electrolyte of the present invention is mainly composed of a compound represented by any one of formulas (1) to (4), an organic solvent and an electrolyte salt, and a high dielectric constant solvent and a low viscosity solvent are used as the organic solvent. It is done.
有機溶媒における高誘電率溶媒の含有割合は、５～３０容量％であることが好ましく、１０～２５容量％がより好ましく、１５～２５容量％が特に好ましい。
一方、有機系電解質における低粘度溶媒の含有割合は、７０～９５容量％であることが好ましく、７５～９０容量％がより好ましく、７５～８５容量％が特に好ましい The content of the high dielectric constant solvent in the organic solvent is preferably 5 to 30% by volume, more preferably 10 to 25% by volume, and particularly preferably 15 to 25% by volume.
On the other hand, the content of the low-viscosity solvent in the organic electrolyte is preferably 70 to 95% by volume, more preferably 75 to 90% by volume, and particularly preferably 75 to 85% by volume.
一方、有機系電解質における低粘度溶媒の含有割合は、７０～９５容量％であることが好ましく、７５～９０容量％がより好ましく、７５～８５容量％が特に好ましい The content of the high dielectric constant solvent in the organic solvent is preferably 5 to 30% by volume, more preferably 10 to 25% by volume, and particularly preferably 15 to 25% by volume.
On the other hand, the content of the low-viscosity solvent in the organic electrolyte is preferably 70 to 95% by volume, more preferably 75 to 90% by volume, and particularly preferably 75 to 85% by volume.
前記高誘電率溶媒としては、エチレンカーボネート、プロピレンカーボネートの他に、例えば、ブチレンカーボネート、γ―ブチルラクトン、γ―バレロラクトン、テトラヒドロフラン、１、４－ジオキサン、Ｎ－メチル－２－ピロリドン、Ｎ－メチル－２－オキサゾリジノン、スルホラン、２－メチルスルホランなどが挙げられる。
Examples of the high dielectric constant solvent include, in addition to ethylene carbonate and propylene carbonate, butylene carbonate, γ-butyllactone, γ-valerolactone, tetrahydrofuran, 1,4-dioxane, N-methyl-2-pyrrolidone, N— And methyl-2-oxazolidinone, sulfolane, 2-methylsulfolane and the like.
前記低粘度溶媒としては、本発明においては、ジエチルカーボネートおよび／またはエチルメチルカーボネートが用いられる。なかでもジエチルカーボネートが特に好ましい。
低粘度溶媒としては、ジメチルカーボネート、メチルプロピルカーボネート、メチルイソプロピルカーボネート、エチルプロピルカーボネート、ジプロピルカーボネート、メチルブチルカーボネート、ジブチルカーボネート、ジメトキシエタン、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、プロピオン酸メチル、プロピオン酸エチル、ギ酸メチル、ギ酸エチル、酪酸メチル、イソ酪酸メチルなどの各種溶媒が知られているが、本発明においては、低粘度溶媒としてジエチルカーボネートおよび／またはエチルメチルカーボネートを７０容量％以上含有する有機溶媒を用い、かつ前記式（１）で示される化合物と組み合わせることにより、蓄電池の耐久性を向上させることができ、本発明の有機系電解質を用いた蓄電池を搭載した電気自動車は、長期にわたる繰り返し充放電による劣化を抑制することが可能となる。 In the present invention, diethyl carbonate and / or ethyl methyl carbonate are used as the low viscosity solvent. Of these, diethyl carbonate is particularly preferable.
Low viscosity solvents include dimethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, methyl butyl carbonate, dibutyl carbonate, dimethoxyethane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, Various solvents such as isobutyl acetate, methyl propionate, ethyl propionate, methyl formate, ethyl formate, methyl butyrate and methyl isobutyrate are known. In the present invention, diethyl carbonate and / or ethyl methyl are used as the low-viscosity solvents. By using an organic solvent containing 70% by volume or more of carbonate and combining with the compound represented by the formula (1), the durability of the storage battery can be improved. Electric vehicle equipped with storage battery using the electrolyte, it is possible to suppress the deterioration due to long-term repeated charging and discharging.
低粘度溶媒としては、ジメチルカーボネート、メチルプロピルカーボネート、メチルイソプロピルカーボネート、エチルプロピルカーボネート、ジプロピルカーボネート、メチルブチルカーボネート、ジブチルカーボネート、ジメトキシエタン、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、プロピオン酸メチル、プロピオン酸エチル、ギ酸メチル、ギ酸エチル、酪酸メチル、イソ酪酸メチルなどの各種溶媒が知られているが、本発明においては、低粘度溶媒としてジエチルカーボネートおよび／またはエチルメチルカーボネートを７０容量％以上含有する有機溶媒を用い、かつ前記式（１）で示される化合物と組み合わせることにより、蓄電池の耐久性を向上させることができ、本発明の有機系電解質を用いた蓄電池を搭載した電気自動車は、長期にわたる繰り返し充放電による劣化を抑制することが可能となる。 In the present invention, diethyl carbonate and / or ethyl methyl carbonate are used as the low viscosity solvent. Of these, diethyl carbonate is particularly preferable.
Low viscosity solvents include dimethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, methyl butyl carbonate, dibutyl carbonate, dimethoxyethane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, Various solvents such as isobutyl acetate, methyl propionate, ethyl propionate, methyl formate, ethyl formate, methyl butyrate and methyl isobutyrate are known. In the present invention, diethyl carbonate and / or ethyl methyl are used as the low-viscosity solvents. By using an organic solvent containing 70% by volume or more of carbonate and combining with the compound represented by the formula (1), the durability of the storage battery can be improved. Electric vehicle equipped with storage battery using the electrolyte, it is possible to suppress the deterioration due to long-term repeated charging and discharging.
電解質塩としては、例えば、六フッ化リン酸リチウム（ＬｉＰＦ６）、四フッ化ホウ酸リチウム（ＬｉＢＦ４）、六フッ化ヒ酸リチウム（ＬｉＡｓＦ６）、六フッ化アンチモン酸リチウム（ＬｉＳｂＦ６）、過塩素酸リチウム（ＬｉＣｌＯ４）および四塩化アルミニウム酸リチウム（ＬｉＡｌＣｌ４）などの無機リチウム塩、並びにトリフルオロメタンスルホン酸リチウム（ＣＦ３ＳＯ３Ｌｉ）、リチウムビス（トリフルオロメタンスルホン）イミド［（ＣＦ３ＳＯ２）２ＮＬｉ］、リチウムビス（ペンタフルオロエタンスルホン）イミド［（Ｃ２Ｆ５ＳＯ２）２ＮＬｉ］およびリチウムトリス（トリフルオロメタンスルホン）メチド［（ＣＦ３ＳＯ２）３ＣＬｉ］などのパーフルオロアルカンスルホン酸誘導体のリチウム塩が挙げられる。電解質塩は１種を単独で用いてもよく、複数種を混合して用いてもよい。
電解質塩は、通常、０．５～３モル／リットル、好ましくは０．８～２モル／リットル、より好ましくは１．０～１．６モル／リットルの濃度で有機系電解質中に含まれていることが望ましい。 As the electrolyte salt, e.g., lithium hexafluorophosphate (LiPF 6), lithium tetrafluoroborate (LiBF 4), lithium hexafluoroarsenate (LiAsF 6), lithium hexafluoro antimonate (LiSbF 6) , Inorganic lithium salts such as lithium perchlorate (LiClO 4 ) and lithium tetrachloroaluminate (LiAlCl 4 ), and lithium trifluoromethanesulfonate (CF 3 SO 3 Li), lithium bis (trifluoromethanesulfone) imide [(CF 3 SO 2 ) 2 NLi], lithium bis (pentafluoroethanesulfone) imide [(C 2 F 5 SO 2 ) 2 NLi] and lithium tris (trifluoromethanesulfone) methide [(CF 3 SO 2 ) 3 CLi] Of perfluoroalkanesulfonic acid derivatives Lithium salts. One electrolyte salt may be used alone, or a plurality of electrolyte salts may be mixed and used.
The electrolyte salt is usually contained in the organic electrolyte at a concentration of 0.5 to 3 mol / liter, preferably 0.8 to 2 mol / liter, more preferably 1.0 to 1.6 mol / liter. It is desirable.
電解質塩は、通常、０．５～３モル／リットル、好ましくは０．８～２モル／リットル、より好ましくは１．０～１．６モル／リットルの濃度で有機系電解質中に含まれていることが望ましい。 As the electrolyte salt, e.g., lithium hexafluorophosphate (LiPF 6), lithium tetrafluoroborate (LiBF 4), lithium hexafluoroarsenate (LiAsF 6), lithium hexafluoro antimonate (LiSbF 6) , Inorganic lithium salts such as lithium perchlorate (LiClO 4 ) and lithium tetrachloroaluminate (LiAlCl 4 ), and lithium trifluoromethanesulfonate (CF 3 SO 3 Li), lithium bis (trifluoromethanesulfone) imide [(CF 3 SO 2 ) 2 NLi], lithium bis (pentafluoroethanesulfone) imide [(C 2 F 5 SO 2 ) 2 NLi] and lithium tris (trifluoromethanesulfone) methide [(CF 3 SO 2 ) 3 CLi] Of perfluoroalkanesulfonic acid derivatives Lithium salts. One electrolyte salt may be used alone, or a plurality of electrolyte salts may be mixed and used.
The electrolyte salt is usually contained in the organic electrolyte at a concentration of 0.5 to 3 mol / liter, preferably 0.8 to 2 mol / liter, more preferably 1.0 to 1.6 mol / liter. It is desirable.
電解質へは本発明による化合物の他に、例えば、ビニレンカーボネート、フルオロエチレンカーボネート、ビニルエチレンカーボネート、１，３－プロパンスルトン、エチレンサルファイトなどの電極保護材等を含有させてもよい。
In addition to the compound according to the present invention, the electrolyte may contain an electrode protective material such as vinylene carbonate, fluoroethylene carbonate, vinyl ethylene carbonate, 1,3-propane sultone, ethylene sulfite, and the like.
また、本発明は、前記した本発明の有機系電解質を用いた有機系電解質蓄電池を提供する。
The present invention also provides an organic electrolyte storage battery using the above-described organic electrolyte of the present invention.
本発明の有機系電解質蓄電池において、正極活物質としてはリチウムを吸蔵、放出可能な材料であれば用いることができる。例えば、リチウム含有複合酸化物ＬｉＭＯ２（ＭはＭｎ、Ｆｅ、Ｃｏ、Ｎｉなどの金属より選ばれる１種のみ、または２種以上の混合物であり、一部をＭｇ、Ａｌ、Ｔｉなどその他カチオンで置換してもよい）、ＬｉＭｎ２Ｏ４、ＬｉＮｉ０．５Ｍｎ１．５Ｏ４などや、ＬｉＦｅＰＯ４、ＬｉＭｎＰＯ４などに代表されるオリビン型材料を用いることもできる。その他、Ｌｉ２ＭｎＯ３、Ｌｉ２ＭＳｉＯ４（Ｍは金属）などのリチウム過剰系材料も用いることができる。
正極としては、リチウムと遷移金属が含まれるものが好ましく、特にコバルトを含む層状酸化物が含まれることが好ましい。 In the organic electrolyte storage battery of the present invention, any material that can occlude and release lithium can be used as the positive electrode active material. For example, the lithium-containing composite oxide LiMO 2 (M is one kind selected from metals such as Mn, Fe, Co, Ni, or a mixture of two or more kinds, and some of them are other cations such as Mg, Al, Ti, etc. Olivine type materials represented by LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , LiFePO 4 , LiMnPO 4, etc. can also be used. In addition, lithium-rich materials such as Li 2 MnO 3 and Li 2 MSiO 4 (M is a metal) can also be used.
The positive electrode preferably contains lithium and a transition metal, and particularly preferably contains a layered oxide containing cobalt.
正極としては、リチウムと遷移金属が含まれるものが好ましく、特にコバルトを含む層状酸化物が含まれることが好ましい。 In the organic electrolyte storage battery of the present invention, any material that can occlude and release lithium can be used as the positive electrode active material. For example, the lithium-containing composite oxide LiMO 2 (M is one kind selected from metals such as Mn, Fe, Co, Ni, or a mixture of two or more kinds, and some of them are other cations such as Mg, Al, Ti, etc. Olivine type materials represented by LiMn 2 O 4 , LiNi 0.5 Mn 1.5 O 4 , LiFePO 4 , LiMnPO 4, etc. can also be used. In addition, lithium-rich materials such as Li 2 MnO 3 and Li 2 MSiO 4 (M is a metal) can also be used.
The positive electrode preferably contains lithium and a transition metal, and particularly preferably contains a layered oxide containing cobalt.
負極には、人造黒鉛または天然黒鉛を含む炭素系負極材料が用いられる。
負極活物質としては、リチウムが挿入可能なもしくはリチウムと反応する負極活物質が用いられる。かかる負極活物質としては、黒鉛を主体とするが、非晶質炭素などの炭素材料、あるいはＬｉ金属、Ｓｉ、Ｓｎ、Ａｌ、などのＬｉと合金を形成する材料、Ｓｉ酸化物、ＳｉとＳｉ以外の他金属元素を含むＳｉ複合酸化物、Ｓｎ酸化物、ＳｎとＳｎ以外の他金属元素を含むＳｎ複合酸化物、Ｌｉ４Ｔｉ５Ｏ１２などを混合して用いてもよい。 A carbon-based negative electrode material containing artificial graphite or natural graphite is used for the negative electrode.
As the negative electrode active material, a negative electrode active material into which lithium can be inserted or reacts with lithium is used. As such a negative electrode active material, graphite is mainly used, but a carbon material such as amorphous carbon, or a material that forms an alloy with Li, such as Li metal, Si, Sn, Al, Si oxide, Si and Si. Si composite oxides containing other metal elements than the above, Sn oxides, Sn composite oxides containing other metal elements other than Sn and Sn, Li 4 Ti 5 O 12, and the like may be mixed and used.
負極活物質としては、リチウムが挿入可能なもしくはリチウムと反応する負極活物質が用いられる。かかる負極活物質としては、黒鉛を主体とするが、非晶質炭素などの炭素材料、あるいはＬｉ金属、Ｓｉ、Ｓｎ、Ａｌ、などのＬｉと合金を形成する材料、Ｓｉ酸化物、ＳｉとＳｉ以外の他金属元素を含むＳｉ複合酸化物、Ｓｎ酸化物、ＳｎとＳｎ以外の他金属元素を含むＳｎ複合酸化物、Ｌｉ４Ｔｉ５Ｏ１２などを混合して用いてもよい。 A carbon-based negative electrode material containing artificial graphite or natural graphite is used for the negative electrode.
As the negative electrode active material, a negative electrode active material into which lithium can be inserted or reacts with lithium is used. As such a negative electrode active material, graphite is mainly used, but a carbon material such as amorphous carbon, or a material that forms an alloy with Li, such as Li metal, Si, Sn, Al, Si oxide, Si and Si. Si composite oxides containing other metal elements than the above, Sn oxides, Sn composite oxides containing other metal elements other than Sn and Sn, Li 4 Ti 5 O 12, and the like may be mixed and used.
セパレータは、電気絶縁性の多孔体から形成されていればよく、例えば、ポリエチレン、ポリプロピレン等のポリオレフィン、ポリエステル、ポリエチレンテレフタレート、ポリイミドなどのポリマー製の膜または繊維不織布が挙げられる。材質は、単独でもよく複数種を用いてもよい。また、セパレータは単層でも良く、多層（複合化膜）であっても良い。また、セラミックなどの無機材料ナノ粒子を含有しても良い。
また、セパレータの両面にポリフッ化ビニリデン等の高分子化合物を塗布して用いても良い。 The separator should just be formed from the electrically insulating porous body, for example, polymer films, such as polyolefin, such as polyethylene and a polypropylene, polyester, polyethylene terephthalate, a polyimide, or a fiber nonwoven fabric. The material may be used alone or in combination. The separator may be a single layer or a multilayer (composite film). Moreover, you may contain inorganic material nanoparticles, such as a ceramic.
Moreover, you may apply | coat and use high molecular compounds, such as a polyvinylidene fluoride, on both surfaces of a separator.
また、セパレータの両面にポリフッ化ビニリデン等の高分子化合物を塗布して用いても良い。 The separator should just be formed from the electrically insulating porous body, for example, polymer films, such as polyolefin, such as polyethylene and a polypropylene, polyester, polyethylene terephthalate, a polyimide, or a fiber nonwoven fabric. The material may be used alone or in combination. The separator may be a single layer or a multilayer (composite film). Moreover, you may contain inorganic material nanoparticles, such as a ceramic.
Moreover, you may apply | coat and use high molecular compounds, such as a polyvinylidene fluoride, on both surfaces of a separator.
本発明の有機系電解質蓄電池では、有機溶媒により膨潤して有機系電解質を保持する保持体となる高分子化合物を含むことによりゲル状となった電解質を用いてもよい。有機溶媒により膨潤する高分子化合物を含むことにより高いイオン伝導率を得ることができ、優れた充放電効率が得られると共に、電池の漏液を防止することができるからである。有機系電解質に高分子化合物が含有されている場合、高分子化合物の含有量は、０．１質量％以上１０質量％以下の範囲内とすることが好ましい。
In the organic electrolyte storage battery of the present invention, an electrolyte that is gelled by containing a polymer compound that swells with an organic solvent and becomes a holding body that holds the organic electrolyte may be used. This is because by including a polymer compound that swells with an organic solvent, high ionic conductivity can be obtained, excellent charge / discharge efficiency can be obtained, and battery leakage can be prevented. When the organic electrolyte contains a polymer compound, the content of the polymer compound is preferably in the range of 0.1% by mass to 10% by mass.
また、セパレータの両面にポリフッ化ビニリデン等の高分子化合物を塗布して用いる場合は、有機系電解質と高分子化合物の質量比を５０：１～１０：１の範囲内とすることが好ましい。この範囲内とすることにより、より高い充放電効率が得られる。
In addition, when a polymer compound such as polyvinylidene fluoride is applied to both sides of the separator, the mass ratio of the organic electrolyte to the polymer compound is preferably in the range of 50: 1 to 10: 1. By setting it within this range, higher charge / discharge efficiency can be obtained.
前記高分子化合物としては、例えば、ポリビニルホルマール、ポリエチレンオキサイド並びにポリエチレンオキサイドを含む架橋体などのエーテル系高分子化合物、ポリメタクリレートなどのエステル系高分子化合物、アクリレート系高分子化合物、およびポリフッ化ビニリデン、並びにフッ化ビニリデンとヘキサフルオロプロピレンとの共重合体などのフッ化ビニリデンの重合体が挙げられる。高分子化合物は１種を単独で用いてもよく、複数種を混合して用いてもよい。特に、高温保存時の膨潤防止効果の観点からは、ポリフッ化ビニリデンなどのフッ素系高分子化合物を用いることが望ましい。
Examples of the polymer compound include polyvinyl formal, polyethylene oxide, and ether-based polymer compounds such as crosslinked products containing polyethylene oxide, ester-based polymer compounds such as polymethacrylate, acrylate-based polymer compounds, and polyvinylidene fluoride, In addition, a vinylidene fluoride polymer such as a copolymer of vinylidene fluoride and hexafluoropropylene may be used. A high molecular compound may be used individually by 1 type, and multiple types may be mixed and used for it. In particular, from the viewpoint of the effect of preventing swelling during high temperature storage, it is desirable to use a fluorine-based polymer compound such as polyvinylidene fluoride.
一般に電池を充電する際の電圧（充電電圧）が高ければ高いほどより多くの電力を電池に充電することができ、また放電時の出力も向上させることができる。一方、充電電圧が高いと電極材料等の劣化を招きやすく、繰り返し性の低下や安全性や経済性の点で問題がある。このことから有機系電解質蓄電池の充電電圧は現状４．１０～４．２０Ｖが一般的である。しかし本発明の有機系電解質蓄電池は高い耐久性を有するためより高い充電電圧を採用できる。具体的には４．２０Ｖより高く、好ましくは４．２５Ｖ以上、より好ましくは４．３５Ｖ以上、さらに好ましくは４．４５Ｖ以上の充電電圧で使用することができる。
Generally, the higher the voltage (charging voltage) when charging a battery, the more power can be charged into the battery, and the output during discharging can be improved. On the other hand, when the charging voltage is high, the electrode material and the like are liable to be deteriorated, and there are problems in terms of reduction in repeatability, safety and economy. Therefore, the current charging voltage of the organic electrolyte storage battery is generally 4.10 to 4.20V. However, since the organic electrolyte storage battery of the present invention has high durability, a higher charging voltage can be adopted. Specifically, it can be used at a charging voltage higher than 4.20V, preferably 4.25V or higher, more preferably 4.35V or higher, and still more preferably 4.45V or higher.
以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
なお、ここでは図１を用いてコイン型の有機系電解質蓄電池について説明するが、本発明の有機系電解質蓄電池のタイプはコイン型に限定されるものではなく、例えば、ボタン型、パウチ型、角型、あるいはスパイラル構造を有する筒型などの有機系電解質蓄電池に適用することもできる。また、有機系電解質蓄電池の大きさも任意であり、大型、小型または薄型としてもよい。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Here, the coin type organic electrolyte storage battery will be described with reference to FIG. 1, but the type of the organic electrolyte storage battery of the present invention is not limited to the coin type. For example, the button type, the pouch type, the corner type, etc. The present invention can also be applied to organic electrolyte storage batteries such as a mold or a cylinder having a spiral structure. The size of the organic electrolyte storage battery is also arbitrary, and may be large, small, or thin.
なお、ここでは図１を用いてコイン型の有機系電解質蓄電池について説明するが、本発明の有機系電解質蓄電池のタイプはコイン型に限定されるものではなく、例えば、ボタン型、パウチ型、角型、あるいはスパイラル構造を有する筒型などの有機系電解質蓄電池に適用することもできる。また、有機系電解質蓄電池の大きさも任意であり、大型、小型または薄型としてもよい。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Here, the coin type organic electrolyte storage battery will be described with reference to FIG. 1, but the type of the organic electrolyte storage battery of the present invention is not limited to the coin type. For example, the button type, the pouch type, the corner type, etc. The present invention can also be applied to organic electrolyte storage batteries such as a mold or a cylinder having a spiral structure. The size of the organic electrolyte storage battery is also arbitrary, and may be large, small, or thin.
図１は、コイン型の有機系電解質蓄電池の構造を示す模式断面図である。この電池は、正極１２と負極１４とがセパレータ１５を介して積層されたものである。正極１２、負極１４およびセパレータ１５はいずれも円板状であり、金属製の外装部品１１および外装部品１３によって画成される空間内に収容されている。外装部品１１、１３の内部は有機系電解質が満たされており、外装部品１１、１３の周縁部はシールガスケット１７を介してかしめられることにより密閉されている。なお、外装部品１３と負極１４の間には金属製のバネ１８とスペーサ１９が配置されている。
FIG. 1 is a schematic cross-sectional view showing the structure of a coin-type organic electrolyte storage battery. In this battery, a positive electrode 12 and a negative electrode 14 are laminated via a separator 15. Each of the positive electrode 12, the negative electrode 14, and the separator 15 has a disk shape, and is accommodated in a space defined by the metal exterior component 11 and the exterior component 13. The interiors of the exterior parts 11 and 13 are filled with an organic electrolyte, and the peripheral parts of the exterior parts 11 and 13 are sealed by caulking through a seal gasket 17. A metal spring 18 and a spacer 19 are disposed between the exterior component 13 and the negative electrode 14.
正極は以下のように作製した。活物質：ＬｉＮｉ１／３Ｍｎ１／３Ｃｏ１／３Ｏ２ ９０重量パーセント、導電助剤：アセチレンブラック５重量パーセント、結着材：ポリフッ化ビニリデン５重量パーセントの混合物にＮ－メチルピロリドン（以下、ＮＭＰと略す）を加え、混練し、スラリーを作製した。作製したスラリーをアルミニウム集電体上に滴下し、マイクロメーター付フィルムアプリケーターおよび自動塗工機を用いて製膜し、オーブン中１００℃、窒素雰囲気下にて乾燥させた。作製した正極を直径１５ｍｍの円形に打ち抜いた後、プレスを行った。正極活物質量は約１６ｍｇであった。
The positive electrode was produced as follows. Active material: LiNi 1/3 Mn 1/3 Co 1/3 O 2 90 weight percent, conductive additive: acetylene black 5 weight percent, binder: polyvinylidene fluoride 5 weight percent in a mixture of N-methylpyrrolidone (hereinafter And abbreviated as NMP) and kneaded to prepare a slurry. The prepared slurry was dropped onto an aluminum current collector, formed into a film using a film applicator with a micrometer and an automatic coating machine, and dried in an oven at 100 ° C. in a nitrogen atmosphere. The produced positive electrode was punched into a circle having a diameter of 15 mm, and then pressed. The amount of the positive electrode active material was about 16 mg.
負極は以下のように作製した。活物質：人造黒鉛９４重量パーセント、導電助剤：アセチレンブラック１重量パーセント、結着材：ポリフッ化ビニリデン５重量パーセントの混合物にＮＭＰを加え、混練し、スラリーを作製した。作製したスラリーを銅集電体上に滴下し、マイクロメーター付フィルムアプリケーターおよび自動塗工機を用いて製膜し、オーブン中１１０℃、窒素雰囲気下にて乾燥させた。作製した負極を直径１５ｍｍの円形に打ち抜いた後、プレスを行った。負極活物質量は約１０ｍｇであった。
The negative electrode was produced as follows. NMP was added to a mixture of active material: 94% by weight of artificial graphite, conductive auxiliary agent: 1% by weight of acetylene black, binder: 5% by weight of polyvinylidene fluoride, and kneaded to prepare a slurry. The prepared slurry was dropped on a copper current collector, formed into a film using a film applicator with a micrometer and an automatic coating machine, and dried in an oven at 110 ° C. in a nitrogen atmosphere. The produced negative electrode was punched into a circle having a diameter of 15 mm, and then pressed. The amount of the negative electrode active material was about 10 mg.
上述の方法で作製した正極、負極と円形に打ち抜いた、厚さ２５マイクロメートルのポリプロピレン製のセパレータ、および種々調製した有機系電解質を用いてコイン型蓄電池を作製した。有機溶媒には、高誘電率溶媒と低粘度溶媒を使用し、これらをそれぞれ所定の体積比で混合した溶媒にＬｉＰＦ６を１モル／リットルの割合で溶解させた。また化合物の純度は全て９７％以上とした。高誘電率溶媒にはエチレンカーボネート（以下ＥＣと略す）を用い、低粘度溶媒には、ジエチルカーボネート（以下ＤＥＣと略す）、もしくはエチルメチルカーボネート（以下ＥＭＣと略す）、またはジメチルカーボネート（以下ＤＭＣと略す）を用いた。
A coin-type storage battery was produced using a positive electrode produced by the above-described method, a negative electrode made of a polypropylene separator having a thickness of 25 micrometers punched out in a circular shape, and various organic electrolytes. As the organic solvent, a high dielectric constant solvent and a low viscosity solvent were used, and LiPF 6 was dissolved at a rate of 1 mol / liter in a solvent in which these were mixed at a predetermined volume ratio. The purity of all the compounds was 97% or more. Ethylene carbonate (hereinafter abbreviated as EC) is used as the high dielectric constant solvent, and diethyl carbonate (hereinafter abbreviated as DEC), ethyl methyl carbonate (hereinafter abbreviated as EMC), or dimethyl carbonate (hereinafter referred to as DMC) as the low viscosity solvent. (Abbreviated) was used.
（実施例１）
以下の表１に示すように有機系電解質を調製し、前記記載のようにコイン型蓄電池を作製した。 (Example 1)
An organic electrolyte was prepared as shown in Table 1 below, and a coin-type storage battery was produced as described above.
以下の表１に示すように有機系電解質を調製し、前記記載のようにコイン型蓄電池を作製した。 (Example 1)
An organic electrolyte was prepared as shown in Table 1 below, and a coin-type storage battery was produced as described above.
（比較例１）
以下の表２に示すように、化合物なし、および化合物を変えた有機系電解質を調整し、実施例１と同様にコイン型蓄電池を作製した。 (Comparative Example 1)
As shown in Table 2 below, a coin-type storage battery was prepared in the same manner as in Example 1 by adjusting the organic electrolyte without the compound and with the compound changed.
以下の表２に示すように、化合物なし、および化合物を変えた有機系電解質を調整し、実施例１と同様にコイン型蓄電池を作製した。 (Comparative Example 1)
As shown in Table 2 below, a coin-type storage battery was prepared in the same manner as in Example 1 by adjusting the organic electrolyte without the compound and with the compound changed.
（比較例２）
以下の表３に示すように、低粘度溶媒をＤＭＣに変更した有機系電解質を調整し、実施例１と同様にコイン型蓄電池を作製した。 (Comparative Example 2)
As shown in Table 3 below, an organic electrolyte in which the low-viscosity solvent was changed to DMC was prepared, and a coin-type storage battery was produced in the same manner as in Example 1.
以下の表３に示すように、低粘度溶媒をＤＭＣに変更した有機系電解質を調整し、実施例１と同様にコイン型蓄電池を作製した。 (Comparative Example 2)
As shown in Table 3 below, an organic electrolyte in which the low-viscosity solvent was changed to DMC was prepared, and a coin-type storage battery was produced in the same manner as in Example 1.
（実施例２）
以下の表４に示すように高誘電率溶媒と低粘度溶媒の割合を変えた有機系電解質を調整し、実施例１と同様にコイン型蓄電池を作製した。 (Example 2)
As shown in Table 4 below, an organic electrolyte in which the ratio of the high dielectric constant solvent and the low viscosity solvent was changed was prepared, and a coin-type storage battery was produced in the same manner as in Example 1.
以下の表４に示すように高誘電率溶媒と低粘度溶媒の割合を変えた有機系電解質を調整し、実施例１と同様にコイン型蓄電池を作製した。 (Example 2)
As shown in Table 4 below, an organic electrolyte in which the ratio of the high dielectric constant solvent and the low viscosity solvent was changed was prepared, and a coin-type storage battery was produced in the same manner as in Example 1.
（比較例３）
以下の表５に示すように高誘電率溶媒と低粘度溶媒の割合を変えた有機系電解質を調整し、実施例１と同様にコイン型蓄電池を作製した。 (Comparative Example 3)
As shown in Table 5 below, an organic electrolyte in which the ratio of the high dielectric constant solvent and the low viscosity solvent was changed was prepared, and a coin-type storage battery was produced in the same manner as in Example 1.
以下の表５に示すように高誘電率溶媒と低粘度溶媒の割合を変えた有機系電解質を調整し、実施例１と同様にコイン型蓄電池を作製した。 (Comparative Example 3)
As shown in Table 5 below, an organic electrolyte in which the ratio of the high dielectric constant solvent and the low viscosity solvent was changed was prepared, and a coin-type storage battery was produced in the same manner as in Example 1.
上述の方法で作製したコイン型蓄電池およびパウチ型蓄電池を室温の恒温器内に設置し、充放電試験を行った。まず０．８４０ｍＡの定電流、４．４５Ｖの定電圧にて８時間充電を行った後、０．８４０ｍＡの定電流で３．００Ｖまで放電を行った。この時の放電容量を初期蓄電容量とする。初期充放電後、１．６８ｍＡの定電流、４．４５Ｖの定電圧にて４時間充電し、充電状態にて６０℃の恒温槽へ静置し、３週間高温保存した。保存後、１．６８ｍＡの電流で３．００Ｖまで放電、１．６８ｍＡの定電流、４．４５Ｖの定電圧にて４時間充電後、再度１．６８ｍＡの電流で３．００Ｖまで放電を行った。この時の放電容量を保存後蓄電容量とする。
各電池における初期蓄電容量および保存後蓄電容量を表６にまとめた。なお、比較１－４の電池は初期充放電時に劣化したため、保存試験は実施していない。 The coin-type storage battery and pouch-type storage battery produced by the above-described method were installed in a room temperature incubator, and a charge / discharge test was performed. First, the battery was charged at a constant current of 0.840 mA for 8 hours at a constant voltage of 4.45 V, and then discharged to 3.00 V at a constant current of 0.840 mA. The discharge capacity at this time is defined as the initial storage capacity. After the initial charge / discharge, the battery was charged with a constant current of 1.68 mA and a constant voltage of 4.45 V for 4 hours, left in a constant temperature bath at 60 ° C. in a charged state, and stored at a high temperature for 3 weeks. After storage, the battery was discharged to 3.00 V at a current of 1.68 mA, charged at a constant current of 1.68 mA for 4 hours at a constant voltage of 4.45 V, and then discharged again to 3.00 V at a current of 1.68 mA. . The discharge capacity at this time is defined as the storage capacity after storage.
Table 6 shows the initial storage capacity and the storage capacity after storage of each battery. Since the battery of Comparative 1-4 deteriorated during the initial charge / discharge, a storage test was not performed.
各電池における初期蓄電容量および保存後蓄電容量を表６にまとめた。なお、比較１－４の電池は初期充放電時に劣化したため、保存試験は実施していない。 The coin-type storage battery and pouch-type storage battery produced by the above-described method were installed in a room temperature incubator, and a charge / discharge test was performed. First, the battery was charged at a constant current of 0.840 mA for 8 hours at a constant voltage of 4.45 V, and then discharged to 3.00 V at a constant current of 0.840 mA. The discharge capacity at this time is defined as the initial storage capacity. After the initial charge / discharge, the battery was charged with a constant current of 1.68 mA and a constant voltage of 4.45 V for 4 hours, left in a constant temperature bath at 60 ° C. in a charged state, and stored at a high temperature for 3 weeks. After storage, the battery was discharged to 3.00 V at a current of 1.68 mA, charged at a constant current of 1.68 mA for 4 hours at a constant voltage of 4.45 V, and then discharged again to 3.00 V at a current of 1.68 mA. . The discharge capacity at this time is defined as the storage capacity after storage.
Table 6 shows the initial storage capacity and the storage capacity after storage of each battery. Since the battery of Comparative 1-4 deteriorated during the initial charge / discharge, a storage test was not performed.
（参考例１）
以下の表７に示すように有機系電解質を調整し、実施例１と同様にコイン型蓄電池を作製した。充電電圧を４．２０Ｖ（参考１－１～１－９）、もしくは４．３５Ｖ（参考１－１０～１－１８）に変更して各電池における初期蓄電容量および保存後蓄電容量を測定した。測定結果は表８にまとめた。 (Reference Example 1)
An organic electrolyte was prepared as shown in Table 7 below, and a coin-type storage battery was produced in the same manner as in Example 1. The charging voltage was changed to 4.20V (Reference 1-1 to 1-9) or 4.35V (Reference 1-10 to 1-18), and the initial storage capacity and the storage capacity after storage of each battery were measured. The measurement results are summarized in Table 8.
以下の表７に示すように有機系電解質を調整し、実施例１と同様にコイン型蓄電池を作製した。充電電圧を４．２０Ｖ（参考１－１～１－９）、もしくは４．３５Ｖ（参考１－１０～１－１８）に変更して各電池における初期蓄電容量および保存後蓄電容量を測定した。測定結果は表８にまとめた。 (Reference Example 1)
An organic electrolyte was prepared as shown in Table 7 below, and a coin-type storage battery was produced in the same manner as in Example 1. The charging voltage was changed to 4.20V (Reference 1-1 to 1-9) or 4.35V (Reference 1-10 to 1-18), and the initial storage capacity and the storage capacity after storage of each battery were measured. The measurement results are summarized in Table 8.
以上の結果より、高誘電率溶媒、およびジエチルカーボネートおよび／またはエチルメチルカーボネートを低粘度溶媒として用いた有機溶媒に、式（１）～（４）のいずれかで示される化合物を適量含有した本発明の有機系電解質は、高温保存後の蓄電容量を増加させる効果、すなわち耐久性を改善させる効果があることが明らかである。また、その耐久性ゆえ従来よりも高い充電電圧で使用することができる。
Based on the above results, a book containing an appropriate amount of a compound represented by any one of formulas (1) to (4) in a high dielectric constant solvent and an organic solvent using diethyl carbonate and / or ethyl methyl carbonate as a low viscosity solvent. It is apparent that the organic electrolyte of the invention has the effect of increasing the storage capacity after high temperature storage, that is, the effect of improving durability. Further, because of its durability, it can be used at a higher charging voltage than before.
本発明の有機系電解質は蓄電池の高温保存後の蓄電容量を増加させる効果があり、本発明の有機系電解質を用いた蓄電池を電気自動車に搭載した場合には電池の耐久性を向上させることで自動車の長期信頼性を向上させることが可能となる。
The organic electrolyte of the present invention has the effect of increasing the storage capacity of the storage battery after high-temperature storage, and when the storage battery using the organic electrolyte of the present invention is mounted on an electric vehicle, the durability of the battery is improved. It is possible to improve the long-term reliability of the automobile.
Claims (6)
- 高誘電率溶媒および低粘度溶媒からなる有機溶媒、並びに下記式（１）～（４）のいずれかで示される化合物を含有する有機電解質であって、低粘度溶媒がジエチルカーボネートおよび／またはエチルメチルカーボネートであり、有機溶媒中の低粘度溶媒の割合が７０容量％以上であることを特徴とする有機系電解質。
- 式（１）～（４）のいずれかで示される化合物が、有機系電解質中に０．０５～１０重量％配合されていることを特徴とする請求項１に記載の有機系電解質。 2. The organic electrolyte according to claim 1, wherein the compound represented by any one of formulas (1) to (4) is mixed in an amount of 0.05 to 10% by weight in the organic electrolyte.
- 式（１）～（４）のいずれかで示される化合物が、１，１－ジシクロヘキシルエタン、１－シクロヘキシル－１－（２，５－ジメチルシクロヘキル）エタン、１－シクロヘキシル－１－（２，３－ジメチルシクロヘキル）エタン、１－シクロヘキシル－１－（２，４－ジメチルシクロヘキル）エタン、１－シクロヘキシル－１－（４－エチルシクロヘキシル）エタン、１，３－ジシクロヘキシルプロパン、１，４－ジシクロヘキシルブタン、１，３－ジシクロヘキシルブタン、トランス－ヒドリンダンおよびシス－ヒドリンダンから選ばれる少なくとも１種であることを特徴とする請求項１または２に記載の有機系電解質。 The compound represented by any one of formulas (1) to (4) is 1,1-dicyclohexylethane, 1-cyclohexyl-1- (2,5-dimethylcyclohexyl) ethane, 1-cyclohexyl-1- (2, 3-dimethylcyclohexyl) ethane, 1-cyclohexyl-1- (2,4-dimethylcyclohexyl) ethane, 1-cyclohexyl-1- (4-ethylcyclohexyl) ethane, 1,3-dicyclohexylpropane, 1,4- 3. The organic electrolyte according to claim 1, wherein the organic electrolyte is at least one selected from dicyclohexylbutane, 1,3-dicyclohexylbutane, trans-hydrindane and cis-hydrindane.
- 請求項１～３のいずれかに記載の有機系電解質を用いたことを特徴とする有機系電解質蓄電池。 An organic electrolyte storage battery using the organic electrolyte according to any one of claims 1 to 3.
- 充電電圧が４．２０Ｖより高いことを特徴とする請求項４に記載の有機系電解質蓄電池。 The organic electrolyte storage battery according to claim 4, wherein the charging voltage is higher than 4.20V.
- 正極にコバルト、ニッケル、マンガンが含まれることを特徴とする請求項４または５に記載の有機系電解質蓄電池。 6. The organic electrolyte storage battery according to claim 4 or 5, wherein the positive electrode contains cobalt, nickel, and manganese.
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| JP2004111359A (en) * | 2002-07-24 | 2004-04-08 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution secondary battery and nonaqueous electrolytic solution |
| JP2012234834A (en) * | 2012-08-31 | 2012-11-29 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte for secondary battery, and nonaqueous electrolyte secondary battery |
| WO2013094603A1 (en) * | 2011-12-22 | 2013-06-27 | Ｊｘ日鉱日石エネルギー株式会社 | Organic electrolyte, and organic electrolyte storage battery |
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| JP2004111359A (en) * | 2002-07-24 | 2004-04-08 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution secondary battery and nonaqueous electrolytic solution |
| WO2013094603A1 (en) * | 2011-12-22 | 2013-06-27 | Ｊｘ日鉱日石エネルギー株式会社 | Organic electrolyte, and organic electrolyte storage battery |
| JP2012234834A (en) * | 2012-08-31 | 2012-11-29 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte for secondary battery, and nonaqueous electrolyte secondary battery |
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| EP4170772A4 (en) * | 2020-11-03 | 2024-05-01 | LG Energy Solution, Ltd. | Non-aqueous electrolyte for lithium secondary battery, and lithium secondary battery comprising same |
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