WO2012176871A1 - Batterie à électrolyte non aqueux, et électrolyte associé - Google Patents

Batterie à électrolyte non aqueux, et électrolyte associé Download PDF

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Publication number
WO2012176871A1
WO2012176871A1 PCT/JP2012/065968 JP2012065968W WO2012176871A1 WO 2012176871 A1 WO2012176871 A1 WO 2012176871A1 JP 2012065968 W JP2012065968 W JP 2012065968W WO 2012176871 A1 WO2012176871 A1 WO 2012176871A1
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Prior art keywords
electrolyte
group
electrolyte battery
battery
nonaqueous electrolyte
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PCT/JP2012/065968
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English (en)
Japanese (ja)
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孝敬 森中
夕季 近藤
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セントラル硝子株式会社
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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
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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 electrolyte for a non-aqueous electrolyte battery that imparts excellent high-temperature durability and output characteristics to a non-aqueous electrolyte battery, and a non-aqueous electrolyte battery using the same.
  • non-aqueous electrolyte batteries such as lithium ion batteries, lithium batteries, and lithium ion capacitors have been actively developed.
  • a non-aqueous electrolyte or a non-aqueous electrolyte quasi-solidified with a gelling agent is used as an ionic conductor.
  • the structure is as follows, and as the solvent, an aprotic solvent, for example, one or several kinds of mixed solvents selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, etc. are used.
  • Lithium salts such as LiPF 6 , LiBF 4 , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) 2 NLi, etc. are used as solutes.
  • Patent Document 1 proposes to improve battery characteristics by adding vinylene carbonate to an electrolytic solution.
  • the electrode is coated with a polymer film formed by polymerization of vinylene carbonate to prevent the electrolytic solution from decomposing on the electrode surface.
  • the internal resistance is increased and the input is increased.
  • Working against output characteristics is a challenge.
  • Patent Documents 2 and 3 describe that high-temperature cycle characteristics and output characteristics are improved by the effect of a film formed on the electrode interface when monofluorophosphate or difluorophosphate is added to the electrolyte. .
  • these effects are not yet sufficient, and the solubility of monofluorophosphate and difluorophosphate is low, so there is a risk of precipitation depending on the concentration, solvent composition, and temperature conditions.
  • the problem is that if the amount is reduced, the effect cannot be obtained.
  • Patent Document 4 describes the use of an imide salt having a sulfonic acid ester group as an electrolyte, but does not describe improvement in characteristics due to use as an additive.
  • Patent Document 5 describes that high voltage stability is improved when an imide salt having a sulfonic acid ester group containing a fluorine atom is used as an electrolyte. However, the effect is not yet sufficient, and there is no description about cycle characteristics and output characteristics.
  • the present invention improves the durability of this type of non-aqueous electrolyte battery, such as cycle characteristics and high-temperature storage stability of 45 ° C. or higher, and is used in large equipment such as electric vehicles, hybrid vehicles, fuel cell vehicle auxiliary power supplies, and power storage.
  • the present invention provides a non-aqueous electrolyte battery electrolyte and a non-aqueous electrolyte battery having more excellent output characteristics so that they can be used in a power storage system for applications requiring power.
  • a non-aqueous electrolyte comprising a positive electrode, a negative electrode made of lithium or a negative electrode material capable of occluding and releasing lithium, a non-aqueous organic solvent, and a solute.
  • the cycle characteristics, high-temperature storage stability, output characteristics, etc. can be improved by using a non-aqueous electrolyte battery electrolyte to which a specific compound group is added.
  • the present inventors have found a non-aqueous electrolyte battery electrolyte that can be used, and a non-aqueous electrolyte battery using the electrolyte, and have reached the present invention.
  • the present invention provides an electrolyte solution for a non-aqueous electrolyte battery comprising a non-aqueous organic solvent and a solute, and at least one selected from the first compound group consisting of monofluorophosphate and difluorophosphate as an additive.
  • R 1 and R 2 are each independently a linear or branched alkyl group or alkenyl group having 1 to 10 carbon atoms, a cycloalkyl group or cycloalkenyl group having 3 to 10 carbon atoms, and , At least one organic group selected from aryl groups having 6 to 10 carbon atoms, and a fluorine atom, an oxygen atom, or an unsaturated bond may be present in the organic group.
  • M is an alkali metal cation, alkaline earth metal cation, or onium cation, and n represents an integer having the same number as the valence of the corresponding cation.
  • an imide salt having a sulfonic acid ester group represented by the formula hereinafter, sometimes referred to as “sulfate ester imide” or simply “imide salt”).
  • the first electrolyte solution is characterized in that the addition amount of the first compound group is in the range of 0.01 to 5.0% by mass with respect to the electrolyte solution for a non-aqueous electrolyte battery. It may be a battery electrolyte (second electrolyte).
  • the amount of the imide salt having a sulfonate group represented by the general formula (I) is 0.01 to 10.0 mass with respect to the non-aqueous electrolyte battery electrolyte. % Non-aqueous electrolyte battery electrolyte solution (third electrolyte solution).
  • the counter cation of the first compound group is at least one counter cation selected from lithium ion, sodium ion, potassium ion, and tetraalkylammonium ion. It may be a non-aqueous electrolyte battery electrolyte solution (fourth electrolyte solution).
  • Any one of the first to fourth electrolytes is selected from the group consisting of LiPF 6 , LiBF 4 , (CF 3 SO 2 ) 2 NLi, and (C 2 F 5 SO 2 ) 2 NLi as the solute. It may be an electrolyte solution for a non-aqueous electrolyte battery (fifth electrolyte solution), characterized in that it is at least one solute.
  • the present invention also provides a non-aqueous electrolysis comprising at least a positive electrode, a negative electrode made of lithium or a negative electrode material capable of occluding and releasing lithium, and a non-aqueous electrolyte battery electrolyte comprising a non-aqueous organic solvent and a solute.
  • a liquid battery includes a non-aqueous electrolyte battery including any one of first to fifth electrolytes.
  • the electrolyte solution for non-aqueous electrolyte battery of the present invention improves the film characteristics of the electrode, and improves the durability of the non-aqueous electrolyte battery using the electrode, such as cycle characteristics and storage stability at a high temperature of 45 ° C or higher.
  • output characteristics can be improved in order to suppress an increase in internal resistance. Therefore, the electrolyte for a non-aqueous electrolyte battery of the present invention is more output from an electric vehicle, a hybrid vehicle, a fuel cell vehicle auxiliary power source, a power storage system, etc. It can be used for high battery.
  • the durability of the lithium secondary battery in a high temperature environment can be further improved, and more excellent. Output characteristics are shown. These performance improvements cannot be achieved by each of the first compound group and the imide salt represented by the general formula (I).
  • the electrolyte solution for a non-aqueous electrolyte battery of the present invention contains the first compound group, an imide salt having a sulfonate group represented by the general formula (I), a non-aqueous organic solvent, and a solute. . If necessary, other commonly known additives can be used in combination.
  • the first compound group used in the present invention is a compound consisting of a group consisting of a monofluorophosphate and a difluorophosphate, and each salt has an anion portion having a structure shown below.
  • the type of the counter cation as long as it does not impair the performance of the non-aqueous electrolyte battery electrolyte and non-aqueous electrolyte battery of the present invention, and various types can be selected. it can.
  • metal cations such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, silver, copper, and iron
  • onium cations such as tetraalkylammonium, tetraalkylphosphonium, and imidazolium derivatives.
  • lithium ion, sodium ion, potassium ion, and tetraalkylammonium ion are preferable from the viewpoint of helping ion conduction in the nonaqueous electrolyte battery.
  • the addition amount of the first compound group is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and further preferably 0.05% by mass with respect to the electrolyte solution for non-aqueous electrolyte batteries.
  • the upper limit is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and still more preferably 2.0% by mass or less. If the amount is less than 0.01% by mass, the effect of improving the cycle characteristics of the non-aqueous electrolyte battery, durability such as high temperature storage stability, and input / output characteristics may not be sufficiently obtained. If it exceeds 1, the ionic conductivity of the electrolyte for non-aqueous electrolyte batteries may be reduced and the internal resistance may be increased. As a result, the effect of improving the output characteristics may not be sufficiently obtained.
  • the lower limit of the amount of the imide salt having a sulfonic acid ester group represented by the general formula (I) used in the present invention is 0.01% by mass or more with respect to the electrolyte for a nonaqueous electrolyte battery.
  • the upper limit is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and still more preferably 0.03% by mass or more, more preferably 0.05% by mass or more. Is in the range of 2.0 mass% or less. If it is less than 0.01% by mass, the effects of improving the durability such as cycle characteristics and high-temperature storage stability of the non-aqueous electrolyte battery and suppressing the increase in internal resistance may not be obtained sufficiently, which is not preferable.
  • the addition ratio of the first compound group and the imide salt having a sulfonic acid ester group represented by the general formula (I) is not particularly limited, but the “first compound group /
  • the molar ratio of the “imide salt represented by the general formula (I)” is preferably 0.01 or more as a lower limit, more preferably 0.1 or more, and preferably 100 or less, more preferably 10 or less as an upper limit. It is. If the molar ratio exceeds 100, the durability improvement effect / input / output characteristic improvement effect may not be sufficiently obtained, and if it is less than 0.01, the durability improvement effect may not be sufficiently obtained. It is not preferable.
  • battery characteristics, particularly durability and output characteristics are each independent by the combined use of the first compound group and an imide salt having a sulfonate group represented by the general formula (I).
  • an imide salt having a sulfonate group represented by the general formula (I) Although the details of the mechanism of significant improvement compared to the case of adding in the above are not clear, both compounds form a film on the electrode to prevent degradation by oxidation-reduction of the electrolyte for non-aqueous electrolyte batteries and to prevent deterioration. The durability is improved by suppressing. Further, when these two types of compound groups coexist, a stronger protective film can be formed by a mixed film made of these two types of compounds.
  • the non-aqueous electrolyte battery electrolyte of the present invention is a large device such as an electric vehicle, a hybrid vehicle, a fuel cell vehicle auxiliary power source, and an electric power storage, and has a higher output than a power storage system for applications that require power. Can be used for batteries.
  • the type of the nonaqueous organic solvent used in the electrolyte solution for a nonaqueous electrolyte battery of the present invention is not particularly limited, and any nonaqueous organic solvent can be used.
  • Specific examples include cyclic carbonates such as propylene carbonate, ethylene carbonate and butylene carbonate, chain carbonates such as diethyl carbonate, dimethyl carbonate and ethyl methyl carbonate, cyclic esters such as ⁇ -butyrolactone and ⁇ -valerolactone, methyl acetate, propion Examples include chain esters such as methyl acid, cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and dioxane, chain ethers such as dimethoxyethane and diethyl ether, and sulfur-containing nonaqueous organic solvents such as dimethyl sulfoxide and sulfolane. .
  • the nonaqueous organic solvent used for this invention may be used individually by 1
  • the kind of solute used for the electrolyte solution for non-aqueous electrolyte batteries of the present invention is not particularly limited, and any lithium salt can be used. Specific examples include LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), LiC (SO 2 CF 3 ) 3 , LiPF 3 (C 3 F 7 ) 3 , LiB (CF 3 ) 4 , LiBF 3 (C 2 F 5 ) and the like An electrolyte lithium salt is mentioned.
  • LiPF 6 LiBF 4 , (CF 3 SO 2 ) 2 NLi, and (C 2 F 5 SO 2 ) 2 NLi are preferable in view of the energy density, output characteristics, life, etc. of the battery.
  • the concentration of these solutes is not particularly limited, but the lower limit is preferably 0.5 mol / L or more, more preferably 0.7 mol / L or more, still more preferably 0.9 mol / L or more, and the upper limit is It is preferably 2.5 mol / L or less, more preferably 2.2 mol / L or less, and still more preferably 2.0 mol / L or less. If the concentration is less than 0.5 mol / L, the ionic conductivity tends to decrease, and the cycle characteristics and output characteristics of the non-aqueous electrolyte battery tend to decrease. On the other hand, if the concentration exceeds 2.5 mol / L, the non-aqueous electrolyte battery is used. As the viscosity of the electrolyte increases, the ionic conductivity also tends to decrease, and the cycle characteristics and output characteristics of the nonaqueous electrolyte battery may be decreased.
  • non-aqueous electrolyte battery electrolyte in a quasi-solid state with a gelling agent or a crosslinked polymer as used in a non-aqueous electrolyte battery called a lithium polymer battery.
  • the non-aqueous electrolyte battery according to the present invention is characterized by using the above-described electrolyte for a non-aqueous electrolyte battery according to the present invention, and the other components are those used in general non-aqueous electrolyte batteries. Is used. That is, it comprises a positive electrode and a negative electrode capable of inserting and extracting lithium, a current collector, a separator, a container and the like.
  • the negative electrode material is not particularly limited, but lithium metal, alloys of lithium and other metals and intermetallic compounds, various carbon materials, artificial graphite, natural graphite, metal oxide, metal nitride, tin (single), A tin compound, silicon (simple substance), a silicon compound, activated carbon, a conductive polymer, or the like is used.
  • the positive electrode material is not particularly limited.
  • lithium-containing transition metal composite oxides such as LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , and lithium-containing transition metals
  • LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 lithium-containing transition metals
  • LiFePO 4 LiCoPO 4
  • LiCoPO 4 LiCoPO 4 called olivine
  • Transition metal phosphate compounds such as LiMnPO 4, oxides such as TiO 2 , V 2 O 5 and MoO 3
  • sulfides such as TiS 2 and FeS
  • conductivity such as polyacetylene, polyparaphenylene, polyaniline and polypyrrole Polymers, activated carbon, polymers that generate radicals, carbon materials, and the like are used.
  • acetylene black, ketjen black, carbon fiber, graphite as a conductive material, polytetrafluoroethylene, polyvinylidene fluoride, SBR resin, etc. as a binder to the positive electrode or negative electrode material, and forming into a sheet shape It can be an electrode sheet.
  • a separator for preventing contact between the positive electrode and the negative electrode a nonwoven fabric or a porous sheet made of polypropylene, polyethylene, paper, glass fiber, or the like is used.
  • a non-aqueous electrolyte battery having a coin shape, a cylindrical shape, a square shape, an aluminum laminate sheet type or the like is assembled from the above elements.
  • LiPF 6 is 1.0 mol / L as a solute in a mixed solvent of ethylene carbonate and ethylmethyl carbonate in a volume ratio of 3: 7, 1.0% by mass of lithium difluorophosphate from the first compound group, and bis (ethyl An electrolyte for a non-aqueous electrolyte battery was prepared so that the amount of sulfonate lithium imide was 1.0% by mass.
  • a cell was prepared using LiCoO 2 as a positive electrode material and graphite as a negative electrode material, and a battery charge / discharge test was actually performed.
  • the test cell was produced as follows.
  • a charge / discharge test was conducted at an ambient temperature of 60 ° C. using the cell produced by the above method, and the cycle characteristics and output characteristics were evaluated. Charging is performed at 4.2V, discharging is performed at 3.0V, and a constant current / constant voltage method is used for 1C (the rated capacity at 1 hour discharge capacity is 1C, and the same applies hereinafter). The charge / discharge cycle was repeated. A value expressed as a percentage of the discharge capacity after 500 cycles with respect to the initial discharge capacity was defined as the capacity maintenance rate. After 500 cycles, the battery was charged at a constant current constant voltage method at an ambient temperature of 25 ° C.
  • Examples 2 to 14, Comparative Examples 1 to 8 The type of the first compound group used in Example 1, the concentration of the first compound group, the type of sulfate ester imide, and the concentration of sulfate ester imide were changed as shown in Table 1, and non-aqueous as in Example 1 An electrolyte solution for an electrolyte battery was prepared and a cell was prepared, and a charge / discharge test was performed. The results are shown in Table 1.
  • Examples 15 to 19, Comparative Examples 9 to 15 The negative electrode body used in Example 1 was changed, and the type of sulfate imide, the concentration of the first compound group and the concentration of sulfate imide used in Example 1 were changed as shown in Table 2, In the same manner as in Example 1, a non-aqueous electrolyte battery electrolyte and a cell were prepared, and a charge / discharge test was performed.
  • the negative electrode active material is Li 4 Ti 5 O 12
  • the negative electrode body is composed of 90% by mass of Li 4 Ti 5 O 12 powder and 5% by mass of polyfluoride as a binder.
  • PVDF vinylidene chloride
  • acetylene black as a conductive agent
  • the negative electrode body is composed of 80% by mass of silicon powder, 5% by mass of polyvinylidene fluoride (PVDF) as a binder, 15% by mass of acetylene black was mixed as a conductive material, N-methylpyrrolidone was further added, and the resulting paste was applied on a copper foil and dried to produce a charge end voltage and discharge during battery evaluation.
  • the end voltage was the same as in Example 1.
  • Table 2 shows the evaluation results of the cycle characteristics and output characteristics of the battery cells.
  • Example 20 to 25 Comparative Examples 16 to 27
  • the positive electrode body and the negative electrode body used in Example 1 were changed, and the type of sulfate ester imide, the concentration of the first compound group, and the concentration of sulfate ester imide used in Example 1 were changed as shown in Table 2. Then, in the same manner as in Example 1, a non-aqueous electrolyte battery electrolyte solution and a cell were prepared, and a charge / discharge test was performed.
  • the positive electrode body whose positive electrode active material is LiNi 1/3 Mn 1/3 Co 1/3 O 2 is 5% by mass as a binder in 90% by mass of LiNi 1/3 Mn 1/3 Co 1/3 O 2 powder.
  • Example 18 As in Example 18, in Examples 24 to 25 and Comparative Examples 24 to 27 in which the negative electrode active material is silicon (single substance), the charge end voltage at the time of battery evaluation was 4.3 V, and the discharge end voltage was 3.0 V. did. Table 2 shows the evaluation results of the cycle characteristics and output characteristics of the battery cells.
  • Examples 26 to 27, Comparative Examples 28 to 31 The positive electrode used in Example 1 was changed, and the type of sulfate imide, the concentration of the first compound group, and the concentration of sulfate imide used in Example 1 were changed as shown in Table 2, In the same manner as in Example 1, a non-aqueous electrolyte battery electrolyte and a cell were prepared, and a charge / discharge test was performed.
  • the positive electrode body in which the positive electrode active material is LiFePO 4 is obtained by adding 90% by mass of LiFePO 4 powder coated with amorphous carbon to 5% by mass of polyvinylidene fluoride (PVDF) as a binder and 5% by mass of acetylene black as a conductive material. %, And further, N-methylpyrrolidone was added, and the resulting paste was applied on an aluminum foil and dried to produce a charge end voltage of 3.6 V and a discharge end voltage of battery evaluation. 2.0V. Table 2 shows the evaluation results of the cycle characteristics and output characteristics of the battery cells.
  • PVDF polyvinylidene fluoride
  • the electrolyte solution for a non-aqueous electrolyte battery of the present invention is used. It was confirmed that the cycle characteristics and output characteristics of the battery cells were superior to the corresponding comparative examples. Therefore, it was shown that by using the electrolyte for a non-aqueous electrolyte battery of the present invention, a non-aqueous electrolyte battery exhibiting excellent cycle characteristics and output characteristics can be obtained regardless of the type of the positive electrode active material.
  • the battery cell using the electrolyte for the non-aqueous electrolyte battery of the present invention the battery cell using the electrolyte for the non-aqueous electrolyte battery of the present invention. It was confirmed that the cycle characteristics and output characteristics were superior to the corresponding comparative examples. Therefore, it was shown that by using the electrolyte for a nonaqueous electrolyte battery of the present invention, a nonaqueous electrolyte battery exhibiting excellent cycle characteristics and output characteristics can be obtained regardless of the type of the negative electrode active material. .

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Abstract

L'invention concerne un électrolyte pour batterie à électrolyte non aqueux constitué par un solvant organique non aqueux et un soluté. Cet électrolyte est caractéristique en ce qu'il contient : au moins un composé choisi dans un premier groupe de composés constitué d'un difluorophosphate et d'un monofluorophosphate en tant qu'additif; et un sel d'imide possédant un groupe ester d'acide sulfonique représenté par la formule générale (I). (Dans la formule : R1 et R2 représentent, chacun de manière indépendante, au moins un groupe organique choisi parmi un groupe alkyle ou un groupe alcényle sous forme linéaire ou ramifiée de 1 à 10 atomes de carbone, un groupe cycloalkyle ou un groupe cycloalcényle de 3 à 10 atomes de carbone, et un groupe aryle de 6 à 10 atomes de carbone; dans ce groupe organique un atome de fluor, un atome d'oxygène, et une liaison insaturée peuvent être présents. M représente un cation de métal alcalin, un cation de métal alcalin terreux, ou un cation d'onium; et n représente un entier identique à la valence du cation.) Cet électrolyte permet de conférer à une batterie à électrolyte non aqueux des propriétés d'endurance sous de hautes températures et des caractéristiques de sortie qui sont excellentes.
PCT/JP2012/065968 2011-06-24 2012-06-22 Batterie à électrolyte non aqueux, et électrolyte associé WO2012176871A1 (fr)

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JP2011-140775 2011-06-24
JP2011140775 2011-06-24
JP2012127645A JP2013030465A (ja) 2011-06-24 2012-06-05 非水電解液電池用電解液及び非水電解液電池
JP2012-127645 2012-06-05

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JP6361486B2 (ja) 2014-12-01 2018-07-25 セントラル硝子株式会社 非水電解液電池用電解液、及びこれを用いた非水電解液電池
JP6665396B2 (ja) 2015-02-19 2020-03-13 セントラル硝子株式会社 非水電解液電池用電解液、及びこれを用いた非水電解液電池
WO2017111143A1 (fr) 2015-12-22 2017-06-29 セントラル硝子株式会社 Électrolyte pour une pile à électrolyte non aqueux et pile à électrolyte non aqueux dans laquelle ce dernier est utilisé
JP6245312B2 (ja) 2016-05-30 2017-12-13 セントラル硝子株式会社 非水系電解液二次電池用電解液及びそれを用いた非水系電解液二次電池
CN117954689A (zh) * 2017-12-06 2024-04-30 中央硝子株式会社 非水电解液电池用电解液和使用其的非水电解液电池
JP7168851B2 (ja) * 2017-12-06 2022-11-10 セントラル硝子株式会社 非水電解液電池用電解液及びそれを用いた非水電解液電池
KR102690813B1 (ko) * 2018-10-26 2024-08-02 삼성전자주식회사 리튬전지

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