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WO2023190273A1 - Solution électrolytique non aqueuse et dispositif électrochimique - Google Patents

Solution électrolytique non aqueuse et dispositif électrochimique Download PDF

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Publication number
WO2023190273A1
WO2023190273A1 PCT/JP2023/012070 JP2023012070W WO2023190273A1 WO 2023190273 A1 WO2023190273 A1 WO 2023190273A1 JP 2023012070 W JP2023012070 W JP 2023012070W WO 2023190273 A1 WO2023190273 A1 WO 2023190273A1
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substance
aqueous electrolyte
containing organic
organic solvent
solvent substance
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Japanese (ja)
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裕之 米丸
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Zeon Corp
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Zeon Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H01G11/80—Gaskets; Sealings
    • 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
    • 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
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/30—Arrangements for facilitating escape of gases
    • H01M50/342—Non-re-sealable arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • 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 a nonaqueous electrolyte that can be used in nonaqueous electrochemical devices such as lithium ion primary batteries, lithium ion secondary batteries, and capacitors, and to electrochemical devices that include the nonaqueous electrolyte.
  • electrochemical devices such as primary batteries, secondary batteries, and capacitors include an exterior body and contents sealed therein, such as electrolyte, electrodes, and separators, for realizing the functions of the device.
  • an electrolytic solution includes an ionic component that functions as a so-called electrolyte and a nonionic solvent component that primarily functions as a solvent.
  • a non-aqueous electrolytic solution containing a non-aqueous solvent as a solvent is often used.
  • Patent Document 1 It is known to use a so-called high-concentration electrolyte solution, which has an extremely high electrolyte concentration, as a non-aqueous electrolyte solution (for example, Patent Document 1).
  • Highly concentrated electrolytes have high chemical stability, electrochemical stability, and low volatility, but they also have disadvantages such as easy salt precipitation, low ionic conductivity at low temperatures, and low capacity retention. It may be disadvantageous. Highly concentrated electrolytes may also have low impregnability into other components such as separators and electrodes due to physical properties such as high viscosity.
  • an object of the present invention to provide a highly concentrated non-aqueous electrolyte that has high chemical and electrochemical stability and low volatility due to the high electrolyte concentration, while suppressing salt precipitation.
  • the object of the present invention is to provide a non-aqueous electrolyte having high ionic conductivity at low temperatures, high capacity retention, and high impregnating property; and an electrochemical device that enjoys such advantages.
  • the present inventor conducted studies to solve the above problems. As a result, the inventors discovered that the above-mentioned problems could be solved by employing specific components constituting a high-concentration non-aqueous electrolyte and blending them in specific proportions, thereby completing the present invention. That is, the present invention is as follows.
  • a non-aqueous electrolyte containing an ionic component and a non-ionic solvent component is a hetero element-containing organic solvent substance (A) which is an organic compound with a fluorination rate of less than 40%; and a fluorine-containing organic solvent substance (B), which is an organic compound with a fluorination rate of 40% or more,
  • the fluorine-containing organic solvent substance (B) contains a fluorine-containing organic solvent substance (Bx) which is a compound containing a ring structure composed of carbon atoms, a carbon-carbon unsaturated bond, or both of these in the molecule.
  • the proportion of the fluorine-containing organic solvent substance (Bx) in 100 volume% of the non-aqueous electrolyte is 10 volume% or more,
  • the molar amount of the hetero element-containing organic solvent substance (A) is within 5 times the cation amount of the ionic component, Non-aqueous electrolyte.
  • the nonionic solvent component contains the hetero element-containing organic solvent substance (A), the fluorine-containing organic solvent substance (B), or an additive (P) as another nonionic solvent component.
  • the ionic component contains a fluorine-containing sulfonylimide anion
  • the fluorine-containing sulfonylimide anion is a bisfluorosulfonylimide anion.
  • the ionic component contains a boron anion
  • the ionic component includes an ionic liquid.
  • the nonionic solvent component contains acetonitrile as the hetero element-containing organic solvent substance (A).
  • the nonionic solvent component contains one or more types selected from the group consisting of ethylene carbonate, fluorinated ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, and sulfolane as the hetero element-containing organic solvent substance (A).
  • the nonionic solvent component contains a flame retardant solvent substance (AR) as the hetero element-containing organic solvent substance (A),
  • the flame retardant solvent substance (AR) is a compound (R1) which is a phosphoric acid ester or a phosphite ester and has 1 to 6 carbon atoms per molecule, and the hydrogen of the compound (R1) is partially removed.
  • the non-aqueous electrolyte according to any one of (1) to (9), which is one or more selected from the group consisting of a fluorinated compound (R2) and a compound having a phosphazene ring (R3).
  • the nonionic solvent component contains a fluorine-containing organic solvent substance (C) other than the fluorine-containing organic solvent substance (Bx) as the fluorine-containing organic solvent substance (B), (1) to (12) )
  • An electrochemical device comprising the non-aqueous electrolyte according to any one of (1) to (14).
  • a highly concentrated non-aqueous electrolyte has high chemical stability, electrochemical stability and low volatility due to the high electrolyte concentration, while salt precipitation is suppressed and low temperature is achieved.
  • nonaqueous electrolytes that have high ionic conductivity, high capacity retention, and high impregnating properties; and electrochemical devices that enjoy such advantages.
  • FIG. 1 is a graph showing the results of Example 3.
  • FIG. 2 is a graph showing the results of Example 4.
  • the "anion amount” of an anion is the molar equivalent of the ion, for example, the anion amount for 1 mole of monovalent anions is 1 mole, and the anion amount for 1 mole of divalent anions is also 1 mole.
  • “Amount of cation” is also a molar equivalent.
  • the volume of a substance for determining the volume ratio and specific gravity is the volume at the temperature and pressure during the preparation and use of the non-aqueous electrolyte, specifically, the volume ratio at 25° C. and 1 atmosphere. Moreover, the boiling point is the temperature at 1 atmosphere.
  • solvent refers to not only a medium in a solution (i.e., a mixture of a liquid medium substance and a solute substance dissolved therein) but also a dispersion liquid (i.e., a liquid medium substance and a solute substance dissolved therein). (a mixture of a substance in a medium and a substance that is a dispersion present dispersed therein as solid particles or emulsion particles) and a medium in a mixture containing both a solute and a dispersion. Also includes.
  • Non-aqueous electrolyte The nonaqueous electrolyte of the present invention includes an ionic component and a nonionic solvent component.
  • the ionic component is a component that functions as an electrolyte in the electrolytic solution.
  • the ionic component is composed of one or more types of ionic substances. Ionic substances are commonly represented as anionic and cationic salts. Examples of anions and cations include various types known as constituents of electrolytes.
  • anions include F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , PF 6 ⁇ , AsF 6 ⁇ , BF 4 ⁇ , B(C 2 O 4 )F 2 ⁇ , B(C 2 O 4 ) 2 - , SbF 6 - , AlCl 4 - , ClO 4 - , CF 3 SO 3 - , C 4 F 9 SO 3 - , CF 3 COO - , (CF 3 CO) 2 N - , (CF 3 SO 2 ) 3 C - , (FSO 2 ) 2 N - (FSI, bisfluorosulfonylimide), (CF 3 SO 2 ) 2 N - (TFSI, bistrifluoromethanesulfonylimide), and (C 2 F 5 SO 2 ) N - are mentioned.
  • imide anions and boron-containing anions are particularly preferred from the viewpoint of obtaining a non-aqueous electrolyte having both heat resistance and oxidation resistance.
  • imide anion fluorine-containing sulfonylimide anions such as bisfluorosulfonylimide anion and bistrifluoromethanesulfonylimide anion are preferred from the viewpoint of ionic conductivity, and bisfluorosulfonylimide anion is particularly preferred.
  • the proportion of imide anions, especially fluorine-containing sulfonylimide anions, to the anions constituting the ionic component is 50 mol% or more. It is preferable that the proportion of boron anions to the anions constituting the ionic component is 50 mol % or more.
  • cations include Li + , Na + , Mg 2+ , TEA (triethylammonium cation), TBA (tributylammonium cation), and EMI (ethylmethylimidazolium cation).
  • the ionic component may include an ionic liquid as an ionic substance that constitutes the ionic component.
  • the ionic liquid is a salt composed of cations and anions, and is liquid at 25° C. and 1 atm, for example.
  • An example of an ionic liquid is EMI-TFSI.
  • the proportion of the ionic component and the solvent substance (A) in the non-aqueous electrolyte of the present invention is not particularly limited, but it should be a high proportion from the perspective of enjoying the advantages of a so-called high-concentration non-aqueous electrolyte. is preferred.
  • the proportion of the ionic component and the solvent substance (A) in the entire non-aqueous electrolyte is preferably 30% by volume or more, more preferably 40% by volume or more.
  • the nonionic solvent component is a component that functions as a solvent to maintain an appropriate concentration of ionic components in the electrolytic solution.
  • the nonionic solvent component includes one or more types of hetero element-containing organic solvent substances (A) and one or more types of fluorine-containing organic solvent substances (B). Below, these may be simply referred to as “solvent substance (A)” and “solvent substance (B).”
  • the solvent substance (A) is a substance containing a hetero element, and its fluorination rate is less than 40%.
  • the solvent substance (A) is a substance that is liquid and can function as a solvent in the environment in which the non-aqueous electrolyte is used.
  • heteroelements that the solvent substance (A) may contain include O, S, N, P and B.
  • the solvent substance (A) may contain O, N, or both as heteroelements.
  • One molecule of the solvent substance (A) may contain one or more hetero elements, and when it contains two or more hetero elements, they may be the same or different.
  • the nonionic solvent component may contain only one type of compound as the solvent substance (A), or may contain two or more types of compounds. When the nonionic solvent component contains two or more types of compounds as the solvent substance (A), desired physical properties of the nonaqueous electrolyte can be easily obtained by adjusting their types and proportions.
  • the solvent substance (A) may be a substance that has a cyclic molecular structure, or may be a substance that does not include a cyclic molecular structure and only has a chain-like molecular structure.
  • the solvent substance (A) may be a substance having a carbon-carbon unsaturated bond, or the solvent substance (A) may be a substance having no carbon-carbon unsaturated bond.
  • the solvent substance (A) is a substance whose fluorination rate is less than 40%.
  • the solvent substance (A) preferably has an oxidation-resistant polar group in its molecular structure.
  • R 1 and R 2 are independently a hydrogen atom or an organic substituent.
  • the organic substituent preferably has a bond extending from its carbon atom to the N atom.
  • Specific examples of R 1 and R 2 include a methyl group, an ethyl group, and a propyl group.
  • the solvent substance (A) include esters; acid anhydrides such as succinic anhydride, glutaric anhydride, itaconic anhydride, maleic anhydride, and diglycolic anhydride; acetone, ethyl Ketones such as methyl ketone, cyclopentanone, and cyclohexanone; Nitriles such as acetonitrile, propionitrile, valeronitrile, malononitrile, succinonitrile, glutaronitrile, adiponitrile, and various trinitrile compounds; Sulfoxides such as dimethyl sulfoxide Sulfones such as dimethylsulfone, ethylmethylsulfone, and diethylsulfone; Sultones such as propane sultone and butane sultone; Oxazoles such as oxazole; Isoxazoles such as isoxazole; Oxazolines such as methyloxazoline; Fura
  • esters include organic acid esters such as formate, acetate, propionate, ⁇ -butyrolactone, valerolactone, glycolide, lactide, dimethyl oxalate, diethyl oxalate, and dimethyl succinate; dimethyl carbonate, carbonic acid Carbonic esters such as diethyl, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, and fluorinated ethylene carbonate; Sulfuric esters such as dimethyl sulfate; Phosphite esters such as trimethyl phosphite and triethyl phosphite; Trimethyl phosphate, phosphorus Examples include phosphoric acid esters such as triethyl acid and tributyl phosphate; and boric acid esters such as trimethyl borate and triethyl borate.
  • organic acid esters such as formate, acetate, propionate, ⁇ -butyrolactone, valerolactone, glyco
  • a compound having two or more of the above characteristics can also be used as the solvent substance (A).
  • examples of such compounds include methyl cyanoacetate, ethyl cyanoacetate, methyl methanesulfonylacetate, methylsulfonylacetonitrile, methoxypropionitrile, and 3,3'-oxydipropionitrile.
  • the nonionic solvent component preferably contains acetonitrile as the solvent substance (A).
  • acetonitrile By using acetonitrile, the effect of excellent ionic conductivity at low temperatures can be obtained.
  • the nonaqueous electrolyte of the present invention in an electrochemical device containing a carbonaceous material as a negative electrode active material by using acetonitrile and an acid anhydride together, the current when using a carbonaceous material for the electrode can be increased. The effect of superior efficiency can be obtained.
  • the nonionic solvent component may contain, as the solvent substance (A), one or more selected from the group consisting of ethylene carbonate, fluorinated ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, and sulfolane. preferable.
  • solvent substance (A) one or more selected from the group consisting of ethylene carbonate, fluorinated ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, and sulfolane. preferable.
  • the nonionic solvent component includes a flame retardant solvent substance (AR) as the solvent substance (A).
  • the flame-retardant solvent substance (AR) is a compound (R1) that is a phosphoric acid ester or a phosphite ester and has 1 to 6 carbon atoms per molecule, and the hydrogen of the compound (R1) is partially fluorinated.
  • the compound is one or more selected from the group consisting of a compound (R2) having a phosphazene ring, and a compound (R3) having a phosphazene ring.
  • the compound (R1) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trisbutoxyethyl phosphate, and phosphorous esters corresponding to these.
  • the compound (R3) include Nippon Kagaku Kogyo Co., Ltd., trade names "Hishicolin-E”, “Hishicolin-O”, and "Hishicolin-D”.
  • the proportion of the flame retardant solvent substance (AR) in 100% by volume of the nonionic solvent component is preferably 5% by volume or more, more preferably 10% by volume or more, while preferably 25% by volume or less, more Preferably it is 20% by volume or less.
  • the proportion of the flame-retardant solvent substance (AR) By setting the proportion of the flame-retardant solvent substance (AR) to the above-mentioned lower limit or more, the flame retardancy of the non-aqueous electrolyte can be improved, and the safety of the electrochemical device can be improved.
  • the proportion of the flame-retardant solvent substance (AR) below the above-mentioned upper limit, an increase in the resistance of the device can be avoided.
  • the upper limit of the molar amount of the solvent substance (A) relative to the cation amount of the ionic component is within 5 times, preferably within 4 times, and more preferably within 3 times.
  • the effect of the solvent substance (B) can be favorably obtained.
  • the flammability of the non-aqueous electrolyte can be effectively reduced.
  • the lower limit of the molar amount of the solvent substance (A) relative to the cation amount of the ionic component can be 0.75 times or more, preferably 1.5 times or more, and more preferably 2.2 times or more.
  • the molar amount of the solvent substance (A) is at least this lower limit, the desired effect as an electrolytic solution can be satisfactorily expressed.
  • solvent substance (B) The solvent substance (B), like the solvent substance (A), can be a substance that is liquid and functions as a solvent in the environment in which the non-aqueous electrolyte is used.
  • the nonionic solvent component may contain only one type of substance or two or more types of substances as the solvent substance (B).
  • the solvent substance (B) has a fluorination rate of 40% or more.
  • the fluorination rate of the solvent substance is less than 100% (that is, it has one or more hydrogen atoms in the molecule).
  • the charge within the molecule becomes non-homogeneous, and the polarity becomes high, making it easier to create a highly concentrated electrolyte and a uniform solution.
  • the non-aqueous electrolyte of the present invention contains a solvent substance (Bx) as part or all of the solvent substance (B).
  • the solvent substance (Bx) contains a ring structure composed of carbon atoms, a carbon-carbon unsaturated bond, or both of these in its molecule. By having a ring structure, it is possible to obtain a higher boiling point than chain molecules with similar molecular size and atomic composition, and the molecule can have fewer hydrogen substitution sites, making it easy to achieve a high fluorination rate. Obtainable.
  • the solvent substance (Bx) has a carbon-carbon unsaturated bond, it can also be a molecule with fewer hydrogen substitution sites, making it easy to obtain a high fluorination rate.
  • the solvent substance (Bx) has a carbon-carbon unsaturated bond
  • the solvent substance (Bx) has a ring structure consisting of carbon atoms and contains a carbon-carbon unsaturated bond in the ring.
  • the ability of the non-aqueous electrolyte to protect the negative electrode can be enhanced, and as a result, for example, the effect of increasing the capacity retention rate of an electrochemical device containing the non-aqueous electrolyte can be obtained.
  • the solvent substance (Bx) contains a ring structure composed of carbon atoms, a carbon-carbon unsaturated bond, or both of these, and has a fluorination rate of 40% or more, ions are generated in the non-aqueous electrolyte. Precipitation of salts of chemical components can be suppressed. The reason for this is unknown, but one possible reason is that the solvent substance (Bx) is interposed between the anion and cation that constitute the salt and suppresses aggregation.
  • the solvent substance (Bx) has one or more structures selected from the group consisting of -CFH-, -CF 2 H, -CH 2 -CF 2 -, -CH 2 CF 3 and -O-, It is preferable that the molecule contains one or more, and more preferably two or more. By having these structures, the polarity of the solvent substance (B) molecules becomes high, and as a result, the above-mentioned effects can be better obtained.
  • the molecules of the solvent substance (Bx) may be molecules consisting only of carbon atoms, hydrogen atoms, oxygen atoms, and fluorine atoms, or may be molecules containing other atoms as well.
  • the solvent substance (Bx) may contain nitrogen atoms, phosphorus atoms, and sulfur atoms.
  • the solvent substance (Bx) may also contain halogen atoms other than fluorine atoms.
  • the solvent substance (Bx) preferably does not contain nitrogen atoms, phosphorus atoms, and sulfur atoms.
  • the molecules of the solvent substance (Bx) are carbon atoms, hydrogen atoms, etc. , a molecule consisting only of oxygen atoms and fluorine atoms is preferable.
  • the solvent substance (Bx) include compounds having a structure in which one or more hydrogen atoms in a hydrocarbon ring or a ring containing an oxygen atom are substituted with a fluorine atom or an organic substituent containing a fluorine atom.
  • the solvent substance and other substances are not limited by the manufacturing process thereof.
  • Preferred examples of the hydrocarbon ring include cyclopentane, cyclohexane, and cyclopentene.
  • the ring containing an oxygen atom is a ring composed of a carbon atom, a hydrogen atom, and an oxygen atom, and preferable examples thereof include tetrahydrofuran and tetrahydropyran.
  • substituents include halogen atoms such as fluorine atoms, alkyl groups, fluorinated alkyl groups, ether groups, ester groups, and hydroxyl groups.
  • solvent substances (Bx) preferable examples of those having a ring structure and those having both a ring structure and a carbon-carbon unsaturated bond include 1,1,2,2,3,3,4-heptafluorocyclo Pentane (fluorination rate: 70%), 3,3,4,4,5,5-hexafluorocyclopentene (fluorination rate: 75%), and 1-methoxy-2,3,3,4,4,5 , 5-heptafluorocyclopentene (fluorination rate: 70%).
  • the boiling point of the solvent substance (Bx) is preferably within a desired temperature range in order to adjust physical properties such as favorable handling properties and generation of internal pressure.
  • the boiling point of the solvent substance (Bx) is preferably 60°C or higher, more preferably 70°C or higher, even more preferably 80°C or higher, even more preferably 90°C or higher, while preferably 170°C or higher.
  • the temperature is preferably 150°C or lower, more preferably 150°C or lower.
  • the solvent substance (Bx) has no flash point. If the solvent substance (Bx) does not have a flash point, the entire non-aqueous electrolyte can easily also have no flash point. As a result, it is possible to reduce the risk of a fire occurring when the electrochemical device overheats for some reason and the non-aqueous electrolyte is released outside the device. "Having no flash point” means that it does not show a flash point at least in the flash point measurement method based on the tag sealing method (JIS K2265-1 (2007)), and more preferably the Cleveland open method (JIS K2265 -4 (2007)), it is evaluated that there is no flash point.
  • the solvent substance (Bx) has low reactivity with gases in the atmosphere. Specifically, it is preferable that the reactivity with gases (including water vapor) constituting the atmosphere is low. Since the solvent substance (Bx) has low reactivity with gases in the atmosphere, it is possible to reduce the danger when the non-aqueous electrolyte is released outside the device. Specifically, the proportion of molecules that are oxidized within 10 minutes after being released into the atmosphere at 25°C is 1% or less, or the proportion of molecules that are hydrolyzed is 1% or less, and more preferably both. preferable.
  • the solvent substance (Bx) has high solubility in water.
  • the lower limit of solubility in water is preferably 10 ppm or more, more preferably 100 ppm or more. When it has such high water solubility, it can easily dissolve ionic components at high concentrations.
  • the upper limit of solubility in water is not particularly limited, but may be, for example, 10,000 ppm or less.
  • the dielectric constant of the solvent substance (Bx) is preferably a large value.
  • the relative permittivity (measurement frequency: 1 kHz) is preferably 2.0 or more, more preferably 5 or more, even more preferably 8 or more, even more preferably 10 or more.
  • the upper limit of the dielectric constant is not particularly limited, but may be, for example, 50 or less.
  • the proportion of the solvent substance (Bx) in 100 volume% of the non-aqueous electrolyte is 10 volume% or more, preferably 20 volume% or more.
  • the solvent substance (Bx) has either a ring structure consisting of carbon atoms or a carbon-carbon unsaturated bond, has the above-mentioned specific fluorination rate, and is a solvent substance in the nonionic solvent component.
  • a non-aqueous electrolyte with high ion conductivity can be obtained, and in particular, the ion conductivity at low temperatures can be improved. Further, the viscosity of the non-aqueous electrolyte can be set within a desired low range. Furthermore, by increasing the proportion of the solvent substance (Bx) in the nonionic solvent component, the impregnation of the nonaqueous electrolyte into porous device components such as the electrode mixture layer and/or the separator is enhanced. be able to.
  • the proportion of the solvent substance (Bx) in 100 volume % of the non-aqueous electrolyte it is more preferable to set the proportion of the solvent substance (Bx) in 100 volume % of the non-aqueous electrolyte to a high value such as 50 volume % or more, since this can improve the safety of an electrochemical device containing the non-aqueous electrolyte. Specifically, since the volatility of the solvent in a highly concentrated electrolytic solution is generally suppressed, the internal pressure is unlikely to increase even if a device containing the electrolytic solution reaches a high temperature. Therefore, when an abnormality occurs inside the device, it is difficult for a user to detect the abnormality from the outside.
  • the non-aqueous electrolyte contains the solvent substance (Bx)
  • internal pressure can be generated at a temperature higher than a certain level, and the temperature at which the internal pressure is generated depends on the type and composition ratio of the solvent substance (Bx). Can be adjusted by selection.
  • the solvent substance (Bx) can be easily released outside the device. In this case, most of the electrolyte is lost, which makes it difficult for the ions to move, and the operation of the device slows down or stops, thereby ensuring high safety.
  • the non-aqueous electrolyte of the present invention contains, as a part of the solvent substance (B), a fluorine-containing solvent substance (C) which is a substance other than the solvent substance (Bx) (hereinafter also simply referred to as "solvent substance (C)"). ) may be included.
  • the solvent substance (C) is a compound having a fluorination rate of 40% or more and containing neither a ring structure composed of carbon atoms nor a carbon-carbon unsaturated bond in the molecule. By including the solvent substance (C), it is possible to easily adjust the viscosity of the nonaqueous electrolyte to a desired range.
  • solvent substances (C) include various fluorinated alkanes and fluorinated ethers.
  • fluorinated alkanes include the trade name "Vertrell XF” (manufactured by Mitsui Chemours Fluoro Products Co., Ltd., 2H,3H-decafluoropentane); 6000'' (CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CH 2 CH 3 ) (manufactured by AGC).
  • fluorinated ethers examples include the trade name "Opteon SF-10" (manufactured by Mitsui Chemours Fluoro Products Co., Ltd.); Fluoroethyl 2,2,2-trifluoroethyl ether); trade name “NOVEC7100” (CF 3 CF 2 CF 2 CF 2 OCH 3 ), "NOVEC 7200” (CF 3 (CF 2 ) 3 0CH 2 CH 3 and CF 3 C(-CF 3 )(-F)CF 2 OCH 2 CH 3 mixture), “NOVEC7300”(CF 3 CF 2 C(-OCH 3 )(-F)C(-CF 3 ) 2 (-F)) , "NOVEC7500” and “NOVEC7600” (manufactured by 3M); and “Galden” (manufactured by Solvay, perfluoropolyether).
  • Opteon SF-10 manufactured by Mitsui Chemours Fluoro Products
  • fluorinated ethers include CF3CHFCF2OCH2CF2CHF2 , CHF2CF2CH2OCF2CHF2 , CF3CHFCF2CH2OCHF2 , CF3CHCF2OCH2CF2 CF 3 _ _ _ _ , CF3CHFCF2OCH2CF3 , CHF2CF2OCH2CF3 , CF3CHFCF2OCH3 , CF3CF2CH2OCHF2 , and CF3CH2OCH2CF3 .
  • the proportion of the solvent substance (A) in 100 volume % of the non-aqueous electrolyte may be 25 to 85 volume %.
  • the nonionic solvent component can include an additive (P) as a solvent material (A), a solvent material (B), or another nonionic solvent component.
  • the additive (P) is one selected from the group consisting of a cyclic sulfate compound (PA), a vinyl ethylene carbonate compound (PB), and a cyclic fluorine compound having an unsaturated bond (PC). It can be more than that.
  • cyclic sulfate compound (PA) examples include 1,3,2-dioxathiolane 2,2-dioxide (ethylene sulfate), 4-methyl-1,3,2-dioxathiolane 2,2-dioxide, and 1,3,2-dioxathiane 2,2-dioxide is mentioned.
  • Examples of the vinyl ethylene carbonate compound (PB) include compounds having a vinyl ethylene carbonate skeleton, such as 3-vinyl ethylene carbonate, 3,4-divinyl ethylene carbonate, and 3-ethynyl ethylene carbonate.
  • cyclic fluorine compounds having unsaturated bonds and ether bonds
  • PC cyclic fluorine compounds having unsaturated bonds and ether bonds
  • examples of cyclic fluorine compounds (PC) having unsaturated bonds and ether bonds include 3,3,4,4,5,5-hexafluorocyclopentene and 1-methoxy-2,3,3,4,4 , 5,5-heptafluorocyclopentene.
  • the nonionic solvent component contains the additive (P)
  • the current efficiency of the device is improved, for example, in the case of a lithium ion battery, the coulombic efficiency during charging and discharging is improved.
  • the amount of additive (P) added is preferably 0.01% by weight or more, more preferably 0.05% by weight or more based on 100% by weight of the nonionic solvent component, On the other hand, it is preferably 10% by weight or less, more preferably 7% by weight or less.
  • the proportion of the nonionic solvent component in 100% by weight of the non-aqueous electrolyte is preferably 30% by weight or more, more preferably 40% by weight or more, while preferably 95% by weight or less, more preferably 90% by weight or less. be.
  • the non-aqueous electrolyte of the present invention may contain arbitrary components in addition to the above-mentioned ionic components and non-ionic solvent components.
  • it may contain a polymer compound with a molecular weight of more than 1000. That is, while the solvent component usually has a molecular weight of 1000 or less, a polymer compound with a weight average molecular weight of more than 1000, preferably more than 10,000, which can be dissolved in the solvent component, is dissolved in the non-aqueous electrolyte. may exist.
  • the ionic conductivity and viscosity of the nonaqueous electrolyte may be adjusted to an appropriate range.
  • the proportion of the polymer compound in 100% by weight of the non-aqueous electrolyte is preferably 50% by weight or less.
  • polymer compounds include polyethylene oxide, polyethylene oxide-propylene oxide copolymers, and polyoxazoline polymers.
  • the non-aqueous electrolyte of the present invention preferably has no flash point. By not having a flash point, the safety of electrochemical devices containing non-aqueous electrolytes can be improved.
  • a non-aqueous electrolyte having no flash point can be obtained by appropriately selecting non-flammable or low combustible solvent substances from the above-exemplified components as the solvent substance (A) and the solvent substance (B).
  • the method for producing a non-aqueous electrolyte of the present invention is not particularly limited, and can be produced by mixing the components described above in an appropriate environment suitable for producing an electrolyte.
  • each component is not particularly limited, it is preferable that the ionic component and the solvent substance (A) are mixed first, and then the solvent substance (B) is further mixed into the resulting mixture.
  • the ionic component can be quickly dissolved and precipitation of the ionic component can be suppressed.
  • some of the components may be mixed in an amount larger than the target ratio, and then the components may be reduced by distilling off or the like.
  • each component is encapsulated inside the device in a state in which a portion of each component is solid, and then the solids are dissolved and mixed inside the device, so that each component is mixed at the target ratio.
  • a non-aqueous electrolyte can also be obtained.
  • part of the solvent substance (B) in a solid state is sealed inside a device along with other components in a liquid state, and then the solvent substance (B) is dissolved, and each component is mixed in a target ratio.
  • a water electrolyte can be obtained.
  • the electrochemical device of the present invention includes the non-aqueous electrolyte of the present invention described above. That is, the nonaqueous electrolyte of the present invention can be used as a component of an electrochemical device. Since the electrochemical device of the present invention contains the non-aqueous electrolyte of the present invention as an electrolyte, it can enjoy advantages such as high capacity retention, high operating performance at low temperatures, and high safety.
  • the electrochemical device of the present invention may include a device exterior and contents such as an electrode, a separator, and the nonaqueous electrolyte of the present invention, which are enclosed in a sealed space inside the device exterior.
  • the electrodes and separators are not particularly limited, and known electrodes and separators that are suitable for the use of the device can be appropriately employed.
  • the non-aqueous electrolyte of the present invention can be of low risk in the event that it leaks out of the device for some reason. It is possible to have a mechanism that releases the seal by the exterior when the temperature rises above a threshold value, so that the operation can be stopped when an abnormality occurs.
  • a threshold may be between 2 atmospheres and 10 atmospheres.
  • electrochemical devices of the present invention include various non-aqueous primary batteries, secondary batteries, electric double layer capacitors, electric double layer transistors, electrochromic display materials, electrochemical luminescent elements, electrochemical actuators, and dye-sensitized solar cells.
  • batteries include lithium primary batteries, lithium ion secondary batteries, lithium metal secondary batteries, sodium ion batteries, potassium ion batteries, magnesium ion batteries, aluminum ion batteries, fluoride ion batteries, and air batteries.
  • the battery is particularly preferably a lithium ion primary battery or a lithium ion secondary battery.
  • Impregnation evaluation A test was conducted to see if electrolytes (01) to (20) could be impregnated into a lithium ion battery separator.
  • a polyolefin separator manufactured by Polypore, product name "Celguard 2325"
  • the 1 cm tip was immersed in an electrolytic solution for 1 second to soak the separator. If the electrolyte penetrated into the site, it was evaluated as "impregnation”, and if it did not, it was evaluated as "not impregnated”. As a result, all cases were evaluated as not being impregnated.
  • LiFSI Lithium bisfluorosulfonylimide (Li + (FSO 2 ) 2 N ⁇ )
  • LiTFSI Lithium bistrifluoromethanesulfonylimide (Li + (CF 3 SO 2 ) 2 N ⁇ )
  • LiBF4 Lithium tetrafluoroborate
  • LiBr Lithium bromide
  • MgTFSI Magnesium bistrifluoromethanesulfonylimide (Mg 2+ ((CF 3 SO 2 ) 2 N ⁇ ) 2 )
  • EMI-TFSI 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide
  • the obtained electrolyte solution was observed to evaluate whether it was uniformly dissolved.
  • the results are shown in Table 2. In the examples, all electrolytic solutions were mixed uniformly, and no salt precipitation was observed. On the other hand, in some of the comparative examples, the electrolytic solution was separated into two layers.
  • a fluorine solvent substance (C) that does not have a cyclic structure or unsaturated bond instead of the solvent substance (B)
  • Solvent substance (Bx) addition amount Addition ratio of solvent substance to the total volume % of the entire non-aqueous electrolyte (unit: volume %)
  • Other solvent substances Types of solvent substances other than the solvent substance (Bx) added here.Other addition amount: Addition amount of other solvent substances.
  • B-1 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name "Zeolora H", manufactured by Nippon Zeon Co., Ltd.)
  • B-2 3,3,4,4,5,5-hexafluorocyclopentene
  • B-3 1-methoxy-2,3,3,4,4,5,5-heptafluorocyclopentene
  • C-1 2H, 3H-decafluoropentane (trade name: "Vertrell XF” manufactured by Mitsui Chemours Fluoro Products Co., Ltd.)
  • C-2 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (trade name "Asahikulin AE-3000", manufactured by AGC)
  • C-3 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether
  • C-4 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetra
  • Example 2 The viscosity of the electrolytic solution, which is a mixture of the electrolytic solution (08) prepared in Production Example 1 and the solvent substance (B-1) added at the concentration shown in Table 3, was measured.
  • the measurement was carried out using an EMS viscometer (manufactured by Kyoto Electronics Industry Co., Ltd., EMS-1000S) in an environment of 25°C, keeping the electrolyte composition unchanged under sealed conditions and no moisture in the air mixed in.
  • the measurement was made at a rotation speed of 1000 rpm.
  • the viscosity measured by this measurement method is basically the same value as the value measured in accordance with JIS Z8803.
  • the measurement results are shown in Table 3.
  • the electrolytic solution (08) without the addition of solvent substance (B-1) exhibited a viscosity of 60 cP at 25°C, and it was confirmed that the viscosity tended to decrease significantly as the amount of solvent substance (B-1) added increased. Ta. By lowering the viscosity, it is expected that the liquid will move more smoothly inside the electrochemical device.
  • (B-1) ratio volume % of (B-1) in the volume % of the entire non-aqueous electrolyte.
  • Example 3 About the electrolytic solution (11) prepared in Production Example 1 and the electrolytic solution (111) of Example 1, which is an electrolytic solution prepared by adding 40% by volume of the solvent substance (B-1) to the electrolytic solution (11). Ionic conductivity was measured. The measurement was carried out in the temperature range of -20 to 80°C, and the measurement was carried out in the frequency range of 1M to 0.1Hz by the AC impedance method using an impedance analyzer manufactured by Solartron. The results are shown in Figure 1.
  • Example 4 Electrolyte solution (01) prepared in Production Example 1, and electrolyte solution in which 60% by volume of solvent substance (B-1), (B-2) or (C-3) was added to electrolyte solution (01). The ionic conductivity of the electrolytes (101-1), (101-4), and (201-2) of Example 1 was measured. The measurement was performed according to the same procedure as in Example 3, except that the temperature range was -20 to 10°C. The results are shown in Figure 2.
  • the ionic conductivity decreased significantly as the temperature decreased.
  • the electrolytic solutions (101-1) and (101-3) which are electrolytic solutions to which the solvent substance (B) was added, the ionic conductivity at low temperatures could be greatly improved.
  • the degree of improvement was relatively greater in electrolyte solution (101-4) than in electrolyte solution (101-1).
  • the electrolytic solution (201-2) which is an electrolytic solution to which the solvent substance (C-3) was added, an improvement effect was observed at temperatures below 0°C, but it tended to get worse at temperatures above 0°C.
  • An activated carbon electrode consisting of a base material and a composite material layer was prepared by pressing the layer.
  • the area weight and density of the composite material layer were 6.1 mg/cm 2 and 0.48 g/cm 3 .
  • the activated carbon electrode was cut out to form a 4 ⁇ 4 cm rectangular test electrode.
  • 15 ⁇ l of the electrolytic solution was dropped onto the surface of the test electrode on the composite material layer side, and the manner in which the electrolytic solution permeated into the composite material layer was observed.
  • the electrolytic solution gradually permeated into the composite material layer, and the time when the surface of the composite material layer lost its luster was defined as the end of impregnation, and the time taken from dropping to the end of impregnation was recorded.
  • the dropping was performed in a glass petri dish with a lid, and the lid was placed immediately after the dropping.
  • the times required for impregnation with electrolyte solution (17), electrolyte solution (117-1), and electrolyte solution (117-2) were 489 seconds, 182 seconds, and 75 seconds, respectively. From this, it was found that the impregnation rate into the electrode composite material layer was improved by adding the solvent substance (B).
  • Example 6 (6-1. Positive electrode) Aluminum foil with a thickness of 20 ⁇ m was prepared as a current collector for the positive electrode. A layer containing 94%, 3%, and 3% by weight of lithium cobalt oxide (positive electrode active material), acetylene black, and PVDF (polyvinylidene fluoride) binder, respectively, is provided on the positive electrode current collector, and the layer is pressed. By doing so, a positive electrode composite material layer was formed, and a lithium ion positive electrode consisting of a positive electrode current collector and a positive electrode composite material layer was prepared. The fabric weight and density of the positive electrode composite material layer were 20 mg/cm 2 and 3.0 g/cm 3 .
  • a copper foil with a thickness of 10 ⁇ m was prepared as a current collector for the negative electrode.
  • a negative electrode composite material layer was formed by pressing the layer, and a lithium ion negative electrode consisting of a negative electrode current collector and a negative electrode composite material layer was prepared.
  • the area weight and density of the negative electrode composite material layer were 10 mg/cm 2 and 1.4 g/cm 3 .
  • An aluminum laminate bag with a polyethylene sealant was prepared.
  • the solvent substance (B-1) volume ratio: 40 vol%) was injected, and the aluminum laminate bag was sealed. As a result, a lithium-ion secondary battery was completed.
  • (6-4. Charge/discharge test of lithium ion secondary battery) The battery obtained in (6-3) was charged and discharged at a rate of 0.5C relative to the designed capacity in an environment of 25°C. As a result, in the voltage range of 4.2 to 3.0 V, the discharge capacity was 145 mAh/g per weight of the positive electrode active material, and repeated charging and discharging was possible. The capacity retention rate after 50 cycles with respect to the initial discharge capacity was as high as 94%.
  • Example 5 (C2-3. Manufacture and evaluation of lithium ion secondary battery) A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 5 except for the following changes. -In place of electrolyte (118), electrolyte (212) prepared in (C2-2) was used. As a result, the discharge capacity was 144 mAh/g per weight of the positive electrode active material, and repeated charging and discharging was possible. The capacity retention rate after 50 cycles with respect to the initial discharge capacity was 91%, which was lower than in Example 5.
  • Example 3 A lithium ion secondary battery was manufactured and evaluated in the same manner as in Example 5 except for the following changes. - In place of the electrolytic solution (118), the preliminary electrolytic solution (21) prepared in (C2-1) of Comparative Example 2 was used as it was. As a result, the discharge capacity was 143 mAh/g per weight of the positive electrode active material, and repeated charging and discharging was possible. The capacity retention rate after 50 cycles with respect to the initial discharge capacity was 94%, which was lower than in Example 5.
  • Example 7 (7-1. Capacitor) Two pieces of the activated carbon electrode obtained in Example 5 were cut out to a size of 3 x 4 cm to obtain test electrodes. An aluminum tab was attached to the end of each test electrode by ultrasonic welding. A sheet of paper with a thickness of 35 ⁇ m (manufactured by Nippon Kokoshi Kogyo, TF4535) was placed as a separator between the pair of test electrodes with tabs. A laminate having a layer structure of layer)/(base material) was obtained.
  • An aluminum laminate bag with a polyethylene sealant was prepared.
  • the resistance value (unit: ⁇ ) of the capacitor obtained in (8-1) was measured by an AC impedance method (using an impedance analyzer manufactured by Solartron, measurement frequency 1 MHz to 0.01 Hz). The ambient temperature of the cell was raised from 25° C., and the relationship between temperature and resistance value was determined. Table 4 shows the relative measured values of the resistance value at each temperature, with the resistance value at 25° C. being 1.
  • Example 9 The electrolytic solution (107-2) prepared in Example 1 was determined by the flash point measurement method in accordance with the tag sealing method (JIS K2265-1 (2007)) and the Cleveland open method (JIS K2265-4 (2007)). , the flash point was measured. No flash point was confirmed when measuring the flash point using the closed tag method, and when measuring the flash point using the Cleveland open method, the prescribed test could not be continued due to boiling of the solvent substance (B), resulting in an evaluation of no flash point. . It has been found that low flammability can be imparted to the electrolyte if the solvent substance (B) is non-flammable.
  • Combustibility was evaluated by taking 100 mg of the electrolytic solution (03) prepared in Production Example 1, placing it in a stainless steel dish with a diameter of 2 cm, applying a burner flame, and observing the state. As a result, it was observed that ignition occurred 5 seconds after the burner was applied, and combustion continued for 8 seconds.
  • Example 10 Combustibility was evaluated by taking 100 mg of the electrolytic solution (103) prepared in Example 1, placing it in a stainless steel dish with a diameter of 2 cm, applying a burner flame, and observing the state. As a result, it was observed that ignition occurred 7 seconds after the burner was applied, and combustion continued for 5 seconds. By comparing Comparative Example 4 and Example 9, it was found that the ignitability and combustion time of the electrolytic solution can be reduced by adding the solvent substance (B-2) that does not have a flash point.
  • Example 11 (11-1. Positive electrode sheet)
  • the experiment was conducted by changing the temperature of the experimental environment to 18°C so that the melting point of the solvent substance (B-1) was below 20.5°C.
  • a poly(ethylene oxide-propylene oxide) copolymer (ethylene oxide unit:propylene oxide unit in molar ratio of 90:10) having a weight average molecular weight of 500,000 was added to the electrolytic solution (08) prepared in Production Example 1 at a concentration of 5% by weight. % and mixed to prepare an electrolytic solution (08-P).
  • the electrolyte of the present invention may be completed inside the device and may include a polymer.

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Abstract

Sont divulgués : une solution électrolytique non aqueuse ; et un dispositif électrochimique. La solution électrolytique non aqueuse comprend un composant ionique et un composant de solvant non ionique. Le composant de solvant non ionique contient une substance de solvant organique contenant un hétéroélément (A) et une substance de solvant organique contenant du fluor (B). La substance de solvant organique contenant du fluor (B) comprend, dans la molécule, une structure cyclique utilisant des atomes de carbone en tant que constituants et/ou une liaison insaturée carbone-carbone, et présente un taux de fluoration supérieur ou égal à 40 %. La proportion de la substance de solvant organique contenant du fluor (B) relativement à 100 % en volume du composant de solvant non ionique est supérieure ou égale à 10 % en volume. La quantité molaire de la substance de solvant organique contenant un hétéroélément (A) est d'au plus 5 fois la quantité cationique du composant ionique.
PCT/JP2023/012070 2022-03-30 2023-03-27 Solution électrolytique non aqueuse et dispositif électrochimique Ceased WO2023190273A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10284036A (ja) * 1997-04-07 1998-10-23 Japan Storage Battery Co Ltd 電 池
JP2000348762A (ja) * 1999-06-04 2000-12-15 Hitachi Ltd 不燃性電解液及びこれを用いたリチウム２次電池
JP2006092815A (ja) * 2004-09-22 2006-04-06 Hitachi Ltd エネルギーデバイス
JP2007234339A (ja) * 2006-02-28 2007-09-13 Three M Innovative Properties Co 溶媒組成物及び電気化学デバイス
WO2012066770A1 (fr) * 2010-11-16 2012-05-24 パナソニック株式会社 Solvant non aqueux pour dispositif de stockage d'électricité
WO2015025882A1 (fr) * 2013-08-21 2015-02-26 積水化学工業株式会社 Électrolyte et batterie secondaire au lithium-ion
WO2022254717A1 (fr) * 2021-06-04 2022-12-08 ＴｅｒａＷａｔｔ Ｔｅｃｈｎｏｌｏｇｙ株式会社 Batterie secondaire au lithium
WO2023042262A1 (fr) * 2021-09-14 2023-03-23 ＴｅｒａＷａｔｔ Ｔｅｃｈｎｏｌｏｇｙ株式会社 Batterie secondaire au lithium

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10284036A (ja) * 1997-04-07 1998-10-23 Japan Storage Battery Co Ltd 電 池
JP2000348762A (ja) * 1999-06-04 2000-12-15 Hitachi Ltd 不燃性電解液及びこれを用いたリチウム２次電池
JP2006092815A (ja) * 2004-09-22 2006-04-06 Hitachi Ltd エネルギーデバイス
JP2007234339A (ja) * 2006-02-28 2007-09-13 Three M Innovative Properties Co 溶媒組成物及び電気化学デバイス
WO2012066770A1 (fr) * 2010-11-16 2012-05-24 パナソニック株式会社 Solvant non aqueux pour dispositif de stockage d'électricité
WO2015025882A1 (fr) * 2013-08-21 2015-02-26 積水化学工業株式会社 Électrolyte et batterie secondaire au lithium-ion
WO2022254717A1 (fr) * 2021-06-04 2022-12-08 ＴｅｒａＷａｔｔ Ｔｅｃｈｎｏｌｏｇｙ株式会社 Batterie secondaire au lithium
WO2023042262A1 (fr) * 2021-09-14 2023-03-23 ＴｅｒａＷａｔｔ Ｔｅｃｈｎｏｌｏｇｙ株式会社 Batterie secondaire au lithium

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