WO2020246522A1 - 非水電解液及び非水電解液電池 - Google Patents

非水電解液及び非水電解液電池 Download PDF

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WO2020246522A1
WO2020246522A1 PCT/JP2020/022015 JP2020022015W WO2020246522A1 WO 2020246522 A1 WO2020246522 A1 WO 2020246522A1 JP 2020022015 W JP2020022015 W JP 2020022015W WO 2020246522 A1 WO2020246522 A1 WO 2020246522A1
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group
general formula
aqueous electrolyte
lithium
aqueous
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English (en)
French (fr)
Japanese (ja)
Inventor
憲治 久保
渉 河端
裕太 池田
孝敬 森中
幹弘 高橋
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Central Glass Co Ltd
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Central Glass Co Ltd
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Priority to US17/596,173 priority Critical patent/US20220255131A1/en
Priority to KR1020217039799A priority patent/KR102959569B1/ko
Priority to EP20818229.5A priority patent/EP3965128B1/en
Priority to CN202080040536.XA priority patent/CN113906530B/zh
Priority to JP2021524887A priority patent/JP7610126B2/ja
Publication of WO2020246522A1 publication Critical patent/WO2020246522A1/ja
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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
    • 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
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • 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
    • H01G11/64—Liquid electrolytes characterised by 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
    • H01M10/052—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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • 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 disclosure relates to a non-aqueous electrolyte solution and a non-aqueous electrolyte solution battery.
  • batteries which are electrochemical devices, information-related equipment and communication equipment, that is, power storage systems for small and high energy density applications such as personal computers, video cameras, digital cameras, mobile phones, and smartphones, electric vehicles, and hybrid vehicles.
  • Fuel cell vehicle auxiliary power supply, power storage system for large-scale, power applications such as power storage are attracting attention.
  • non-aqueous electrolyte batteries such as lithium-ion batteries, which have high energy density and voltage and high capacity, and are currently being actively researched and developed.
  • Non-aqueous electrolyte solution used in the battery is a solvent such as cyclic carbonate, chain carbonate, or ester, and lithium hexafluorophosphate (hereinafter referred to as LiPF 6 ) or lithium bis (fluorosulfonylimide) as a solute.
  • a non-aqueous electrolyte solution in which a fluorine-containing electrolyte such as (hereinafter LiFSI) and lithium tetrafluoroborate (hereinafter LiBF 4 ) is dissolved is often used because it is suitable for obtaining a high-voltage and high-capacity battery. ..
  • LiFSI fluorine-containing electrolyte
  • LiBF 4 lithium tetrafluoroborate
  • a non-aqueous electrolyte battery using such a non-aqueous electrolyte is not always satisfactory in terms of battery characteristics such as cycle characteristics and output characteristics.
  • the negative electrode and the lithium cation, or the negative electrode and the electrolytic solution solvent react, and lithium oxide, lithium carbonate, or alkylcarbonate is formed on the surface of the negative electrode.
  • a film containing lithium as the main component is formed.
  • the film on the surface of the electrode is called Solid Electrolyte Interface (SEI), and its properties have a great influence on the battery performance, such as suppressing further reduction decomposition of the solvent and suppressing deterioration of the battery performance.
  • SEI Solid Electrolyte Interface
  • a film of decomposition products is formed on the surface of the positive electrode, which is also known to play an important role in suppressing oxidative decomposition of the solvent and suppressing gas generation inside the battery.
  • Patent Document 1 discloses that an additive having a specific structure containing a functional group having two different heteroatoms, a phosphorus atom and a sulfur atom, improves the life characteristics and storage characteristics of a battery at high temperatures. There is.
  • the present disclosure has been made in view of the above circumstances, and has an effect of improving the capacity retention rate after a long cycle at a high temperature (60 ° C or higher) and a low temperature (0 ° C or lower, particularly ⁇ 20 ° C or lower) after high temperature storage. It is an object of the present invention to provide a non-aqueous electrolytic solution and a non-aqueous electrolytic solution battery capable of exhibiting the effect of suppressing an increase in resistance in a well-balanced manner.
  • the present inventors have added a salt compound represented by the general formula (1) as an additive in the non-aqueous electrolytic solution in a specific range with respect to the total amount of the non-aqueous electrolytic solution. It was found that the effect of improving the capacity retention rate after a long-term cycle at high temperature and the effect of suppressing the increase in resistance at low temperature after high temperature storage can be exhibited in a well-balanced manner by using the content of.
  • ⁇ 1> It is a non-aqueous electrolyte solution It contains a salt compound represented by the following general formula (1), a solute, and a non-aqueous organic solvent.
  • a non-aqueous electrolytic solution in which the content of the salt compound represented by the general formula (1) with respect to the total amount of the non-aqueous electrolytic solution is 0.003% by mass to 0.1% by mass.
  • R 1 and R 2 independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, and any hydrogen atom of the alkyl group is replaced with a fluorine atom.
  • X 1 and X 2 each independently represent a halogen atom.
  • M 1 + represents an alkali metal cation, an ammonium ion or an organic cation.
  • n represents an integer of 1 to 6. When n is an integer of 2 or more, the plurality of R 1s may be the same or different, and the plurality of R 2s may be the same or different.
  • ⁇ 2> The non-aqueous electrolytic solution according to ⁇ 1>, which contains a compound represented by the following general formula (2).
  • R 3 represents a hydrocarbon group having 2 to 5 carbon atoms.
  • a hetero atom may be contained between the carbon atoms in the hydrocarbon group. Further, any hydrogen atom of the hydrocarbon group may be substituted with a halogen atom.
  • X 3 and X 4 each independently represent a halogen atom.
  • M 2 + represents an alkali metal cation, an ammonium ion or an organic cation.
  • ⁇ 4> The non-aqueous electrolytic solution according to any one of ⁇ 1> to ⁇ 3>, wherein the non-aqueous organic solvent contains at least one selected from the group consisting of cyclic carbonate and chain carbonate.
  • the solute is at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions, hexafluorophosphate anion, tetrafluoroborate anion, trifluoromethanesulfonic acid anion, fluorosulfonic acid anion, Bis (trifluoromethanesulfonyl) imide anion, bis (pentafluoroethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, (trifluoromethanesulfonyl) (fluorosulfonyl) imide anion, bis (difluorophosphonyl) imide anion, (difluoro) ⁇ 1> to ⁇ 4 which are pairs of at least one anion selected from the group consisting of phosphonyl) (fluorosulfonyl) imide anion and (difluorophosphonyl) (trifluo) ⁇
  • a negative electrode having at least one selected from the group consisting of a positive electrode, a negative electrode material containing a lithium metal, and a negative electrode material capable of occluding and releasing lithium, sodium, potassium, or magnesium, and any of ⁇ 1> to ⁇ 5>.
  • the effect of improving the capacity retention rate after a long cycle at a high temperature (60 ° C. or higher) and the effect of suppressing an increase in resistance at a low temperature (0 ° C. or lower, particularly ⁇ 20 ° C. or lower) after high temperature storage can be achieved. It is possible to provide a non-aqueous electrolyte solution and a non-aqueous electrolyte solution battery that can be exhibited in a well-balanced manner.
  • 3 is a plot of the high temperature cycle capacity retention rate and the low temperature internal resistance after high temperature storage with respect to the concentration of component (I) according to Examples and Comparative Examples. 3 is a plot of the high temperature cycle capacity retention rate and the low temperature internal resistance after high temperature storage with respect to the concentration of component (I) according to Examples and Comparative Examples. 3 is a plot of the high temperature cycle capacity retention rate and the low temperature internal resistance after high temperature storage with respect to the concentration of component (I) according to Examples and Comparative Examples. 3 is a plot of the high temperature cycle capacity retention rate and the low temperature internal resistance after high temperature storage with respect to the concentration of component (I) according to Examples and Comparative Examples.
  • 3 is a plot of the high temperature cycle capacity retention rate and the low temperature internal resistance after high temperature storage with respect to the concentration of component (I) according to Examples and Comparative Examples. 3 is a plot of the high temperature cycle capacity retention rate and the low temperature internal resistance after high temperature storage with respect to the concentration of component (I) according to Examples and Comparative Examples.
  • the non-aqueous electrolyte solution of the present disclosure is The content of the salt compound represented by the general formula (1) with respect to the total amount of the non-aqueous electrolytic solution containing the salt compound represented by the following general formula (1), the solute, and the non-aqueous organic solvent is 0. It is 003% by mass to 0.1% by mass.
  • R 1 and R 2 independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, and any hydrogen atom of the alkyl group is replaced with a fluorine atom.
  • X 1 and X 2 each independently represent a halogen atom.
  • M 1 + represents an alkali metal cation, an ammonium ion or an organic cation.
  • n represents an integer of 1 to 6. When n is an integer of 2 or more, the plurality of R 1s may be the same or different, and the plurality of R 2s may be the same or different.
  • the salt compound represented by the general formula (1) will be described.
  • the salt compound represented by the general formula (1) is also referred to as the component (I).
  • R 1 and R 2 independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, and any hydrogen atom of the alkyl group is replaced with a fluorine atom.
  • X 1 and X 2 each independently represent a halogen atom.
  • M 1 + represents an alkali metal cation, an ammonium ion or an organic cation.
  • n represents an integer of 1 to 6. When n is an integer of 2 or more, the plurality of R 1s may be the same or different, and the plurality of R 2s may be the same or different.
  • R 1 and R 2 independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms.
  • Examples of the alkyl group when R 1 and R 2 represent an alkyl group having 1 to 6 carbon atoms include a linear or branched alkyl group, and specifically, a methyl group, an ethyl group, and an n-propyl group. , I-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group and the like. Any hydrogen atom of the alkyl group may be substituted with a fluorine atom.
  • Alkyl groups in which any hydrogen atom is replaced with a fluorine atom include trifluoromethyl group, difluoromethyl group, fluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-difluoroethyl group and 2-. Fluoroethyl group and the like can be mentioned.
  • the alkyl group is preferably a fluorine-substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, an i-propyl group, an n-butyl group, or a trifluoromethyl group, and a methyl group is particularly preferable. ..
  • R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a fluorine-substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and R 1 It is particularly preferable that both and R 2 are hydrogen atoms.
  • X 1 and X 2 each independently represent a halogen atom.
  • the halogen atom represented by X 1 and X 2 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • X 1 and X 2 may be the same or different, but are preferably the same, and both are preferably fluorine atoms.
  • M 1 + represents an alkali metal cation, an ammonium ion (NH 4 + ) or an organic cation.
  • the alkali metal cation M 1 + represents a lithium cation, sodium cation, potassium cation, and the like.
  • the organic cation M 1 + represents a methyl ammonium ion (MeNH 3 +), dimethyl ammonium ion (Me 2 NH 2 +), trimethylammonium ion (Me 3 NH +), ethylammonium ion (EtNH 3 +), diethyl Ammonium ion (Et 2 NH 2 + ), triethylammonium ion (Et 3 NH + ), tri-n-propylammonium ion (n-Pr 3 NH + ), tri-i-propylammonium ion (i-Pr 3 NH +) ), n-butyl ammonium ion (n-BuNH 3 +), tri -n- butyl ammonium ions (n-Bu 3 NH +) , sec- butyl ammonium ion (sec-BuNH 3 +), tert- butyl ammonium ion ( t-BuNH 3 +), diiso
  • n represents an integer of 1 to 6.
  • n is preferably an integer of 1 to 4, more preferably 2 or 3, and particularly preferably 2.
  • the anion in the salt compound represented by the general formula (1) is preferably at least one selected from the group consisting of the following formulas (1-1) to (1-18). More preferably, at least one selected from the group consisting of formulas (1-1), (1-3), (1-5), (1-6), (1-13) and (1-15). Yes, more preferably at least one selected from the group consisting of formulas (1-1), (1-3), and (1-6).
  • the method for synthesizing the salt compound represented by the general formula (1) is not particularly limited, and various known synthetic methods can be used. For example, it can be obtained by reacting a cyclic sulfate ester with an alkali metal hydroxide to open the ring, and then further performing an addition reaction with phosphorus oxyhalide.
  • the phosphorus oxyhalide includes, for example, oxychlorodifluorophosphorus, phosphorus oxyfluoride, phosphorus oxychloride and the like. Can be used.
  • a known fluoride for example, HF, NaF, KF, etc.
  • a known fluoride for example, HF, NaF, KF, etc.
  • the content of the salt compound represented by the above general formula (1) with respect to the total amount of the non-aqueous electrolyte solution of the present disclosure is 0.003 mass% (30 mass ppm) to 0.1 mass% (1000 mass ppm). , 0.0045 mass% (45 mass ppm) to 0.070 mass% (700 mass ppm), preferably 0.006 mass% (60 mass ppm) to 0.060 mass% (600 mass ppm). It is more preferably 0.0075 mass% (75 mass ppm) to 0.055 mass% (550 mass ppm).
  • salt compound represented by the general formula (1) only one type may be used, or a plurality of types may be used in combination.
  • the non-aqueous electrolyte solution of the present disclosure contains a solute.
  • the solute is preferably an ionic salt, for example, at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions, hexafluorophosphate anion, tetrafluoroborate anion, and trifluoromethane.
  • the cation of the ionic salt which is the solute is lithium, sodium, potassium, or magnesium, and the anions are hexafluorophosphate anion, tetrafluoroborate anion, trifluoromethanesulfonic acid anion, and bis (trifluoromethanesulfonyl) imide.
  • the preferable concentration of these solutes is not particularly limited, but the lower limit is 0.5 mol / L or more, preferably 0.7 mol / L or more, more preferably 0.9 mol / L or more, and the upper limit is 2.
  • the range is 5 mol / L or less, preferably 2.2 mol / L or less, and more preferably 2.0 mol / L or less.
  • solutes may be used alone or in combination of two or more.
  • the ionic salt listed as the solute has a negative electrode film as an "other additive" when the content in the non-aqueous electrolyte solution is smaller than the lower limit of 0.5 mol / L, which is the lower limit of the suitable concentration of the solute. It can exert a forming effect and a positive electrode protection effect.
  • Non-aqueous organic solvent used in the non-aqueous electrolytic solution of the present disclosure is not particularly limited, and any non-aqueous organic solvent can be used. Specifically, ethyl methyl carbonate (hereinafter referred to as "EMC”), dimethyl carbonate (hereinafter referred to as "DMC”), diethyl carbonate (hereinafter referred to as "DEC”), methyl propyl carbonate, ethyl propyl carbonate, Methylbutyl carbonate, 2,2,2-trifluoroethylmethyl carbonate, 2,2,2-trifluoroethylethyl carbonate, 2,2,2-trifluoroethylpropyl carbonate, bis (2,2,2-trifluoro) Ethyl) carbonate, 1,1,1,3,3,3-hexafluoro-1-propylmethyl carbonate, 1,1,1,3,3,3-hexafluoro-1-propyleth
  • the non-aqueous organic solvent contains at least one selected from the group consisting of cyclic carbonate and chain carbonate because it is excellent in cycle characteristics at high temperature. Further, it is preferable that the non-aqueous organic solvent contains an ester because it is excellent in input / output characteristics at a low temperature.
  • the cyclic carbonate include EC, PC, butylene carbonate, FEC, and the like, and at least one selected from the group consisting of EC, PC, and FEC is preferable.
  • chain carbonate examples include EMC, DMC, DEC, methylpropyl carbonate, ethylpropyl carbonate, 2,2,2-trifluoroethylmethyl carbonate, 2,2,2-trifluoroethylethyl carbonate, 1,1, Examples thereof include 1,3,3,3-hexafluoro-1-propylmethyl carbonate and 1,1,1,3,3,3-hexafluoro-1-propylethyl carbonate, among which EMC, DMC, DEC, etc. And at least one selected from the group consisting of methylpropyl carbonate.
  • ester examples include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate and the like.
  • the non-aqueous electrolyte solution of the present disclosure may contain a polymer and is generally called a polymer solid electrolyte.
  • Polymer solid electrolytes also include those containing a non-aqueous organic solvent as a plasticizer.
  • the polymer is not particularly limited as long as it is an aprotic polymer capable of dissolving the above salt compound, solute and other additives described below.
  • examples thereof include polymers having a polyethylene oxide in the main chain or side chains, homopolymers or copolymers of polyvinylidene fluoride, methacrylic acid ester polymers, polyacrylonitrile and the like.
  • the aprotic non-aqueous organic solvent among the above non-aqueous organic solvents is preferable.
  • the non-aqueous electrolyte solution of the present disclosure may contain any of the compounds represented by the following general formulas (2) to (6) to improve the capacity retention rate after a long cycle at a higher temperature or after high temperature storage. It is preferable from the viewpoint of suppressing the increase in resistance at low temperatures, and it is more preferable to contain at least one of the compound represented by the general formula (2) and the compound represented by the general formula (3).
  • R 3 represents a hydrocarbon group having 2 to 5 carbon atoms.
  • a hetero atom may be contained between the carbon atoms in the hydrocarbon group. Further, any hydrogen atom of the hydrocarbon group may be substituted with a halogen atom.
  • R 3 represents a hydrocarbon group having 2 to 5 carbon atoms.
  • the hydrocarbon group represented by R 3 include a linear or branched alkylene group, an alkenylene group, an alkynylene group and the like.
  • the alkylene group is an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, an s-butylene group, a t-butylene group, or an n-pentylene group. , -CH 2 CH (C 3 H 7 ) -group and the like.
  • alkenylene group when R 3 represents an alkenylene group include an ethenylene group and a propenylene group.
  • alkynylene group when R 3 represents an alkynylene group include an ethynylene group and a propynylene group.
  • the hydrocarbon group represented by R 3 may contain a hetero atom between carbon atoms and carbon atom bonds.
  • the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like.
  • any hydrogen atom may be substituted with a halogen atom.
  • the hydrocarbon group in which an arbitrary hydrogen atom is replaced with a fluorine atom include a tetrafluoroethylene group, a 1,2-difluoroethylene group, a 2,2-difluoroethylene group, a fluoroethylene group, and a (trifluoromethyl) ethylene group.
  • a fluorine atom examples include a tetrafluoroethylene group, a 1,2-difluoroethylene group, a 2,2-difluoroethylene group, a fluoroethylene group, and a (trifluoromethyl) ethylene group.
  • R 3 is preferably an unsubstituted alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group.
  • the content of the compound represented by the general formula (2) in the non-aqueous electrolytic solution is the total amount of the non-aqueous electrolytic solution. On the other hand, 0.01% by mass or more and 8.0% by mass or less are preferable.
  • the non-aqueous electrolytic solution of the present disclosure contains a compound represented by the general formula (2), it may contain only one type of compound represented by the general formula (2), or may contain two or more types.
  • X 3 and X 4 each independently represent a halogen atom.
  • M 2 + represents an alkali metal cation, an ammonium ion or an organic cation.
  • X 3 and X 4 represent halogen atoms.
  • the halogen atom represented by X 3 and X 4 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • X 3 and X 4 may be the same or different, but are preferably the same, and both are preferably fluorine atoms.
  • M 2 + represents an alkali metal cation, ammonium ion (NH 4 +) or an organic cation.
  • the alkali metal cation M 2 + represents a lithium cation, sodium cation, potassium cation, and the like.
  • the organic cation M 2 + represents a methyl ammonium ion (MeNH 3 +), dimethyl ammonium ion (Me 2 NH 2 +), trimethylammonium ion (Me 3 NH +), ethylammonium ion (EtNH 3 +), diethyl Ammonium ion (Et 2 NH 2 + ), triethylammonium ion (Et 3 NH + ), tri-n-propylammonium ion (n-Pr 3 NH + ), tri-i-propylammonium ion (i-Pr 3 NH +) ), n-butyl ammonium ion (n-BuNH 3 +), tri -n- butyl ammonium ions (n-Bu 3 NH +) , sec- butyl ammonium ion (sec-BuNH 3 +), tert- butyl ammonium ion ( t-BuNH 3 +), diiso
  • the content of the compound represented by the general formula (3) in the non-aqueous electrolytic solution is the total amount of the non-aqueous electrolytic solution. On the other hand, it is preferably 0.01% by mass or more and 8.0% by mass or less.
  • the non-aqueous electrolytic solution of the present disclosure may contain only one type of compound represented by the general formula (3), or may contain two or more types.
  • R 4 represents a hydrocarbon group having 2 to 6 carbon atoms.
  • a hetero atom may be contained between the carbon atoms in the hydrocarbon group. Further, any hydrogen atom of the hydrocarbon group may be substituted with a halogen atom.
  • R 4 represents a hydrocarbon group having 2 to 6 carbon atoms.
  • the hydrocarbon group represented by R 4 include a linear or branched alkylene group, an alkenylene group, an alkynylene group and the like.
  • the alkylene group is an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, an s-butylene group, a t-butylene group, or an n-pentylene group.
  • -CH 2 CH (C 3 H 7 ) -group n-hexylene group and the like.
  • alkenylene group when R 4 represents an alkenylene group include an ethenylene group and a propenylene group.
  • alkynylene group when R 4 represents an alkynylene group include a propynylene group and the like.
  • the hydrocarbon group represented by R 4 may contain a hetero atom between carbon atoms and carbon atom bonds.
  • the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like.
  • any hydrogen atom may be substituted with a halogen atom.
  • the hydrocarbon group in which an arbitrary hydrogen atom is replaced with a fluorine atom include a tetrafluoroethylene group, a 1,2-difluoroethylene group, a 2,2-difluoroethylene group, a fluoroethylene group, and a (trifluoromethyl) ethylene group.
  • a fluorine atom examples include a tetrafluoroethylene group, a 1,2-difluoroethylene group, a 2,2-difluoroethylene group, a fluoroethylene group, and a (trifluoromethyl) ethylene group.
  • R 4 is preferably an unsubstituted alkylene group having 3 to 4 carbon atoms, and more preferably a propylene group.
  • the content of the compound represented by the general formula (4) in the non-aqueous electrolytic solution is the total amount of the non-aqueous electrolytic solution. On the other hand, it is preferably 0.01% by mass or more and 8.0% by mass or less.
  • the non-aqueous electrolytic solution of the present disclosure contains a compound represented by the general formula (4), it may contain only one compound represented by the general formula (4) or may contain two or more kinds.
  • R 5 are each independently a substituent having at least one of an unsaturated bond and an aromatic ring.
  • R 5 is an alkenyl group, an alkynyl group, an aryl group, an alkenyloxy group, alkynyloxy group, and is preferably a group selected from an aryloxy group.
  • the alkenyl group is preferably a group selected from an ethenyl group and a 2-propenyl group (allyl group), and the alkynyl group is preferably an ethynyl group.
  • the aryl group is preferably a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, a 4-fluorophenyl group, a 4-tert-butylphenyl group, or a 4-tert-amylphenyl group.
  • the alkenyloxy group is preferably a group selected from a vinyloxy group and a 2-propenyloxy group (allyloxy group).
  • the alkynyloxy group is preferably a propargyloxy group
  • the aryloxy group is a phenoxy group, a 2-methylphenoxy group, a 4-methylphenoxy group, a 4-fluorophenoxy group, a 4-tert-butylphenoxy group, or a 4-tert-amyl. Phenoxy groups are preferred.
  • the content of the compound represented by the general formula (5) in the non-aqueous electrolytic solution is the total amount of the non-aqueous electrolytic solution. On the other hand, it is preferably 0.01% by mass or more and 8.0% by mass or less.
  • the non-aqueous electrolytic solution of the present disclosure may contain only one type of compound represented by the general formula (5), or may contain two or more types.
  • the content of the compound represented by the general formula (6) in the non-aqueous electrolytic solution is the total amount of the non-aqueous electrolytic solution. On the other hand, it is preferably 0.01% by mass or more and 8.0% by mass or less.
  • the non-aqueous electrolytic solution of the present disclosure contains a compound represented by the general formula (6), it may contain only one type of compound represented by the general formula (6), or may contain two or more types.
  • other additives other than the compounds represented by the above general formulas (2) to (6) include cyclohexylbenzene, cyclohexylfluorobenzene, fluorobenzene (hereinafter, may be referred to as FB), and Biphenyl, difluoroanisole, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, 2-fluorobiphenyl, vinylene carbonate, dimethylvinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, methylpropargyl carbonate, ethylpropargyl carbonate, dipropargyl Carbonate, maleic anhydride, succinic anhydride, methylenemethanedisulfonate, dimethylenemethanedisulfonate, trimethylenemethanedisulfonate, methyl methanesulfonate, lithium difluorobis (oxalate) (hereinafter,
  • LDFOB lithium difluorooxalatoboate
  • LTFOP lithium tetrafluorooxalatrate
  • tris sodium tetrafluorooxalatrate, potassium tetrafluorooxalatrate, tris.
  • ESF Etensulfonylfluoride
  • TSF trifluoromethanesulfonylfluoride
  • MSF methanesulfonylflu
  • the content of the other additive in the non-aqueous electrolytic solution is preferably 0.01% by mass or more and 8.0% by mass or less with respect to the total amount of the non-aqueous electrolytic solution.
  • the inclusion of at least one of the compounds represented by the above general formulas (2) to (6) improves the capacity retention rate after a long-term cycle at a higher temperature and the higher temperature. It is preferable from the viewpoint of suppressing the increase in resistance at a low temperature after storage, and it is more preferable to contain at least one of the compound represented by the general formula (2) and the compound represented by the general formula (3).
  • the inclusion of a compound is also mentioned as a preferred embodiment.
  • the above compound is contained, not only the capacity retention rate after a long-term cycle at a higher temperature can be improved and the resistance increase at a low temperature after high temperature storage can be suppressed, and further, when a Ni-containing electrode is used, an electrolytic solution is obtained from the electrode. This is preferable from the viewpoint of reducing the elution of the Ni component into the water.
  • the lithium salt of the boron complex having an oxalic acid group is lithium difluorooxalatoboate
  • the lithium salt of the phosphorus complex having an oxalic acid group is lithium tetrafluorooxalatrate and difluorobis (oxalate) phosphate.
  • it is at least one selected from the group consisting of lithium, in addition to improving the capacity retention rate after a long cycle at a higher temperature and suppressing the increase in resistance at a low temperature after high temperature storage, the elution of Ni component from the positive electrode is suppressed. It is more preferable because the effect is particularly excellent.
  • At least one selected from the group consisting of lithium and (trifluoromethanesulfonyl) (fluorosulfonyl) imidelithyl is used to improve the capacity retention rate after a long cycle at a higher temperature and suppress the increase in resistance at a low temperature after high temperature storage.
  • Phylate acid is mentioned, and among them, at least one selected from the group consisting of lithium difluorophosphate, lithium ethylfluorophosphate, and bis (difluorophosphonyl) imide lithium, the capacity is maintained after a long cycle at a higher temperature.
  • non-aqueous electrolyte solution as a pseudo-solid with a gelling agent or a crosslinked polymer, as in the case of using it in a non-aqueous electrolyte battery called a polymer battery.
  • the non-aqueous electrolyte solution can be prepared by dissolving (II) a solute and (I) a salt compound represented by the general formula (1) in (III) a non-aqueous organic solvent.
  • dissolving the (II) solute in the (III) non-aqueous organic solvent it is effective to prevent the liquid temperature of the non-aqueous organic solvent from exceeding 40 ° C. from the viewpoint of preventing deterioration of the non-aqueous organic solvent and the solute. Is.
  • the liquid temperature By setting the liquid temperature to 40 ° C.
  • the solute when the solute dissolves, the solute reacts with water in the system and decomposes to suppress the production of free acids such as hydrofluoric acid (HF), resulting in This is because it is possible to suppress the decomposition of the non-aqueous organic solvent. It is also effective to add solutes little by little to dissolve and prepare them from the viewpoint of suppressing the production of free acids such as HF.
  • the solute When the solute is dissolved in the non-aqueous organic solvent, the solute may be dissolved while cooling the non-aqueous organic solvent, and the liquid temperature is not particularly limited, but is preferably ⁇ 20 to 40 ° C., more preferably 0 to 40 ° C.
  • the salt compound represented by the general formula (1) or other additives it is preferable to control the liquid temperature of the non-aqueous electrolytic solution to ⁇ 10 ° C. or higher and 40 ° C. or lower.
  • the upper limit of the liquid temperature is more preferably 30 ° C. or lower, and particularly preferably 20 ° C. or lower.
  • the non-aqueous electrolyte solution of the present disclosure can be preferably used for a non-aqueous electrolyte battery (preferably a secondary battery).
  • the non-aqueous electrolyte battery of the present disclosure includes at least (a) the above-mentioned non-aqueous electrolyte solution of the present disclosure, (b) a positive electrode, and (c) a negative electrode material containing a lithium metal, lithium, sodium, potassium, or magnesium. Includes a negative electrode having at least one selected from the group consisting of negative electrode materials capable of occluding and releasing. Further, it is preferable to include (d) a separator, an exterior body and the like.
  • the positive electrode preferably contains at least one oxide and / or polyanion compound as the positive electrode active material.
  • the positive electrode active material constituting the positive electrode is not particularly limited as long as it is various materials capable of charging and discharging.
  • the positive electrode active material constituting the positive electrode is not particularly limited as long as it is various materials capable of charging and discharging.
  • a lithium transition metal composite oxide containing at least one metal of nickel, manganese, and cobalt and having a layered structure
  • B a lithium manganese composite oxide having a spinel structure
  • C examples thereof include lithium-containing olivine-type phosphates and (D) lithium excess layered transition metal oxides having a layered rock salt-type structure containing at least one kind.
  • lithium transition metal composite oxide containing at least one or more metals of (A) nickel, manganese, and cobalt and having a layered structure, which is an example of the positive electrode active material, include, for example, lithium-cobalt composite oxide and lithium. ⁇ Nickel composite oxide, lithium nickel cobalt composite oxide, lithium nickel cobalt aluminum composite oxide, lithium cobalt manganese composite oxide, lithium nickel manganese composite oxide, lithium nickel manganese Examples include cobalt composite oxides.
  • transition metal atoms that are the main constituents of these lithium transition metal composite oxides are Al, Ti, V, Cr, Fe, Cu, Zn, Mg, Ga, Zr, Si, B, Ba, Y, Sn. Those substituted with other elements such as may be used.
  • lithium-cobalt composite oxide and the lithium-nickel composite oxide include lithium cobalt oxide (LiCo 0.98 Mg 0.) to which dissimilar elements such as LiCoO 2 , LiNiO 2 and Mg, Zr, Al and Ti are added .
  • 01 Zr 0.01 O 2 LiCo 0.98 Mg 0.01 Al 0.01 O 2 , LiCo 0.975 Mg 0.01 Zr 0.005 Al 0.01 O 2 etc.
  • WO2014 / 034043 Lithium cobalt oxide or the like in which a rare earth compound is adhered to the described surface may be used.
  • WO2014 / 034043 Lithium cobalt oxide or the like in which a rare earth compound is adhered to the described surface may be used.
  • a part of the particle surface of the LiCoO 2 particle powder coated with aluminum oxide may be used.
  • the lithium-nickel-cobalt composite oxide and the lithium-nickel-cobalt-aluminum composite oxide are represented by the general formula [11].
  • M 11 is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, and B, a is 0.9 ⁇ a ⁇ 1.2, and b, c. Satisfies the conditions of 0.1 ⁇ b ⁇ 0.3 and 0 ⁇ c ⁇ 0.1.
  • These can be prepared according to, for example, the production method described in JP-A-2009-137834 and the like.
  • LiNi 0.8 Co 0.2 O 2 LiNi 0.85 Co 0.10 Al 0.05 O 2 , LiNi 0.87 Co 0.10 Al 0.03 O 2 , LiNi 0.6.
  • Examples thereof include Co 0.3 Al 0.1 O 2 .
  • lithium-cobalt-manganese composite oxide and the lithium-nickel-manganese composite oxide include LiNi 0.5 Mn 0.5 O 2 and LiCo 0.5 Mn 0.5 O 2 .
  • lithium-nickel-manganese-cobalt composite oxide examples include a lithium-containing composite oxide represented by the general formula [12].
  • M 12 is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, B, and Sn
  • d is 0.9 ⁇ d ⁇ 1.2
  • the lithium-nickel-manganese-cobalt composite oxide preferably contains manganese in the range shown in the general formula [12] in order to improve structural stability and improve safety at high temperatures in a lithium secondary battery.
  • those further containing cobalt in the range represented by the general formula [12] are more preferable.
  • lithium manganese composite oxide having a spinel structure (B) Lithium-manganese composite oxide having a spinel structure
  • the lithium manganese composite oxide having a spinel structure (B) which is an example of the positive electrode active material, include a spinel-type lithium manganese composite oxide represented by the general formula [13].
  • M 13 is at least one metal element selected from the group consisting of Ni, Co, Fe, Mg, Cr, Cu, Al and Ti
  • j is 1.05 ⁇ j ⁇ 1.15.
  • k is 0 ⁇ k ⁇ 0.20.
  • LiMnO 2 , LiMn 2 O 4 , Limn 1.95 Al 0.05 O 4 , Limn 1.9 Al 0.1 O 4 , Limn 1.9 Ni 0.1 O 4 , Limn 1 .5 Ni 0.5 O 4 and the like can be mentioned.
  • (C) Lithium-containing olivine phosphate examples of the (C) lithium-containing olivine-type phosphate, which is an example of the positive electrode active material, include those represented by the general formula [14].
  • M 14 is at least one selected from Co, Ni, Mn, Cu, Zn, Nb, Mg, Al, Ti, W, Zr and Cd, and n is 0 ⁇ n ⁇ 1. is there.
  • LiFePO 4, LiCoPO 4, LiNiPO 4, LiMnPO 4, and among them LiFePO 4 and / or LiMnPO 4 are preferred.
  • Examples of the lithium excess layered transition metal oxide having a layered rock salt type structure (D), which is an example of the positive electrode active material, include those represented by the general formula [15]. xLiM 15 O 2 ⁇ (1-x) Li 2 M 16 O 3 [15] Wherein [15], x is a number satisfying the 0 ⁇ x ⁇ 1, M 15 is at least one or more metal elements mean oxidation number is 3 +, M 16 is the average oxidation number 4 is at least one metal element is +. In the formula [15], M 15 is one kind of metal element preferably selected from trivalent Mn, Ni, Co, Fe, V, and Cr, but is an equal amount of divalent and tetravalent metals.
  • M 16 is one or more metal elements preferably selected from Mn, Zr, and Ti. Specifically, 0.5 [LiNi 0.5 Mn 0.5 O 2 ], 0.5 [Li 2 MnO 3 ], 0.5 [LiNi 1/3 Co 1/3 Mn 1/3 O 2 ] -0.5 [Li 2 MnO 3 ], 0.5 [LiNi 0.375 Co 0.25 Mn 0.375 O 2 ] -0.5 [Li 2 MnO 3 ], 0.5 [LiNi 0.375 Co 0.125 Fe 0.125 Mn 0.375 O 2 ] ⁇ 0.5 [Li 2 MnO 3 ], 0.45 [LiNi 0.375 Co 0.25 Mn 0.375 O 2 ] ⁇ 0.10 [Li 2 TiO 3 ], 0.45 [Li 2 MnO 3 ] and the like.
  • the positive electrode active material represented by the general formula [15] is known to exhibit a high capacity at a high voltage charge of 4.4 V (Li standard) or higher (for example, US Pat. No. 7,135,252). ..
  • These positive electrode active materials can be prepared according to, for example, the production methods described in JP-A-2008-270201, WO2013 / 118661, JP2013-030284, and the like.
  • the positive electrode active material may contain at least one selected from the above (A) to (D) as a main component, but other materials include, for example, FeS 2 , TiS 2 , TiO 2 , and V. 2 O 5, MoO 3, MoS 2 or the like transition elements chalcogenide or polyacetylene, polyparaphenylene, polyaniline, and a conductive polymer such as polypyrrole, activated carbon, a polymer that generates radicals, carbon materials, and the like.
  • the positive electrode has a positive electrode current collector.
  • the positive electrode current collector for example, aluminum, stainless steel, nickel, titanium, alloys thereof, or the like can be used.
  • a positive electrode active material layer is formed on at least one surface of a positive electrode current collector.
  • the positive electrode active material layer is composed of, for example, the above-mentioned positive electrode active material, a binder, and, if necessary, a conductive agent.
  • the binder polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, styrene butadiene rubber (SBR), carboxymethyl cellulose, methyl cellulose, cellulose acetate phthalate, hydroxypropyl methyl cellulose, polyvinyl alcohol And so on.
  • a carbon material such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (granular graphite or flake graphite), fluorinated graphite can be used.
  • acetylene black or Ketjen black having low crystallinity it is preferable to use acetylene black or Ketjen black having low crystallinity.
  • the negative electrode material is not particularly limited, but in the case of a lithium battery and a lithium ion battery, a lithium metal, an alloy of a lithium metal and another metal, an intermetal compound, various carbon materials (artificial graphite, natural graphite, etc.), a metal Oxides, metal nitrides, tin (elemental substance), tin compounds, silicon (elemental substance), silicon compounds, activated carbon, conductive polymers and the like are used.
  • the carbon materials include, for example, graphitized carbon, non-graphitized carbon (hard carbon) having a (002) plane spacing of 0.37 nm or more, and graphite having a (002) plane spacing of 0.34 nm or less. And so on. More specifically, there are pyrolytic carbon, cokes, glassy carbon fiber, calcined organic polymer compound, activated carbon, carbon black and the like. Among them, coke includes pitch coke, needle coke, petroleum coke and the like.
  • the calcined product of an organic polymer compound refers to a product obtained by calcining a phenol resin, a furan resin, or the like at an appropriate temperature to carbonize it.
  • the carbon material is preferable because the change in the crystal structure due to the occlusion and release of lithium is very small, so that a high energy density can be obtained and excellent cycle characteristics can be obtained.
  • the shape of the carbon material may be fibrous, spherical, granular or scaly. Further, a graphite material whose surface is coated with amorphous carbon or amorphous carbon is more preferable because the reactivity between the material surface and the non-aqueous electrolytic solution is low.
  • the negative electrode preferably contains at least one type of negative electrode active material.
  • the negative electrode active material constituting the negative electrode can be dope / dedope of lithium ions.
  • the negative electrode active material constituting the negative electrode can be dope / dedope of lithium ions.
  • E a carbon material having a d-value of the lattice surface (002 surface) of 0.340 nm or less in X-ray diffraction
  • F carbon having a d-value of the lattice surface (002 surface) of more than 0.340 nm in X-ray diffraction.
  • examples thereof include an alloy with lithium and one containing at least one selected from (I) lithium titanium oxide.
  • One of these negative electrode active materials can be used alone, and two or more of them can be used in combination.
  • Examples of the carbon material having a d-value of 0.340 nm or less on the lattice plane (002 plane) in (E) X-ray diffraction, which is an example of the negative electrode activated carbon, include thermally decomposed carbons and coke (for example, pitch coke and needle coke, etc.). Petroleum coke, etc.), graphite, organic polymer compound calcined material (for example, phenol resin, furan resin, etc. fired at an appropriate temperature and carbonized), carbon fiber, activated carbon, etc. are mentioned, and these are graphitized. It may be.
  • the carbon material has a (002) plane spacing (d002) measured by X-ray diffraction method of 0.340 nm or less, and among them, graphite having a true density of 1.70 g / cm 3 or more, or graphite thereof.
  • d002 plane spacing measured by X-ray diffraction method of 0.340 nm or less
  • graphite having a true density of 1.70 g / cm 3 or more, or graphite thereof.
  • a highly crystalline carbon material having similar properties is preferable.
  • Amorphous carbon is mentioned as a carbon material in which the d value of the lattice plane (002 plane) in (F) X-ray diffraction, which is an example of the negative electrode active material, exceeds 0.340 nm, and this is a high temperature of 2000 ° C. or higher.
  • non-graphitized carbon (hard carbon), mesocarbon microbeads (MCMB) calcined at 1500 ° C. or lower, mesopaise bitch carbon fiber (MCF) and the like are exemplified.
  • Carbotron (registered trademark) P manufactured by Kureha Corporation is a typical example.
  • oxide of one or more metals selected from (G) Si, Sn, Al examples of the negative electrode active material, include silicon oxide, tin oxide, and the like, which can be doped and dedoped with lithium ions. ..
  • SiO x and the like having a structure in which ultrafine particles of Si are dispersed in SiO 2 . When this material is used as the negative electrode active material, charging and discharging are smoothly performed because Si that reacts with Li is ultrafine particles, while the SiO x particles themselves having the above structure have a small surface area, so that the negative electrode active material layer.
  • the paintability of the composition (paste) for forming the negative electrode mixture and the adhesiveness of the negative electrode mixture layer to the current collector are also good. Since SiO x has a large volume change due to charge and discharge, the capacity can be increased and good charge / discharge cycle characteristics can be achieved by using SiO x and the graphite of the negative electrode active material (E) in a specific ratio in combination with the negative electrode active material. Can be compatible with.
  • the negative electrode active material (H) one or more metals selected from Si, Sn, and Al, alloys containing these metals, and alloys of these metals or alloys with lithium include, for example, silicon, tin, and aluminum. Examples thereof include metals, silicon alloys, tin alloys, aluminum alloys, etc., and materials in which these metals and alloys are alloyed with lithium during charge and discharge can also be used.
  • metal simple substances such as silicon (Si) and tin (Sn) described in WO2004 / 100293 and Japanese Patent Application Laid-Open No. 2008-016424, and the metal alloys thereof.
  • the metal is used for an electrode, it is preferable because it can develop a high charge capacity and the volume expansion / contraction due to charging / discharging is relatively small.
  • these metals are known to exhibit a high charging capacity because they are alloyed with Li during charging when they are used as the negative electrode of a lithium ion secondary battery, which is also preferable.
  • a negative electrode active material formed of silicon pillars having a submicron diameter a negative electrode active material made of fibers composed of silicon, and the like described in WO2004 / 042551, WO2007 / 083155, etc. may be used. ..
  • lithium titanate oxide (I) which is an example of the negative electrode active material
  • lithium titanate having a spinel structure examples include Li 4 + ⁇ Ti 5 O 12 ( ⁇ changes within the range of 0 ⁇ ⁇ ⁇ 3 depending on the charge / discharge reaction).
  • lithium titanate having a rams delite structure for example, Li 2 + ⁇ Ti 3 O 7 ( ⁇ changes within the range of 0 ⁇ ⁇ ⁇ 3 depending on the charge / discharge reaction) can be mentioned.
  • negative electrode active materials can be prepared according to, for example, the production methods described in JP-A-2007-018883, JP-A-2009-176752, and the like.
  • sodium ion secondary battery cations in the non-aqueous electrolyte is sodium mainly hard carbon and TiO 2, V 2 O 5, MoO 3 oxide such like are used as the negative electrode active material.
  • sodium-containing transition metal composite oxides such as NaFeO 2 , NaCrO 2 , NanoNiO 2 , NamnO 2 and NaCoO 2 are used as positive electrode active materials.
  • Substituted with the metal of Na 2 FeP 2 O 7 , NaCo 3 (PO 4 ) 2 P 2 O 7 and other transition metal phosphate compounds, TiS 2 , FeS 2 and other sulfides, or polyacetylene and polypara Conductive polymers such as phenylene, polyaniline, and polypyrrole, activated carbon, radical-generating polymers, carbon materials, and the like are used.
  • the negative electrode has a negative electrode current collector.
  • the negative electrode current collector for example, copper, stainless steel, nickel, titanium, alloys thereof, or the like can be used.
  • a negative electrode active material layer is formed on at least one surface of a negative electrode current collector.
  • the negative electrode active material layer is composed of, for example, the above-mentioned negative electrode active material, a binder, and, if necessary, a conductive agent.
  • the binder polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, styrene butadiene rubber (SBR), carboxymethyl cellulose, methyl cellulose, cellulose acetate phthalate, hydroxypropyl methyl cellulose, polyvinyl alcohol And so on.
  • a carbon material such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (granular graphite or flake graphite), fluorinated graphite can be used.
  • the electrode is obtained, for example, by dispersing and kneading an active material, a binder, and a conductive agent, if necessary, in a solvent such as N-methyl-2-pyrrolidone (NMP) or water in a predetermined blending amount. It can be obtained by applying the paste to a current collector and drying it to form an active material layer. It is preferable that the obtained electrode is compressed by a method such as a roll press to adjust the electrode to an appropriate density.
  • NMP N-methyl-2-pyrrolidone
  • the non-aqueous electrolyte battery may include (d) a separator.
  • a separator for preventing contact between the positive electrode (b) and the negative electrode (c)
  • polyolefins such as polypropylene and polyethylene, and non-woven fabrics and porous sheets made of cellulose, paper, glass fiber and the like are used. These films are preferably microporous so that the non-aqueous electrolytic solution soaks in and ions easily permeate.
  • the polyolefin separator include a film such as a microporous polymer film such as a porous polyolefin film that electrically insulates the positive electrode and the negative electrode and allows lithium ions to permeate.
  • the porous polyethylene film may be used alone, or the porous polyethylene film and the porous polypropylene film may be laminated and used as a multi-layer film. Further, a film obtained by combining a porous polyethylene film and a polypropylene film can be mentioned.
  • a metal can such as a coin type, a cylindrical type, or a square type, or a laminated exterior body can be used.
  • the metal can material include a nickel-plated iron steel plate, a stainless steel plate, a nickel-plated stainless steel plate, aluminum or an alloy thereof, nickel, titanium and the like.
  • the laminated exterior body for example, an aluminum laminated film, a SUS laminated film, a silica-coated polypropylene, a laminated film such as polyethylene, or the like can be used.
  • the configuration of the non-aqueous electrolytic solution battery according to the present embodiment is not particularly limited, but for example, an electrode element in which a positive electrode and a negative electrode are arranged to face each other and a non-aqueous electrolytic solution are contained in an exterior body.
  • the shape of the non-aqueous electrolyte battery is not particularly limited, but an electrochemical device having a shape such as a coin shape, a cylinder shape, a square shape, or an aluminum laminate sheet type can be assembled from each of the above elements.
  • Example 1-1 Preparation of non-aqueous electrolyte solution according to Examples and Comparative Examples
  • a mixed solvent having a volume ratio of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate having a volume ratio of 2.5: 4: 3.5 is used as the non-aqueous organic solvent, and LiPF 6 as a solute has a concentration of 1.0 mol / L in the solvent.
  • LiPF 6 LiPF 6 as a solute has a concentration of 1.0 mol / L in the solvent.
  • the addition was carried out with care so that the liquid temperature was in the range of 20 to 30 ° C.
  • the salt compound (1-1-Li) was dissolved so as to have a concentration of 0.005 mass% (50 mass ppm) with respect to the total amount of the non-aqueous electrolytic solution.
  • the above preparation was also carried out while maintaining the liquid temperature in the range of 20 to 30 ° C.
  • Table 1 shows the preparation conditions for the non-aqueous electrolyte solution.
  • "-" in all the tables indicates no addition.
  • Examples 1-2 to 1-5 (Preparation of non-aqueous electrolyte No. 1-2 to 1-5) Non-aqueous electrolyte solution No. 1 except that the concentrations of the salt compounds (1-1-Li) were changed as shown in Table 1. Similar to 1-1, the non-aqueous electrolyte solution No. 1-2 to 1-5 were prepared.
  • Examples 2-1 to 2-5 Comparative Examples 2-1 to 2-4> (Preparation of non-aqueous electrolyte Nos. 2-1 to 2-5 and comparative electrolytes No. 2-1 to 2-4) As shown in Table 2, the non-aqueous electrolyte solution No. 1 was used except that the salt compound (1-3-Li) was used instead of the salt compound (1-1-Li). 1-1 to 1-5, Comparative Electrolyte No. Similar to 1-1 to 1-4, the non-aqueous electrolyte solution No. 2-1 to 2-5, Comparative Electrolyte No. 2-1 to 2-4 were prepared.
  • Examples 3-1 to 3-5 Comparative examples 3-1 to 3-4> (Preparation of non-aqueous electrolyte Nos. 3-1 to 3-5 and comparative electrolytes Nos. 3-1 to 3-4) As shown in Table 3, the non-aqueous electrolyte solution No. 1 was used except that the salt compound (1-6-Li) was used instead of the salt compound (1-1-Li). 1-1 to 1-5, Comparative Electrolyte No. Similar to 1-1 to 1-4, the non-aqueous electrolyte solution No. 3-1 to 3-5, Comparative Electrolyte No. 3-1 to 3-4 were prepared.
  • Examples 4-1 to 4-5, Comparative Examples 4-1 to 4-4, Comparative Example 0-1> (Preparation of non-aqueous electrolyte Nos. 4-1 to 4-5, comparative electrolytes No. 4-1 to 4-4, comparative electrolyte No. 0-1) After dissolution of the salt compound (1-1-Li), non-aqueous except that lithium difluorophosphate (LiPO 2 F 2 ) was further added as another additive to the concentration shown in Table 4.
  • Examples 5-1 to 5-5, Comparative Examples 5-1 to 5-4, Comparative Example 0-2> (Preparation of non-aqueous electrolyte No. 5-1 to 5-5, comparative electrolyte No. 5-1 to 5-4, comparative electrolyte No. 0-2) After dissolution of the salt compound (1-1-Li), ethylene sulfate (Esa) was further added as another additive so as to have the concentration shown in Table 5, except that the non-aqueous electrolyte solution No. 1-1 to 1-5, Comparative Electrolyte No. 1-1 to 1-4, Comparative Electrolyte No. Similar to 0, the non-aqueous electrolyte solution No. 5-1 to 5-5, Comparative Electrolyte No. 5-1 to 5-4, Comparative Electrolyte No. 0-2 was prepared.
  • Esa ethylene sulfate
  • a non-aqueous electrolytic solution battery (test cell) was prepared as follows, using LiNi 0.6 Co 0.2 Mn 0.2 O 2 as a positive electrode material and graphite as a negative electrode material. ..
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • PVDF of 10% by mass as a binder was mixed with 90% by mass of graphite powder, and NMP was further added to form a slurry. This slurry was applied onto a copper foil and dried at 120 ° C. for 12 hours to prepare a test negative electrode body.
  • a non-aqueous electrolytic solution was impregnated into a polyethylene separator to assemble a 50 mAh cell having an aluminum laminate exterior.
  • a constant current constant voltage charge is performed at a charge upper limit voltage of 4.3 V and a 0.2 C rate (10 mA), and a charge / discharge cycle of discharging at a 0.2 C rate (10 mA) constant current up to a discharge end voltage of 3.0 V is performed three times. Repeated. The capacity obtained at this time was defined as the initial discharge capacity (25 ° C.). After this conditioning, a charge / discharge test was carried out at an environmental temperature of 60 ° C.
  • constant current constant voltage charging is performed at a 3C rate (150mA) up to a charging upper limit voltage of 4.3V
  • a charging / discharging cycle is performed in which discharging is performed at a 3C rate (150mA) constant current up to a discharge end voltage of 3.0V. Repeated 500 times. Subsequently, the non-aqueous electrolyte battery was cooled to 25 ° C., discharged to 3.0 V again, and then charged with a constant current and constant voltage to 4.3 V at a rate of 0.2 C at 25 ° C.
  • Non-aqueous electrolyte No. 1-1 to 1-5 Comparative Non-aqueous Electrolyte No.
  • the results of 1-1 to 1-4 were compared. More specifically, the comparative non-aqueous electrolyte solution No. Based on Comparative Example 0 using 0, the capacity retention rate after 500 cycles at 60 ° C. was set to 100, and the results of each of the other Examples and Comparative Examples were expressed as relative values. The results are shown in Table 7 and FIG.
  • Non-aqueous electrolyte No. 2-1 to 2-5 Comparative Non-aqueous Electrolyte No.
  • the results of 2-1 to 2-4 were compared. More specifically, the comparative non-aqueous electrolyte solution No. Based on Comparative Example 0 using 0, the capacity retention rate after 500 cycles at 60 ° C. was set to 100, and the results of each of the other Examples and Comparative Examples were expressed as relative values. The results are shown in Table 8 and FIG.
  • Non-aqueous electrolyte No. 3-1 to 3-5 Comparative Non-aqueous Electrolyte No.
  • the results of 3-1 to 3-4 were compared. More specifically, the comparative non-aqueous electrolyte solution No. Based on Comparative Example 0 using 0, the capacity retention rate after 500 cycles at 60 ° C. was set to 100, and the results of each of the other Examples and Comparative Examples were expressed as relative values. The results are shown in Table 9 and FIG.
  • Non-aqueous electrolyte No. 4-1 to 4-5 Comparative Non-aqueous Electrolyte No.
  • the results of 4-1 to 4-4 were compared. More specifically, the comparative non-aqueous electrolyte solution No. Based on Comparative Example 0-1 using 0-1 and the capacity retention rate after 500 cycles at 60 ° C. was set to 100, the results of each of the other Examples and Comparative Examples were expressed as relative values. The results are shown in Table 10 and FIG.
  • Non-aqueous electrolyte No. 5-1 to 5-5 Comparative Non-aqueous Electrolyte No.
  • the results of 5-1 to 5-4 were compared. More specifically, the comparative non-aqueous electrolyte solution No.
  • the results of each of the other Examples and Comparative Examples were expressed as relative values, with Comparative Example 0-2 using 0-2 as a reference, and the capacity retention rate after 500 cycles at 60 ° C. was set to 100. The results are shown in Table 11 and FIG.
  • Non-aqueous electrolyte No. 6-1 to 6-5 Comparative Non-aqueous Electrolyte No.
  • the results of 6-1 to 6-4 were compared. More specifically, the comparative non-aqueous electrolyte solution No. Based on Comparative Example 0-3 using 0-3, the capacity retention rate after 500 cycles at 60 ° C. was set to 100, and the results of each of the other Examples and Comparative Examples were expressed as relative values.
  • the results are shown in Table 12 and FIG.
  • the horizontal axis of the plots in FIGS. 1 to 6 is a logarithmic scale. In FIGS. 1 to 6, the concentration of the component (I) on the horizontal axis indicates the concentration of the component (I) with respect to the total amount of the non-aqueous electrolytic solution.
  • ⁇ Evaluation 2 Measurement of internal resistance of non-aqueous electrolyte battery after storage at 60 ° C for 10 days (low temperature internal resistance after high temperature storage)> A battery subjected to the same conditioning as in Evaluation 1 described above was charged with a constant current and constant voltage at a charging upper limit voltage of 4.3 V and a 0.1 C rate (5 mA), and then taken out from a charging / discharging device maintained at 25 ° C. It was placed in a constant temperature bath at ° C and stored for 10 days. After that, it is placed in a charging / discharging device maintained at 25 ° C.
  • Non-aqueous electrolyte No. 1-1 to 1-5 Comparative Non-aqueous Electrolyte No.
  • the results of 1-1 to 1-4 were compared. More specifically, the comparative non-aqueous electrolyte solution No. Comparative Example 0 using 0 was used as a reference, the absolute value of the DC resistance was set to 100, and the results of each of the other Examples and Comparative Examples were expressed as relative values. The results are shown in Table 7 and FIG.
  • Non-aqueous electrolyte No. 2-1 to 2-5 Comparative Non-aqueous Electrolyte No.
  • the results of 2-1 to 2-4 were compared. More specifically, the comparative non-aqueous electrolyte solution No. Comparative Example 0 using 0 was used as a reference, the absolute value of the DC resistance was set to 100, and the results of each of the other Examples and Comparative Examples were expressed as relative values. The results are shown in Table 8 and FIG.
  • Non-aqueous electrolyte No. 3-1 to 3-5 Comparative Non-aqueous Electrolyte No.
  • the results of 3-1 to 3-4 were compared. More specifically, the comparative non-aqueous electrolyte solution No. Comparative Example 0 using 0 was used as a reference, the absolute value of the DC resistance was set to 100, and the results of each of the other Examples and Comparative Examples were expressed as relative values. The results are shown in Table 9 and FIG.
  • Non-aqueous electrolyte No. 4-1 to 4-5 Comparative Non-aqueous Electrolyte No.
  • the results of 4-1 to 4-4 were compared. More specifically, the comparative non-aqueous electrolyte solution No.
  • the results of each of the other Examples and Comparative Examples were expressed as relative values, with Comparative Example 0-1 using 0-1 as a reference and the absolute value of the DC resistance being 100. The results are shown in Table 10 and FIG.
  • Non-aqueous electrolyte No. 5-1 to 5-5 Comparative Non-aqueous Electrolyte No.
  • the results of 5-1 to 5-4 were compared. More specifically, the comparative non-aqueous electrolyte solution No. Based on Comparative Example 0-2 using 0-2, the absolute value of the DC resistance was set to 100, and the results of each of the other Examples and Comparative Examples were expressed as relative values. The results are shown in Table 11 and FIG.
  • Non-aqueous electrolyte No. 6-1 to 6-5 Comparative Non-aqueous Electrolyte No.
  • the results of 6-1 to 6-4 were compared. More specifically, the comparative non-aqueous electrolyte solution No. Based on Comparative Example 0-3 using 0-3, the absolute value of the DC resistance was set to 100, and the results of each of the other Examples and Comparative Examples were expressed as relative values. The results are shown in Table 12 and FIG.
  • the concentration of the salt compound represented by the general formula (1), other additives or other components indicates the concentration with respect to the total amount of the non-aqueous electrolytic solution. Further, in Table 5, Esa represents ethylene sulfate.
  • the results of Examples 1-3, 4-3, 5-3, and 6-3 are relatively compared with Comparative Example 0 as a reference and the capacity retention rate after 500 cycles at 60 ° C. as 100.
  • the results of Examples 1-3, 4-3, 5-3, and 6-3 are relatively compared with Comparative Example 0 as a reference and the low temperature internal resistance after high temperature storage as 100.
  • the capacity retention rate after a long cycle at a high temperature 60 ° C. or higher
  • the effect of improving the capacity retention rate after a long cycle at a high temperature (60 ° C. or higher) and the effect of suppressing an increase in resistance at a low temperature (0 ° C. or lower, particularly ⁇ 20 ° C. or lower) after high temperature storage are exhibited.
  • a non-aqueous electrolyte solution that can be exhibited in a well-balanced manner, and a non-aqueous electrolyte solution battery can be provided.

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EP20818229.5A EP3965128B1 (en) 2019-06-05 2020-06-03 Nonaqueous electrolyte solution, and nonaqueous electrolyte battery
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CN116344936A (zh) * 2023-04-12 2023-06-27 武汉理工大学 一种电解液添加剂、电解液以及钠离子电池
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