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WO2016002481A1 - Solution d'électrolyte pour batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux utilisant celle-ci - Google Patents

Solution d'électrolyte pour batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux utilisant celle-ci Download PDF

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Publication number
WO2016002481A1
WO2016002481A1 PCT/JP2015/067049 JP2015067049W WO2016002481A1 WO 2016002481 A1 WO2016002481 A1 WO 2016002481A1 JP 2015067049 W JP2015067049 W JP 2015067049W WO 2016002481 A1 WO2016002481 A1 WO 2016002481A1
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group
electrolyte
aqueous electrolyte
oxalato
electrolyte battery
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English (en)
Japanese (ja)
Inventor
孝敬 森中
幹弘 高橋
益隆 新免
誠 久保
渉 河端
寛樹 松崎
建太 山本
憲治 久保
勝也 久保
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Central Glass Co Ltd
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Central Glass Co Ltd
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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrolyte for a non-aqueous electrolyte battery containing at least lithium hexafluorophosphate as a solute and a non-aqueous electrolyte battery using the same.
  • non-aqueous electrolyte batteries such as lithium ion batteries, lithium batteries, and lithium ion capacitors have been actively developed.
  • Non-aqueous electrolyte battery One problem with such a non-aqueous electrolyte battery is that the battery is swollen due to gas generation accompanying the electrochemical decomposition reaction of the components contained in the electrolyte during use of the battery, and the battery characteristics are deteriorated accordingly.
  • the present applicant has previously determined that the high-temperature cycle characteristics and 45 ° C. of the non-aqueous electrolyte battery can be obtained without impairing the battery characteristics by suppressing the gas generation associated with the electrochemical decomposition reaction of the components contained in the electrolyte.
  • Patent Document 1 A patent application was filed for an invention relating to an electrolyte solution for a non-aqueous electrolyte battery for improving durability such as high-temperature storage stability
  • This electrolyte is In a non-aqueous electrolyte battery electrolyte containing a non-aqueous organic solvent and a solute, First compound consisting of bis (oxalato) borate, difluoro (oxalato) borate, tris (oxalato) phosphate, difluorobis (oxalato) phosphate, tetrafluoro (oxalato) phosphate as additives At least one compound selected from the group; It includes at least one compound selected from the group consisting of an imide salt having a predetermined structure and an imide salt having a sulfonate group, and an imide salt having a predetermined structure and having a phosphoryl group. .
  • the electrolyte for a non-aqueous electrolyte battery described above it is possible to suppress the generation of gas accompanying the electrochemical decomposition reaction of components contained in the electrolyte, thereby reducing the performance of the non-aqueous electrolyte battery.
  • durability such as high-temperature cycle characteristics and high-temperature storage stability of 45 ° C. or higher can be improved
  • the amount of gas generated when used as a battery is preferably as small as possible, and the amount of gas generated can be further suppressed without impairing battery characteristics.
  • An electrolyte for a non-aqueous electrolyte battery may be required.
  • the present invention provides an electrolyte for a non-aqueous electrolyte battery that can further suppress the amount of gas generated during a charge / discharge cycle without impairing the battery characteristics when used in a non-aqueous electrolyte battery, and uses the same.
  • An object of the present invention is to provide a nonaqueous electrolyte battery.
  • non-aqueous electrolyte for a non-aqueous electrolyte battery containing a non-aqueous solvent and a solute, Containing at least lithium hexafluorophosphate as a solute, Containing at least one imide salt having a phosphoryl group in which at least one fluorine atom is bonded to a phosphorus atom; Substantially free of bis (oxalato) borate, difluoro (oxalato) borate, tris (oxalato) phosphate, difluorobis (oxalato) phosphate, and tetrafluoro (oxalato) phosphate, non- As an electrolyte for water electrolyte batteries, It has been found that when the electrolyte is used in a non-aqueous electrolyte battery, the amount of gas generation can be further suppressed without
  • the present invention provides a nonaqueous electrolyte solution for a nonaqueous electrolyte battery containing a nonaqueous solvent and a solute, Containing at least lithium hexafluorophosphate as a solute, Containing at least one imide salt having a phosphoryl group represented by the general formula (I) (hereinafter sometimes simply referred to as “imide salt”), Substantially free of bis (oxalato) borate, difluoro (oxalato) borate, tris (oxalato) phosphate, difluorobis (oxalato) phosphate, and tetrafluoro (oxalato) phosphate.
  • imide salt having a phosphoryl group represented by the general formula (I) (hereinafter sometimes simply referred to as “imide salt”)
  • R 1 to R 4 are each independently a fluorine atom or an organic group represented by —OR 5 ;
  • R 5 is a linear or branched alkyl group, alkenyl group having 1 to 10 carbon atoms, or And at least one organic group selected from an alkynyl group, a cycloalkyl group or a cycloalkenyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and a fluorine atom or an oxygen atom in the organic group
  • Unsaturated bonds can also be present.
  • M represents an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer equal to the valence of the corresponding cation. However, at least one of R 1 to R 4 represents a fluorine atom. ]
  • the imide salt represented by the general formula (I) the more PF bonds, the more excellent the cycle characteristics and the internal resistance characteristics when the electrolyte containing the imide salt is used in a non-aqueous electrolyte battery. Since it is easy to exhibit, it is preferable that the imide salt represented by the general formula (I) is a compound in which R 1 to R 4 are all fluorine atoms.
  • the imide salt represented by the general formula (I) is a compound in which the organic group represented by R 5 is at least one group selected from a hydrocarbon group having 6 or less carbon atoms which may contain a fluorine atom. It is preferable that
  • the group represented by R 5 is a methyl group, an ethyl group, a propyl group, a vinyl group, an allyl group, an ethynyl group, a 2-propynyl group, a phenyl group, From 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, and 1,1,1,3,3,3-hexafluoroisopropyl group A compound which is at least one selected group is preferable.
  • the counter cation of the imide salt represented by the general formula (I) is preferably at least one counter cation selected from the group consisting of lithium ions, sodium ions, potassium ions, and tetraalkylammonium ions.
  • the addition amount of the imide salt represented by the general formula (I) is preferably in the range of 0.01 to 5.0% by mass with respect to the total amount of the electrolyte for the nonaqueous electrolyte battery.
  • the imide salt represented by the general formula (I) is preferably highly pure, and particularly preferably the Cl (chlorine) content is 5000 mass ppm or less, particularly 1000 mass ppm or less. Further preferred.
  • lithium tetrafluoroborate LiBF 4
  • bis (fluorosulfonyl) imide lithium LiN (FSO 2 ) 2
  • bis (trifluoromethanesulfonyl) imide lithium LiN (CF 3 SO 2 ) 2
  • at least one selected from the group consisting of lithium difluorophosphate LiPO 2 F 2
  • LiBF 4 lithium tetrafluoroborate
  • bis (fluorosulfonyl) imide lithium LiN (FSO 2 ) 2
  • bis (trifluoromethanesulfonyl) imide lithium LiN (CF 3 SO 2 ) 2
  • at least one selected from the group consisting of lithium difluorophosphate LiPO 2 F 2
  • the non-aqueous solvent is at least one selected from the group consisting of cyclic carbonates, chain carbonates, cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids. Is preferred.
  • the present invention also provides a nonaqueous electrolyte battery comprising at least a positive electrode, a negative electrode, and an electrolyte for a nonaqueous electrolyte battery, wherein the electrolyte for the nonaqueous electrolyte battery is the above-described electrolysis for a nonaqueous electrolyte battery. It is a nonaqueous electrolyte battery characterized by being a liquid.
  • the electrolyte of the present invention When the electrolyte of the present invention is used in a non-aqueous electrolyte battery, the amount of gas generated during a high-temperature charge / discharge cycle can be greatly suppressed, and battery characteristics (cycle characteristics, internal resistance characteristics) associated with gas generation can be reduced. ) Can be suppressed.
  • the non-aqueous electrolyte battery electrolyte of the present invention is a non-aqueous electrolyte battery non-aqueous electrolyte solution containing a non-aqueous solvent and a solute. Containing at least lithium hexafluorophosphate as a solute, Containing at least one imide salt having a phosphoryl group represented by the general formula (I), Substantially free of bis (oxalato) borate, difluoro (oxalato) borate, tris (oxalato) phosphate, difluorobis (oxalato) phosphate, and tetrafluoro (oxalato) phosphate. It is the electrolyte solution for non-aqueous electrolyte batteries characterized.
  • the electrolyte substantially comprises bis (oxalato) borate, difluoro (oxalato) borate, tris (oxalato) phosphate, difluorobis (oxalato) phosphate, and tetrafluoro (oxalato) phosphate.
  • the electrolyte is used in a non-aqueous electrolyte battery, the amount of gas generated can be further suppressed. “Substantially not contained” means that the concentration of the total amount of the above compounds in the electrolytic solution is 100 ppm by mass or less.
  • examples of the alkyl group represented by R 5 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, pentyl group, 2, 2 -Carbon atoms such as difluoroethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl, and 1,1,1,3,3,3-hexafluoroisopropyl
  • Examples of the alkenyl group include vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, and 1,3-butadienyl group.
  • Examples include alkenyl groups having 2 to 8 carbon atoms or fluorine-containing alkenyl groups.
  • alkynyl groups include ethynyl group, 2-propynyl group, and 1,1 dimethyl-2-propynyl group. Examples thereof include alkynyl groups having 2 to 8 carbon atoms or fluorine-containing alkynyl groups.
  • cycloalkyl groups include cycloalkyl groups having 3 to 10 carbon atoms such as cyclopentyl groups and cyclohexyl groups or fluorine-containing cycloalkyl groups.
  • Examples of the cycloalkenyl group include a cycloalkenyl group having 3 to 10 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group or a fluorine-containing cycloalkenyl group.
  • Examples of the aryl group include a phenyl group, a tolyl group, and Examples thereof include aryl groups having 6 to 10 carbon atoms such as xylyl groups and fluorine-containing aryl groups.
  • examples of the anion of the imide salt represented by the general formula (I) include the following compound Nos. 1-No. 10 etc. are mentioned.
  • the imide salt used in the present invention is not limited by the following examples.
  • R 1 to R 4 is a fluorine atom. The reason is not clear, but unless at least one is a fluorine atom, the effect of suppressing the internal resistance of a battery using the electrolytic solution is not sufficient.
  • the organic group represented by R 5 is preferably at least one group selected from hydrocarbon groups having 6 or less carbon atoms which may contain a fluorine atom.
  • the number of carbon atoms is large, the internal resistance tends to be relatively large when a film is formed on the electrode. It is preferable that the number of carbon atoms is 6 or less because the above-mentioned internal resistance tends to be smaller.
  • methyl group, ethyl group, propyl group, vinyl group, allyl group, ethynyl group, 2-propynyl group, phenyl group, 2 , 2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, and 1,1,1,3,3,3-hexafluoroisopropyl group It is preferable that at least one group is obtained because a nonaqueous electrolyte battery that is superior in cycle characteristics and internal resistance characteristics can be obtained.
  • the imide salt represented by the above general formula (I) is preferably highly pure, and in particular, the Cl (chlorine) content is preferably 5000 ppm by mass or less, more preferably 1000 ppm by mass or less, and still more preferably Is 100 mass ppm or less.
  • Cl (chlorine) remains at a high concentration is not preferable because it tends to corrode battery members.
  • an imide salt (compound No. 1) in which all of R 1 to R 4 are fluorine atoms is, for example, Z. Anorg. Allg. Chem. 412 ( 1), 65-70, (1975).
  • An imide salt in which at least one of R 1 to R 4 has an organic group represented by —OR 5 is exemplified by, for example, Compound No. 1 can be obtained by adding a corresponding alcohol (HOR 5 ) and a base to react.
  • the electrolytic solution of the present invention tends to be able to suppress decomposition of lithium hexafluorophosphate, which is a solute, during high temperature storage.
  • the imide salt represented by the general formula (I) at least one of R 1 to R 4 is preferably a fluorine atom because the effect of improving the thermal stability of lithium hexafluorophosphate is easily exhibited.
  • the imide salt interacts with phosphorus pentafluoride to prevent phosphorus pentafluoride from causing a reaction other than the above reaction formula, so that the equilibrium of the above reaction formula is prevented from being tilted to the right. It is estimated that the thermal stability of lithium acid acid is improved.
  • the imide salt is a salt having a high degree of ionic dissociation in the solution, it does not cause a decrease in the ionic conductivity of the electrolytic solution. Does not increase resistance. Further, when a fluorine atom is bonded to phosphorus of an imide salt, the electron withdrawing effect causes delocalization of electrons in the anion, and the degree of ion dissociation can be further increased. In addition, it is considered that the imide salt according to the present invention is partially decomposed at the interface between the positive electrode and the electrolytic solution and the interface between the negative electrode and the electrolytic solution to form a film.
  • This film suppresses direct contact between the non-aqueous solvent or solute and the active material, prevents decomposition of the non-aqueous solvent or solute, and suppresses deterioration of battery performance.
  • the mechanism is not clear, it is thought that when fluorine atoms are bonded to phosphorus of imide salt, the charge of the film formed by the electron withdrawing effect is biased, and the film has high lithium conductivity, that is, low resistance. .
  • the above effect tends to increase as the number of PF bonds increases in the imide salt represented by the general formula (I).
  • a suitable addition amount of the imide salt used in the present invention is 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, based on the total amount of the nonaqueous electrolytic solution.
  • an upper limit is 5.0 mass% or less, Preferably it is 4.0 mass% or less, More preferably, it is 3.0 mass% or less. If the amount added is less than 0.01% by mass, it is not preferable because the effect of improving battery characteristics is hardly obtained. On the other hand, if the amount added exceeds 5.0% by mass, it is not preferable because it is not only useless because no further effect is obtained, but also because resistance is increased due to excessive film formation and deterioration of battery performance is likely to occur. .
  • These imide salts may be used alone as long as they do not exceed 5.0% by mass, or two or more of them may be used in any combination and ratio according to the application.
  • the type of the non-aqueous solvent used in the non-aqueous electrolyte battery electrolyte of the present invention is not particularly limited, and any non-aqueous solvent can be used.
  • Specific examples include cyclic carbonates such as propylene carbonate, ethylene carbonate, and butylene carbonate, chain carbonates such as diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate, cyclic esters such as ⁇ -butyrolactone and ⁇ -valerolactone, methyl acetate, and propion.
  • Examples include chain esters such as methyl acid, cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and dioxane, chain ethers such as dimethoxyethane and diethyl ether, sulfone compounds such as dimethyl sulfoxide and sulfolane, and sulfoxide compounds.
  • chain esters such as methyl acid
  • cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and dioxane
  • chain ethers such as dimethoxyethane and diethyl ether
  • sulfone compounds such as dimethyl sulfoxide and sulfolane
  • sulfoxide compounds e.g., butanethoxyethane and diethyl ether
  • sulfone compounds such as dimethyl sulfoxide and sulfolane
  • sulfoxide compounds e.g.,
  • propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate are particularly preferred from the viewpoint of electrochemical stability against redox and chemical stability related to the reaction with heat and the above solute.
  • the kind of the other solute that may coexist with lithium hexafluorophosphate used in the electrolyte solution for a non-aqueous electrolyte battery of the present invention is not particularly limited, and a conventionally known lithium salt can be used.
  • One kind of these solutes may be used alone, or two or more kinds thereof may be used in any combination and in any ratio according to the application.
  • LiBF 4 LiN (CF 3 SO 2 ) 2 , LiN (FSO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , and LiPO 2 F 2 is preferred.
  • the suitable 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.
  • the upper limit is 2.5 mol / L or less, preferably 2.0 mol / L or less, and more preferably 1.5 mol / L or less. If the concentration is less than 0.5 mol / L, the ionic conductivity tends to decrease and the cycle characteristics and output characteristics of the nonaqueous electrolyte battery tend to decrease. On the other hand, if the concentration exceeds 2.5 mol / L, the nonaqueous electrolyte battery is used. When the viscosity of the electrolytic solution increases, the ionic conductivity also tends to be lowered, and the cycle characteristics and output characteristics of the nonaqueous electrolytic battery may be lowered.
  • the temperature of the non-aqueous electrolyte may increase due to the heat of dissolution of the solute.
  • the liquid temperature rises remarkably decomposition of the lithium salt containing fluorine atoms is accelerated and hydrogen fluoride may be generated. Hydrogen fluoride is not preferable because it causes deterioration of battery performance.
  • the liquid temperature when dissolving the solute in the non-aqueous solvent is not particularly limited, but is preferably ⁇ 20 to 80 ° C., more preferably 0 to 60 ° C.
  • the electrolyte solution for a non-aqueous electrolyte battery of the present invention is generally used as long as the gist of the present invention is not impaired.
  • non-aqueous electrolyte battery electrolyte in a quasi-solid state with a gelling agent or a crosslinked polymer as used in a non-aqueous electrolyte battery called a lithium polymer battery.
  • the non-aqueous electrolyte battery according to the present invention is characterized by using the above-described electrolyte for a non-aqueous electrolyte battery according to the present invention, and the other components are those used in general non-aqueous electrolyte batteries. Is used. That is, it comprises a positive electrode and a negative electrode capable of inserting and extracting lithium, a current collector, a separator, a container, and the like.
  • the negative electrode material is not particularly limited, but lithium metal, alloys of lithium and other metals or intermetallic compounds, various carbon materials, artificial graphite, natural graphite, metal oxides, metal nitrides, tin (single), A tin compound, silicon (simple substance), a silicon compound, activated carbon, a conductive polymer, or the like is used.
  • the positive electrode material is not particularly limited.
  • lithium-containing transition metal composite oxides such as LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , and lithium-containing transition metals A composite oxide in which a plurality of transition metals such as Co, Mn, Ni, etc.
  • transition metal in the lithium-containing transition metal composite oxide is replaced with a metal other than the transition metal, olivine and LiFePO 4, LiCoPO 4, phosphoric acid compound of a transition metal such as LiMnPO 4 called, oxides such as TiO 2, V 2 O 5, MoO 3, TiS 2, sulfides such as FeS, or polyacetylene, polyparaphenylene, polyaniline , And conductive polymers such as polypyrrole, activated carbon, polymers that generate radicals, carbon materials, etc. It is use.
  • acetylene black, ketjen black, carbon fiber, graphite as a conductive material, polytetrafluoroethylene, polyvinylidene fluoride, SBR resin, etc. as a binder to the positive electrode or negative electrode material, and forming into a sheet shape It can be an electrode sheet.
  • a separator for preventing contact between the positive electrode and the negative electrode a nonwoven fabric or a porous sheet made of polypropylene, polyethylene, paper, glass fiber, or the like is used.
  • a non-aqueous electrolyte battery having a coin shape, cylindrical shape, square shape, aluminum laminate sheet shape or the like is assembled from the above elements.
  • Table 1 shows the preparation conditions of the non-aqueous electrolyte
  • Table 2 shows the storage stability evaluation results of the electrolyte
  • Table 3 shows the evaluation results of the battery using the electrolyte.
  • the values of the cycle characteristics, internal resistance characteristics, and gas generation amount of the batteries in Table 3 are the values of the electrolyte No. 1 before standing for one month after preparation. This is a relative value when the discharge capacity retention rate and internal resistance after the cycle test of the laminate cell produced using No. 33 and the amount of gas generated due to cycle characteristic evaluation are set to 100, respectively.
  • a mixed solvent of ethylene carbonate and ethyl methyl carbonate in a volume ratio of 1: 2 was used as the non-aqueous solvent, LiPF 6 was 1.0 mol / L as a solute in the solvent, and the imide compound No. 1 was used as an additive.
  • 1 lithium salt (Cl content in the imide salt is 90 mass ppm) was dissolved to a concentration of 0.03% by mass to prepare an electrolyte for a non-aqueous electrolyte battery. The above preparation was carried out while maintaining the liquid temperature in the range of 20-30 ° C.
  • the free acid of the electrolyte was measured by neutralization titration.
  • the measurement sample is an electrolytic solution within one day after preparation (electrolytic solution before standing at 75 ° C.) and an electrolytic solution after one month of standing at 75 ° C. after preparation.
  • the free acid was measured at room temperature.
  • As a titration indicator a 0.1 w / v% bromophenol blue ethanol (50%) solution was used.
  • Examples 1-2 to 1-29 A nonaqueous electrolytic solution was prepared in the same procedure as in Example 1-1 except that the conditions for preparing the nonaqueous electrolytic solution shown in Table 1 were followed. In addition, all Cl content in the imide salt used in the Example was about 90 mass ppm. In addition, in Examples 1-24 to 1-29, other electrolytes other than the imide salt and lithium hexafluorophosphate in Example 1-1 (hereinafter, may be simply referred to as “other electrolytes”) It is an experiment example regarding the electrolyte solution which contains.
  • Examples 1-2 to 1-29 bis (oxalato) borate, difluoro (oxalato) borate, tris (oxalato) phosphate, difluorobis (oxalato) phosphate in the electrolytic solution
  • the total concentration of tetrafluoro (oxalato) phosphate was less than 100 ppm by mass.
  • Table 2 shows the results of evaluating the storage stability of the electrolytic solution
  • Table 3 shows the results of evaluating batteries using the electrolytic solution.
  • Comparative Examples 1-1 to 1-10 A nonaqueous electrolytic solution was prepared in the same procedure as in Example 1-1 except that the conditions for preparing the nonaqueous electrolytic solution shown in Table 1 were followed.
  • Comparative Examples 1-1 to 1-3 each of the following compound Nos. 11, no. 12 lithium salt is used, or instead of compound no. 13 is an experimental example relating to an electrolytic solution using 13 (amide compound).
  • Comparative Example 1-4 was prepared in the same manner as Example 1-1 except that neither imide salt nor other electrolyte was added. It is an experiment example regarding electrolyte solution.
  • Comparative Examples 1-1 to 1-4 bis (oxalato) borate, difluoro (oxalato) borate, tris (oxalato) phosphate, difluorobis (oxalato) phosphate in the electrolytic solution
  • the total concentration of tetrafluoro (oxalato) phosphate was less than 100 ppm by mass.
  • Comparative Examples 1-5 to 1-10 as other electrolytes, were bis (oxalato) lithium borate, difluorobis (oxalato) lithium phosphate, tetrafluoro (oxalato) lithium phosphate, difluoro (oxalato), respectively.
  • Example 4 shows the evaluation results of the battery in which the negative electrode body used in Example 1-1 was changed.
  • a non-aqueous electrolyte No. 1 is used as an electrolyte for a non-aqueous electrolyte battery.
  • the cycle characteristics, internal resistance characteristics, and gas generation amount were evaluated in the same manner as in Example 1-1.
  • the negative electrode active material is Li 4 Ti 5 O 12
  • the negative electrode body is 90% by mass of Li 4 Ti 5 O 12 powder.
  • Example 33 are set to 100 (Comparative Example 2-1).
  • the negative electrode active material is graphite (silicon-containing)
  • the negative electrode body is composed of 80% by mass of graphite powder and 10% by mass of silicon powder.
  • PVDF polyvinylidene fluoride
  • Examples 3-1 to 3-4, Comparative examples 3-1 to 3-2 Table 4 shows the evaluation results of the batteries in which the positive electrode used in Example 1-1 was changed.
  • a non-aqueous electrolyte No. 1 is used as an electrolyte for a non-aqueous electrolyte battery.
  • the cycle characteristics, internal resistance characteristics, and gas generation amount were evaluated in the same manner as in Example 1-1.
  • the positive electrode body in which the positive electrode active material is LiCoO 2 is a mixture of 90% by mass of LiCoO 2 powder, 5% by mass of polyvinylidene fluoride (PVDF) as a binder and 5% by mass of acetylene black as a conductive material, and N-methyl. Pyrrolidone was added, and the resulting paste was applied on an aluminum foil and dried. The end-of-charge voltage during battery evaluation was 4.2 V, and the end-of-discharge voltage was 3.0 V.
  • the values of the cycle characteristics, internal resistance characteristics, and gas generation amount of the batteries are the same as those of the electrolyte No. 1 before standing for one month after preparation. This is a relative value when the discharge capacity retention rate after the cycle test, the internal resistance, and the gas generation amount associated with the cycle characteristic evaluation of the laminate cell produced using No. 33 are each 100 (Comparative Example 3-1).
  • Example 4-1 to 4-4 Comparative Examples 4-1 to 4-2
  • Table 4 shows the evaluation results of the batteries in which the positive electrode used in Example 1-1 was changed.
  • a non-aqueous electrolyte No. 1 is used as an electrolyte for a non-aqueous electrolyte battery.
  • the cycle characteristics, internal resistance characteristics, and gas generation amount were evaluated in the same manner as in Example 1-1.
  • the positive electrode body in which the positive electrode active material is LiNi 0.8 Co 0.15 Al 0.05 O 2 is composed of 90% by mass of LiNi 0.8 Co 0.15 Al 0.05 O 2 powder, 5% by mass of polyvinylidene fluoride (PVDF) as a binder, and acetylene as a conductive material. Black was mixed at 5% by mass, N-methylpyrrolidone was further added, and the obtained paste was applied on an aluminum foil and dried.
  • the end-of-charge voltage during battery evaluation was 4.2 V, and the end-of-discharge voltage was 3.0 V.
  • Examples 4-1 to 4-4 and Comparative Example 4-2 the values of the cycle characteristics, internal resistance characteristics, and gas generation amount of the batteries are the same as those of the electrolyte No. 1 before standing for one month after preparation. This is a relative value when the discharge capacity retention rate, the internal resistance, and the gas generation amount associated with the cycle characteristics evaluation after the cycle test of the laminate cell produced using No. 33 are each 100 (Comparative Example 4-1).
  • Examples 5-1 to 5-4, Comparative Examples 5-1 to 5-2 Table 4 shows the evaluation results of the batteries in which the positive electrode used in Example 1-1 was changed.
  • a non-aqueous electrolyte No. 1 is used as an electrolyte for a non-aqueous electrolyte battery.
  • the cycle characteristics, internal resistance characteristics, and gas generation amount were evaluated in the same manner as in Example 1-1.
  • the positive electrode body in which the positive electrode active material is LiFePO 4 is obtained by adding 90% by mass of LiFePO 4 powder coated with amorphous carbon to 5% by mass of polyvinylidene fluoride (PVDF) as a binder and 5% by mass of acetylene black as a conductive material. %, Further N-methylpyrrolidone was added, and the resulting paste was applied on an aluminum foil and dried.
  • the end-of-charge voltage during battery evaluation was 4.1 V, and the end-of-discharge voltage was 2.5 V.
  • the values of the cycle characteristics, internal resistance characteristics, and gas generation amount of the batteries are the same as those of the electrolyte solution No. This is a relative value when the discharge capacity retention rate after the cycle test, the internal resistance, and the gas generation amount associated with the cycle characteristic evaluation of the laminate cell produced using No. 33 are each 100 (Comparative Example 5-1).
  • the laminate cell using the electrolyte for the non-aqueous electrolyte battery of the present invention It was confirmed that the cycle characteristics, internal resistance characteristics, and gas generation amount were superior to the corresponding comparative examples. Therefore, by using the electrolyte for a non-aqueous electrolyte battery of the present invention, a non-aqueous electrolyte battery exhibiting excellent cycle characteristics, internal resistance characteristics, and gas generation amount suppression can be obtained regardless of the type of the positive electrode active material. It was shown that.
  • the laminate cell using the electrolyte solution for a non-aqueous electrolyte battery of the present invention. It was confirmed that the cycle characteristics, internal resistance characteristics, and gas generation amount were superior to the corresponding comparative examples. Therefore, by using the electrolyte for a non-aqueous electrolyte battery of the present invention, a non-aqueous electrolyte battery exhibiting excellent cycle characteristics, internal resistance characteristics, and gas generation amount suppression can be obtained regardless of the type of the negative electrode active material. It was shown that.

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Abstract

La présente invention concerne une solution d'électrolyte pour batteries à électrolyte non aqueux contenant un solvant non aqueux et un soluté, qui contient au moins de l'hexafluorophosphate de lithium en tant que soluté, tout en contenant au moins un sel d'imide représenté par la formule M[R1R2OPNPOR3R4]m et ayant un groupe phosphoryle, mais ne contenant sensiblement pas un bis(oxalato)borate, un difluoro(oxalato)borate, un tris(oxalato)phosphate, un difluorobis(oxalato)phosphate et un tétrafluoro(oxalato)phosphate. La solution d'électrolyte pour batteries à électrolyte non aqueux est capable de supprimer plus avant la quantité de génération de gaz sans détériorer les caractéristiques de la batterie.
PCT/JP2015/067049 2014-07-01 2015-06-12 Solution d'électrolyte pour batteries à électrolyte non aqueux, et batterie à électrolyte non aqueux utilisant celle-ci Ceased WO2016002481A1 (fr)

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WO2018190304A1 (fr) * 2017-04-10 2018-10-18 セントラル硝子株式会社 Procédé de production de sel de phosphoryle imide, procédé de production d'une solution d'électrolyte non aqueuse contenant ledit sel, et procédé de production de batterie secondaire non aqueuse
CN112186254A (zh) * 2020-09-30 2021-01-05 香河昆仑化学制品有限公司 一种含二氟草酸磷酰亚胺锂的电解液及使用该电解液的锂离子电池
CN112186250A (zh) * 2020-09-30 2021-01-05 香河昆仑化学制品有限公司 一种含双草酸磷酰亚胺锂的电解液及使用该电解液的锂离子电池
CN112736284A (zh) * 2020-12-28 2021-04-30 远景动力技术(江苏)有限公司 低阻抗长循环的非水电解液及基于其的锂离子电池
WO2025121312A1 (fr) * 2023-12-07 2025-06-12 セントラル硝子株式会社 Solution électrolytique non aqueuse pour batterie à solution électrolytique non aqueuse, et batterie à solution électrolytique non aqueuse

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KR102148895B1 (ko) 2016-07-01 2020-08-27 샌트랄 글래스 컴퍼니 리미티드 비수계 전해액, 및 비수계 전해액 이차전지
JP6860782B2 (ja) 2016-07-01 2021-04-21 セントラル硝子株式会社 非水系電解液用添加剤、該添加剤を用いる非水系電解液、及び非水系電解液二次電池
JP6874215B2 (ja) * 2018-04-06 2021-05-19 株式会社東芝 非水電解質電池及び電池パック
CN116670828A (zh) 2020-12-24 2023-08-29 罗姆股份有限公司 半导体器件

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WO2018190304A1 (fr) * 2017-04-10 2018-10-18 セントラル硝子株式会社 Procédé de production de sel de phosphoryle imide, procédé de production d'une solution d'électrolyte non aqueuse contenant ledit sel, et procédé de production de batterie secondaire non aqueuse
JPWO2018190304A1 (ja) * 2017-04-10 2020-04-02 セントラル硝子株式会社 ホスホリルイミド塩の製造方法、該塩を含む非水電解液の製造方法及び非水二次電池の製造方法
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JP7128422B2 (ja) 2017-04-10 2022-08-31 セントラル硝子株式会社 ホスホリルイミド塩の製造方法、該塩を含む非水電解液の製造方法及び非水二次電池の製造方法
CN112186254A (zh) * 2020-09-30 2021-01-05 香河昆仑化学制品有限公司 一种含二氟草酸磷酰亚胺锂的电解液及使用该电解液的锂离子电池
CN112186250A (zh) * 2020-09-30 2021-01-05 香河昆仑化学制品有限公司 一种含双草酸磷酰亚胺锂的电解液及使用该电解液的锂离子电池
CN112186254B (zh) * 2020-09-30 2022-11-25 香河昆仑新能源材料股份有限公司 一种含二氟草酸磷酰亚胺锂的电解液及使用该电解液的锂离子电池
CN112736284A (zh) * 2020-12-28 2021-04-30 远景动力技术(江苏)有限公司 低阻抗长循环的非水电解液及基于其的锂离子电池
WO2025121312A1 (fr) * 2023-12-07 2025-06-12 セントラル硝子株式会社 Solution électrolytique non aqueuse pour batterie à solution électrolytique non aqueuse, et batterie à solution électrolytique non aqueuse

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