WO2019093411A1 - Électrolyte présentant des propriétés d'extinction d'incendie, et batterie secondaire comprenant ledit électrolyte - Google Patents

Électrolyte présentant des propriétés d'extinction d'incendie, et batterie secondaire comprenant ledit électrolyte Download PDF

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WO2019093411A1
WO2019093411A1 PCT/JP2018/041448 JP2018041448W WO2019093411A1 WO 2019093411 A1 WO2019093411 A1 WO 2019093411A1 JP 2018041448 W JP2018041448 W JP 2018041448W WO 2019093411 A1 WO2019093411 A1 WO 2019093411A1
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secondary battery
electrolyte
battery according
lithium
electrolyte solution
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PCT/JP2018/041448
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English (en)
Japanese (ja)
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山田　淳夫
裕貴 山田
ワン・ジェンフイ
拡嗣 高田
栄一 中村
シャン・ルイ
ゼン・キフェン
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国立大学法人 東京大学
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Priority to JP2019552370A priority Critical patent/JPWO2019093411A1/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
    • H01M10/052—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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 secondary battery having fire extinguishing properties, and a secondary battery including the electrolyte.
  • Lithium ion batteries having high energy density are expected to be widely used as large-sized storage batteries for electric vehicles, power storage applications, etc., in addition to small mobile equipment applications such as mobile phones and notebook computers. In recent years, a secondary battery that can be manufactured at low cost has been required.
  • sodium ion batteries use sodium, which is inexpensive and resource-rich compared to lithium, which is classified as a rare metal, and thus is expected to be much cheaper than lithium ion secondary batteries, It is considered as a strong candidate for the next generation storage battery (for example, Patent Document 1).
  • sodium ion batteries have problems such as low charge / discharge cycle stability (reversibility) and insufficient safety.
  • this invention makes it a subject to provide the electrolyte solution for secondary batteries which has the safety
  • the present inventors can provide excellent battery characteristics by using a specific combination of an organic solvent constituting an electrolytic solution and a high concentration alkali metal salt, In addition to the flame retardancy, the inventors have newly found that a highly safe electrolyte for a secondary battery having a fire-extinguishing function can be obtained, and the present invention has been completed. It has also been found that, by using such an electrolytic solution, it is possible to provide a secondary battery having both energy density and safety, which have been considered as a trade-off relationship.
  • the present invention is an electrolyte for a secondary battery having ⁇ 1> fire extinguishing properties in one aspect, comprising a non-aqueous solvent and an alkali metal salt, and the amount of the non-aqueous solvent with respect to 1 mol of the alkali metal salt.
  • the electrolyte solution for secondary batteries as described in said ⁇ 1> which does not have an ignition point in the temperature range lower than the boiling point of the ⁇ 2> above-mentioned electrolyte solution;
  • the electrolyte solution for secondary batteries as described in said ⁇ 1> or ⁇ 2> whose ⁇ 3> self-extinguishing time is 1 second / g or less; ⁇ 4>
  • the anion which comprises the ⁇ 7> above-mentioned alkali metal salt is an anion containing 1 or more group selected from the group which consists of a fluoro sulfonyl group, a trifluoromethane sulfonyl group, and a perfluoro ethane sulfonyl group, said ⁇ 1>-
  • the electrolyte solution for secondary batteries as described in any one of ⁇ 6>; ⁇ 8>
  • the anion is bis (fluorosulfonyl) amide ([N (FSO 2 ) 2 ] ⁇ ), (fluorosulfonyl) (trifluorosulfonyl) amide ([N (CF 3 SO 2 ) (FSO 2 )] ⁇ ), bis (trifluoromethanesulfonyl) amide ([N (CF 3 SO 2 ) 2] -), bis (perfluoro-ethanesulf
  • the electrolyte solution for a secondary battery according to any one of the above ⁇ 1> to ⁇ 9> which does not contain a normal temperature molten salt having a melting point of 50 ° C. or less as a ⁇ 10> salt alone; and ⁇ 11> the secondary battery
  • the present invention provides an electrolyte solution for a secondary battery according to any one of the above ⁇ 1> to ⁇ 10>, which is a lithium ion secondary battery or a sodium ion secondary battery.
  • the present invention ⁇ 12> A secondary battery comprising a positive electrode, a negative electrode, and the electrolyte for a secondary battery according to any one of the above ⁇ 1> to ⁇ 11>;
  • the secondary battery as described in said ⁇ 12> which is a ⁇ 13> lithium ion secondary battery;
  • ⁇ 14> The secondary battery according to ⁇ 13>, wherein the operating voltage is 2.3 V or more;
  • ⁇ 16> The secondary battery according to any one of ⁇ 13> to ⁇ 15>, wherein the positive electrode contains an active material selected from a metal oxide having a lithium element, a polyanion compound, or a sulfur compound.
  • the secondary battery as described in said ⁇ 12> which is a ⁇ 18> sodium ion secondary battery; ⁇ 19>
  • the secondary battery according to ⁇ 18>, wherein the operating voltage is 2.0 V or more;
  • ⁇ 20> The secondary battery according to ⁇ 18> or ⁇ 19>, wherein the positive electrode is a transition metal oxide; ⁇ 21>
  • the electrolyte solution for a secondary battery of the present invention has not only a flame retardancy but also a fire extinguishing function by not having a flash point (further, an ignition point) in a temperature range lower than the boiling point of the electrolyte. is there. Furthermore, since the vapor generated and diffused when the temperature of the electrolytic solution rises can be a extinguishant, the ignition risk of the battery can be actively reduced over a wide range.
  • the electrolyte for a secondary battery of the present invention provides excellent effects in that it can provide excellent battery characteristics. That is, conventionally, it has been considered essential to use a carbonate ester solvent for stable operation of the negative electrode, but in the battery using the electrolyte solution for a secondary battery of the present invention, 1000 times or more (continuously for time) Even if it is repeatedly charged and discharged for over 1 year, it hardly deteriorates and the voltage resistance is sufficiently high. Therefore, even when the battery is overcharged or the like, the risk of ignition can be avoided, and a secondary battery having high battery characteristics and excellent battery characteristics such as long life can be constructed.
  • FIG. 1 is an image showing the results of a combustion test in which the electrolytic solution of the present invention (left figure) and the electrolytic solution of the comparative example (right figure) were allowed to penetrate the separator and the combustion test was performed.
  • FIG. 2 is a graph showing a comparison of voltage-volume curves when using LiFSA / TMP electrolytes of various concentrations.
  • FIG. 4 is a graph showing a plot of cycle number, capacity and coulombic efficiency obtained in the charge and discharge cycle in FIG.
  • FIG. 1 is an image showing the results of a combustion test in which the electrolytic solution of the present invention (left figure) and the electrolytic solution of the comparative example (right figure) were allowed to penetrate the separator and the combustion test was performed.
  • FIG. 2 is
  • FIG. 6 is a graph showing a plot of cycle number, capacity and coulombic efficiency obtained in the charge and discharge cycle in FIG.
  • FIG. 7 is a graph showing a voltage-capacity curve in a hard carbon electrode (half cell) when a LiFSA / TMP / HFE electrolytic solution (1: 1.8: 8.1) is used.
  • FIG. 8 is a graph showing a comparison of voltage-volume curves when using NaFSA / TMP electrolytes of various concentrations.
  • FIG. 9 is a graph showing a voltage-capacity curve in a hard carbon electrode (half cell) when 3.3 M NaFSA / TMP electrolytic solution (1: 1.8) is used.
  • FIG. 10 is a graph showing the charge / discharge curve of the hard carbon electrode when using 1.0 M NaPF 6 / EC: DEC electrolyte solution.
  • FIG. 11 is a plot of cycle number, capacity and coulombic efficiency obtained in charge and discharge cycles when using 3.3 M NaFSA / TMP electrolyte and using 1.0 M NaPF 6 / EC: DEC electrolyte FIG.
  • FIG. 10 is a graph showing the charge / discharge curve of the hard carbon electrode when using 1.0 M NaPF 6 / EC: DEC electrolyte solution.
  • FIG. 11 is a plot of cycle number, capacity and coulombic efficiency obtained in charge and discharge cycles when using 3.3 M NaFSA / TMP electrolyte and using 1.0 M NaPF 6 / EC: DEC electroly
  • the inset is a graph showing the voltage-capacitance curve at that time.
  • Electrolyte The electrolyte for a secondary battery of the present invention is characterized by having a extinguishing property. More specifically, the electrolyte for a secondary battery of the present invention does not have a flash point in a temperature range lower than the boiling point of the electrolyte. Furthermore, it is preferable that the ignition point does not exist in a temperature range lower than the boiling point of the electrolytic solution.
  • flash point is the lowest temperature at which a liquid is heated and a fire source is brought close to igniting it, and is a representative value representing the fire hazard of various liquids such as fuel.
  • the flash point of kerosene and light oil is 40-70 ° C.
  • ignition point refers to the lowest temperature at which a substance, when heated in air, will ignite without a fire source.
  • sulfur 232 ° C., hydrogen sulfide 260 ° C., light oil 250 ° C., kerosene 255 ° C., gasoline 300 ° C., propane 432 ° C. and the like are representative values.
  • Typical commonly used commercial electrolytes are flammable liquids (flash point 40 ° C or less) that are classified into kerosene and light oil in the same group under the Fire Service Law. It is the main cause.
  • the electrolyte solution for secondary batteries of the present invention does not have a flash point and / or an ignition point in a temperature range lower than the boiling point, it not only has the flame retardant property of being hard to burn but also exceeds this. It also has fire extinguishing properties.
  • the boiling point of the electrolytic solution is about 200 ° C., and in this case, the electrolytic solution for secondary batteries of the present invention is 200 It is preferred not to have a flash point and / or an ignition point in a temperature range lower than around C.
  • the electrolyte solution for secondary batteries which has such a fire-extinguishing property and can exhibit battery characteristics of a practical level as described later has been newly found in the present invention.
  • the electrolyte solution for a secondary battery of the present invention is vaporized before the flash point or ignition point when the ambient temperature reaches a temperature higher than the boiling point, and the vapor can function as a extinguishing agent. Have an advantage.
  • the self-extinguishing time can be used as an index indicating such a extinguishing function.
  • self-extinguishing time (sec / g) means the duration of combustion per gram of ignited sample.
  • the electrolyte solution for a secondary battery of the present invention preferably has a self-extinguishing time of 1 second / g or less, and more preferably, a self-extinguishing time of approximately 0 seconds / g.
  • the nonaqueous solvent contained in the electrolyte for a secondary battery of the present invention is preferably a flame retardant organic solvent.
  • Such flame retardant organic solvents can typically include phosphoric acid esters, fluorinated solvents, or combinations thereof.
  • the phosphate ester can be a phosphate monoester, a phosphate diester, or a phosphate triester.
  • the phosphoric acid ester in which the alkyl group etc. of an ester part comprise cyclic structure can be used.
  • trimethyl phosphate is particularly preferable in view of low viscosity and high oxidation stability.
  • a fluorine-containing substituent can be introduced into these phosphoric esters, and for example, an alkyl fluoride such as a trifluoromethyl group can be introduced at any position in the alkyl chain of the ester moiety.
  • an alkyl fluoride such as a trifluoromethyl group
  • fluorinated ethers such as hydrofluoroether can be mentioned.
  • TMP trimethyl phosphate
  • TEP triethyl phosphate
  • TEP triethyl phosphate
  • a phosphoric acid ester which comprises cyclic structure and a compound which introduce
  • the electrolyte solution for a secondary battery of the present invention may optionally be a mixed solvent containing another solvent other than the above-mentioned flame retardant organic solvent.
  • suitable other solvents include, for example, ethers such as ethyl methyl ether and dipropyl ether; nitriles of methoxypropionitrile; esters such as methyl acetate; amines such as triethylamine; alcohols such as methanol; Ketones; fluorine-containing alkanes and the like can be used.
  • aprotic organic solvents such as 1,2-dimethoxyethane, acetonitrile, tetrahydrofuran, dimethylsulfoxide, ⁇ -butyrolactone, and sulfolane can also be used.
  • the flame retardant organic solvent is present in the largest proportion in all solvents, and preferably 70 to 100 mol%, more preferably in molar ratio to all solvents. It is present in a proportion of 80 to 100 mol%.
  • the flame retardant organic solvent is a single solvent (ie 100%). This is because, when the solvent other than the flame retardant solvent is contained, the fire extinguishing property may not be sufficiently exhibited depending on the ratio.
  • the electrolyte for a secondary battery of the present invention is characterized by containing a high concentration of an alkali metal salt.
  • the mixing ratio of the alkali metal salt to the solvent in the electrolytic solution is 4 mol or less, preferably 3 mol or less, more preferably 2 mol or less of solvent per 1 mol of alkali metal salt.
  • the lower limit of the solvent amount is not particularly limited as long as precipitation of the alkali metal salt does not occur and the electrochemical reaction in the positive electrode and the negative electrode proceeds, but for example, 1 mol or more of the solvent per 1 mol of alkali metal salt And preferably 2 mol or more of the solvent per 1 mol of the alkali metal salt.
  • the alkali metal salt used in the electrolyte for a secondary battery of the present invention is preferably a lithium salt or a sodium salt.
  • a lithium salt is preferable when the secondary battery is a lithium ion battery
  • a sodium salt is preferable when the secondary battery is a sodium ion battery.
  • the mixture which combined two or more types of alkali metal salts can also be used.
  • the anion constituting the alkali metal salt is preferably an anion containing one or more groups selected from the group consisting of a fluorosulfonyl group, a trifluoromethanesulfonyl group, and a perfluoroethanesulfonyl group.
  • bis (fluorosulfonyl) amide ([N (FSO 2 ) 2 ] ⁇ ), (fluorosulfonyl) (trifluorosulfonyl) amide ([N (CF 3 SO 2 ) (FSO 2 )] ⁇ ), bis (trifluorosulfonyl) amide b methanesulfonyl) amide ([N (CF 3 SO 2 ) 2] -), bis (perfluoro-ethanesulfonyl) amide ([N (C 2 F 5 SO 2) 2] -) or (perfluoro ethanesulfonyl) (tri Fluoroethanemethanesulfonyl) amide ([N (C 2 F 5 SO 2 ) (CF 3 SO 2 )] ⁇ ) is preferred.
  • alkali metal salt examples include lithium bis (fluorosulfonyl) amide (LiFSA), lithium (fluorosulfonyl) (trifluorosulfonyl) amide, lithium bis (trifluoromethanesulfonyl) amide (LiTFSA), lithium bis ( perfluoro ethanesulfonyl) amide -) (LiBETA) or lithium (perfluoro ethanesulfonyl) (trifluoroethane sulfonyl) amide; or sodium bis (fluorosulfonyl) amide (NaFSA), sodium (fluorosulfonyl) (trifluorosulfonyl ) amide, sodium bis (trifluoromethanesulfonyl) amide (NaTFSA), sodium bis (perfluoro ethanesulfonyl) amide -) (NABE A) or sodium (perfluoro e
  • alkali metal salts are lithium bis (fluorosulfonyl) amide (LiFSA) or sodium bis (fluorosulfonyl) amide (NaFSA). These salts have weak cation-anion interactions and have high ion conductivity even at high concentrations.
  • supporting electrolytes known in the art can be included.
  • a supporting electrolyte is, for example, LiPF 6 , LiBF 4 , LiClO 4 , LiNO 3 , LiCl, Li 2 SO 4, Li 2 S, etc. and any of these when the secondary battery is a lithium ion battery. What is selected from the combination is mentioned.
  • the electrolyte solution for a secondary battery of the present invention may also contain other components as necessary for the purpose of improving its function and the like. However, it is preferable that the electrolyte solution for a secondary battery of the present invention does not contain a normal temperature molten salt having a melting point of 50 ° C. or less as a single salt. Specific examples of such molten salts include imidazolium salts and tetrafluoroborates. It is because the electrolyte solution for secondary batteries of this invention already has sufficient ionic conductivity, without adding such a molten salt. More preferably, in the electrolyte solution for a secondary battery of the present invention, the non-aqueous solvent is a flame retardant organic solvent, and the electrolyte comprises only the flame retardant organic solvent and an alkali metal salt.
  • Other components include, for example, conventionally known overcharge inhibitors, dehydrating agents, deoxidizers, and property improving assistants for improving capacity retention characteristics and cycle characteristics after high temperature storage.
  • aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran and the like; 2-fluoro Partially fluorinated compounds of the above-mentioned aromatic compounds such as biphenyl, o-cyclohexyl fluorobenzene, p-cyclohexyl fluorobenzene and the like; fluorine-containing anisole such as 2,4-difluoroanisole, 2, 5-difluoroanisole and 2, 6-difluoroaniol Compounds are mentioned.
  • the overcharge inhibitor may be used alone or in combination of two or more.
  • the content of the overcharge inhibitor in the electrolyte is preferably 0.01 to 5% by mass.
  • the electrolytic solution contains 0.1% by mass or more of the overcharge preventing agent, it becomes easier to suppress the rupture and ignition of the secondary battery due to the overcharge, and the secondary battery can be used more stably.
  • the dehydrating agent examples include molecular sieves, sodium sulfate, magnesium sulfate, calcium hydride, sodium hydride, potassium hydride, lithium aluminum hydride and the like.
  • the solvent used for the electrolytic solution of the present invention may be one which has been dehydrated by the above-mentioned dehydrating agent and then subjected to rectification. Moreover, you may use the solvent which only dewatered by the said dehydrating agent, without performing rectification.
  • property improvement aids for improving the capacity retention characteristics and cycle characteristics after high temperature storage include succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, diasteric anhydride, and the like.
  • Carboxylic acid anhydrides such as glycolic acid, cyclohexanedicarboxylic acid anhydride, cyclopentanetetracarboxylic acid dianhydride, phenylsuccinic acid anhydride; ethylene sulfite, 1,3-propane sultone, 1,4-butane sultone, methanesulfonic acid Methyl, busulfan, sulfolane, sulfolene, dimethyl sulfone, diphenyl sulfone, methylphenyl sulfone, dibutyl disulfide, dicyclohexyl disulfide, tetramethylthiuram monosulfide, N, N-dimethylmethanesulfonamide, N, N-diethylmethane Sulfur-containing compounds such as Ruhon'amido; heptane, octane, hydrocarbon compounds such as cycloheptan
  • the secondary battery of the present invention comprises a positive electrode, a negative electrode, and the electrolytic solution of the present invention.
  • the secondary battery can be a lithium ion secondary battery or a sodium ion secondary battery.
  • the secondary battery of the present invention preferably has an operating voltage of 2.3 V or more.
  • the secondary battery of the present invention preferably has an operating voltage of 2.0 V or more.
  • Negative electrode As a negative electrode in the secondary battery of this invention, the electrode structure well-known in the said technical field can be used.
  • a negative electrode active material capable of electrochemically absorbing and desorbing lithium ions can be mentioned.
  • known negative electrode active materials for lithium ion secondary batteries can be used.
  • natural graphite (graphite), Highly Oriented Graphitic Graphite (HOPG), amorphous Carbonaceous materials such as carbon can be mentioned.
  • Still other examples include metal compounds such as lithium metal, metal nitrides.
  • lithium element lithium aluminum alloy, lithium tin alloy, lithium lead alloy, lithium silicon alloy etc.
  • metal nitride containing a lithium element lithium cobalt nitride, lithium iron nitride, lithium manganese nitride etc.
  • These negative electrode active materials may be used alone or in combination of two or more.
  • carbonaceous materials such as natural graphite (graphite), highly oriented graphite (HOPG), amorphous carbon and the like can be used. From the viewpoint of increasing the voltage and energy density of the secondary battery and reducing the number of series required for driving the device, it is desirable to use a negative electrode whose working potential is lower than 0.5 V with respect to the metal lithium potential.
  • an electrode containing an anode active material capable of electrochemically absorbing and desorbing sodium ions can be used.
  • negative electrode active materials known negative electrode active materials for sodium ion secondary batteries can be used.
  • hard carbon, soft carbon, carbon black, ketjen black, acetylene black, activated carbon, carbon nanotubes, carbon Carbon materials such as fibers and amorphous carbon can be mentioned.
  • a sodium ion metal or an alloy containing a sodium ion element, a metal oxide, a metal nitride, or the like can also be used.
  • the negative electrode active material a carbonaceous material such as hard carbon having a disordered structure is preferable.
  • the negative electrode may contain only the negative electrode active material, and contains at least one of a conductive material and a binder (binder) in addition to the negative electrode active material, and a negative electrode current collector as a negative electrode composite material It may be in a form attached to For example, in the case where the negative electrode active material is foil-like, it can be a negative electrode containing only the negative electrode active material. On the other hand, when the negative electrode active material is in the form of powder, it can be a negative electrode having the negative electrode active material and a binder.
  • a doctor blade method, a molding method using a pressure bonding press, or the like can be used as a method of forming a negative electrode using a powdery negative electrode active material.
  • conductive materials such as carbon materials and metal fibers, metal powders such as copper, silver, nickel and aluminum, and organic conductive materials such as polyphenylene derivatives can be used.
  • carbon material graphite, soft carbon, hard carbon, carbon black, ketjen black, acetylene black, graphite, activated carbon, carbon nanotube, carbon fiber and the like can be used.
  • synthetic resins containing an aromatic ring, mesoporous carbon obtained by firing petroleum pitch or the like can also be used.
  • a fluorine-based resin such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene tetrafluoroethylene (ETFE) or the like, polyethylene, polypropylene or the like can be preferably used.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • ETFE ethylene tetrafluoroethylene
  • polyethylene polypropylene or the like
  • the negative electrode current collector a rod-like body, a plate-like body, a foil-like body, a net-like body or the like mainly composed of copper, nickel, aluminum, stainless steel or the like can be used.
  • a positive electrode of the secondary battery of the present invention an electrode configuration known in the relevant technical field can be used.
  • the secondary battery is a lithium ion battery
  • one or more of lithium cobaltate (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), lithium nickelate (LiNiO 2 ) and the like can be used as the positive electrode active material Lithium-containing transition metal oxides including transition metals, transition metal sulfides, metal oxides, lithium iron phosphate (LiFePO 4 ), lithium iron pyrophosphate (Li 2 FeP 2 O 7 ), and other one or more transition metals And lithium-containing polyanion-based compounds, sulfur-based compounds (Li 2 S) and the like.
  • the positive electrode may contain a conductive material and a binder. Preferably, it is lithium manganate.
  • a known positive electrode active material can be used.
  • conductive material and the binder those similar to the above-mentioned negative electrode can be used.
  • positive electrode collector metal copper, nickel, aluminum, stainless steel etc. can be used, for example.
  • the separator used in the secondary battery of the present invention is not particularly limited as long as it has a function of electrically separating the positive electrode layer and the negative electrode layer, but, for example, polyethylene (PE)
  • PE polyethylene
  • porous insulating materials such as porous sheets made of resins such as polypropylene (PP), polyester, cellulose, and polyamide, and nonwoven fabrics such as nonwoven fabric and glass fiber nonwoven fabric.
  • the shape of the secondary battery of the present invention is not particularly limited as long as it can accommodate the positive electrode, the negative electrode, and the electrolytic solution, but for example, cylindrical, coin, flat, laminate type Etc. can be mentioned.
  • electrolyte solution and secondary battery of this invention are suitable for the use as a secondary battery, using as a primary battery is not excluded.
  • LiFSA lithium bis (fluorosulfonyl) amide
  • TMP trimethyl phosphate
  • a mixed solution was prepared at a molar ratio of 83. These are 1.0 M, 2.3 M and 5.3 M LiFSA / TMP electrolytes, respectively, in volume molar concentrations of LiFSA.
  • a solution was prepared by mixing sodium bis (fluorosulfonyl) amide (NaFSA) and trimethyl phosphate (TMP) as electrolytes at a molar ratio of 1: 7.6, 1: 3, and 1: 1.8.
  • the measurement of the flash point uses the measurement apparatus sealed type (manufacturer: STANHOPE-SETA, model: 70000-0), and the test conditions conform to the Japanese Fire Service Law (sample volume 2 mL, retention time 1 minute) I am going.
  • the measurement was performed a plurality of times, the average value was taken, and the pressure of the measurement environment was taken into consideration, and the value corrected for the case of 1 atm (101.3 kPa) was adopted using the following equation.
  • Tc T0 + 0.25 * (101.3-P) (In the formula, Tc: flash point (° C.), T 0: measurement flash point (° C.), P: pressure at the time of measurement (kPa)).
  • the LiFSA / TMP electrolyte solution and the NaFSA / TMP electrolyte solution of the present invention did not exhibit a flash point in the temperature range up to the boiling point (around 200 ° C.). Moreover, as for the LiFSA / TMP electrolyte solution and NaFSA / TMP electrolyte solution of this invention, self-extinguishing time was 0 s / g in all. On the other hand, Comparative Example 1.0 M NaPF 6 / [EC: DEC] had a flash point around 37.5 ° C., and the self-extinguishing time was about 43 s / g. Similarly, in the comparative example 1.0 M LiPF 6 / EC: DEC, a flash point was observed around 25.3 ° C.
  • Li-ion battery A solution in which lithium bis (fluorosulfonyl) amide (LiFSA) and trimethyl phosphate (TMP) were mixed at a molar ratio of 1: 7.8, 1: 3.0, and 1: 0.83 as electrolytes (1.
  • Constant current charge and discharge measurements were performed using 0 M, 2.3 M, and 5.3 M LiFSA / TMP). The measurement was performed using a half cell consisting of a natural graphite electrode and a metallic lithium electrode. The temperature was 25 ° C., the voltage range was 0 to 2.5 V, the number of cycles was 1, and the current value was 37.2 mA / g based on the weight of the natural graphite electrode.
  • the obtained voltage-capacity curve is shown in FIG.
  • the temperature was 25 ° C.
  • the voltage range was 0 to 2.5 V
  • the current value was 74.4 mA / g based on the weight of the natural graphite electrode.
  • the obtained voltage-capacity curve is shown in FIG.
  • a plot of cycle number versus capacity and coulombic efficiency is shown in FIG.
  • a full cell consisting of a LiNi 0.5 Mn 1.5 O 4 positive electrode and a natural graphite negative electrode was constructed using 5.3 M LiFSA / TMP as an electrolytic solution, and a 100 cycle charge-discharge cycle test was conducted.
  • the temperature was 25 ° C.
  • the voltage range was 3.5 to 4.8 V
  • the current value was 29.4 mA / g based on the weight of LiNi 0.5 Mn 1.5 O 4 .
  • the weight ratio of LiNi 0.5 Mn 1.5 O 4 to natural graphite used was 2.8: 1 (1: 1 in theoretical volume ratio).
  • the obtained voltage-capacity curve is shown in FIG.
  • a plot of the number of cycles and capacity and coulombic efficiency based on the positive electrode is shown in FIG.
  • the voltage flat portion in the charge / discharge process was observed at around 4.5 to 4.7V.
  • This reversibly operates a lithium ion battery having an operating voltage of about 4.6 V, which is higher than the 3.8 V lithium ion battery currently put into practical use, using the electrolyte solution of the present invention
  • FIG. 6 it was demonstrated that the capacity did not deteriorate even after 100 times of repeated charging and discharging, and a high coulombic efficiency of almost 100% was maintained.
  • the battery characteristics were evaluated using a mixed solvent of TMP and hydrofluoroether (HFE) as a flame retardant organic solvent.
  • the measurement was performed using a half cell consisting of a graphite electrode and a metal lithium electrode.
  • the temperature was 25 ° C.
  • the voltage range was 0 to 2.5 V
  • the current value was 74.4 mA / g based on the weight of the natural graphite electrode.
  • the obtained voltage-capacity curve is shown in FIG. This result demonstrates that the lithium insertion and desorption reaction to the natural graphite electrode reversibly proceeds even after eight charge and discharge cycles in an electrolyte solution using a mixed solvent of TMP / HFE. .
  • the temperature was 25 ° C.
  • the voltage range was 0 to 2.5 V
  • the current value was 50 mA / g based on the weight of the hard carbon electrode.
  • the obtained voltage-capacity curve is shown in FIG.
  • the capacity decreases even after 1,200 cycles of charging and discharging (15 consecutive months or more). Not observed at all, it maintained a high efficiency of almost 100%.
  • the capacity tends to decrease as charge and discharge cycles are repeated, and the capacity was 0 mAh / g before reaching 200 cycles.
  • a full cell consisting of a Na 3 V 2 (PO 4 ) 3 positive electrode and a hard carbon negative electrode was constructed using 3.3 M NaFSA / TMP as an electrolytic solution, and a charge / discharge cycle test of 100 cycles was conducted.
  • the temperature was 25 ° C.
  • the voltage range was 1.8 to 3.5 V
  • the current value was 50 mA / g based on the weight of hard carbon.
  • the weight ratio of Na 3 V 2 (PO 4 ) 3 to hard carbon used was 2.5: 1 (theoretical volume ratio 1.2: 1).
  • a plot of the number of cycles obtained and capacity and coulombic efficiency based on the negative electrode is shown in FIG. Also, the voltage-capacitance curve is shown as an inset in FIG.

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Abstract

Le problème décrit par la présente invention est de pourvoir à un électrolyte pour batteries secondaires qui soit sûr en termes de risque d'inflammation, et avec lequel d'excellentes caractéristiques de batterie puissent être obtenues. La solution de l'invention porte sur un électrolyte pour batteries secondaires qui présente des propriétés d'extinction d'incendie, caractérisé en ce qu'il comprend un solvant non aqueux et un sel de métal alcalin, et caractérisé en ce que : la quantité du solvant non aqueux est inférieure ou égale à 4 moles pour 1 mole du sel de métal alcalin ; et le point éclair n'est pas dans une plage de température inférieure au point d'ébullition de l'électrolyte.
PCT/JP2018/041448 2017-11-08 2018-11-08 Électrolyte présentant des propriétés d'extinction d'incendie, et batterie secondaire comprenant ledit électrolyte WO2019093411A1 (fr)

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JPWO2021166771A1 (fr) * 2020-02-17 2021-08-26
JP2022535856A (ja) * 2019-07-16 2022-08-10 ファクトリアル インク． 高電圧カソード材料及びその他の用途のための電解質
CN115051034A (zh) * 2022-07-15 2022-09-13 南开大学 一种宽温域钠离子电池电解液
CN115663287A (zh) * 2022-12-13 2023-01-31 湖南法恩莱特新能源科技有限公司 一种耐高压阻燃的钠离子电解液及其制备方法和钠离子电池
WO2023095775A1 (fr) * 2021-11-26 2023-06-01 日本電気硝子株式会社 Batterie secondaire au sodium-ion

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CN115051034A (zh) * 2022-07-15 2022-09-13 南开大学 一种宽温域钠离子电池电解液
CN115663287A (zh) * 2022-12-13 2023-01-31 湖南法恩莱特新能源科技有限公司 一种耐高压阻燃的钠离子电解液及其制备方法和钠离子电池

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