WO2016076145A1 - Batterie rechargeable à électrolyte non aqueux - Google Patents

Batterie rechargeable à électrolyte non aqueux Download PDF

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WO2016076145A1
WO2016076145A1 PCT/JP2015/080745 JP2015080745W WO2016076145A1 WO 2016076145 A1 WO2016076145 A1 WO 2016076145A1 JP 2015080745 W JP2015080745 W JP 2015080745W WO 2016076145 A1 WO2016076145 A1 WO 2016076145A1
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negative electrode
group
secondary battery
carbon atoms
electrolyte secondary
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PCT/JP2015/080745
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English (en)
Japanese (ja)
Inventor
和徳 小関
和樹 田川
裕知 渡辺
矢野　亨
智史 横溝
雄太 野原
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新日鉄住金化学株式会社
株式会社Adeka
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Priority to JP2016558981A priority Critical patent/JP6647211B2/ja
Publication of WO2016076145A1 publication Critical patent/WO2016076145A1/fr

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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
    • 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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery, and to a non-aqueous electrolyte secondary battery having a non-aqueous electrolyte containing a negative electrode active material containing a specific carbon material and a specific polyvalent carboxylic acid ester compound.
  • non-aqueous electrolyte secondary batteries having high voltage and high energy density have been widely used as power sources. Also, from the viewpoint of environmental problems, battery cars and hybrid cars using electric power as a part of power have been put into practical use.
  • the discharge capacity is an important characteristic so that the current that is the energy source of the hybrid vehicle can be sufficiently supplied.
  • the non-aqueous electrolyte secondary battery preferably maintains a high charge capacity up to a high current density and is also required to have a high charge capacity maintenance rate.
  • the hybrid vehicle needs to have long-term reliability, that is, less capacity deterioration after long-term use than the portable electronic device.
  • the non-aqueous electrolyte secondary battery has a negative electrode active material that is reductively decomposed on the surface of the negative electrode active material made of a carbon material regardless of whether it is a high crystalline carbon or a low crystalline carbon during the initial charge.
  • a film called SEI Solid Electrolyte Interface
  • This film has the effect of suppressing the decomposition of the electrolyte solution in the negative electrode, but if the stability of the film is low, there is a problem that the reductive decomposition of the electrolyte solution occurs due to repeated charge and discharge, which causes the battery capacity to deteriorate. .
  • additives for the non-aqueous electrolyte have been proposed in order to improve the stability and electrical characteristics of the non-aqueous electrolyte secondary battery.
  • additives include 1,3-propane sultone (for example, see Patent Document 1), vinyl ethylene carbonate (for example, see Patent Document 2), vinylene carbonate (for example, see Patent Document 3), 1, 3-Propane sultone, butane sultone (for example, see Patent Document 4), vinylene carbonate (for example, see Patent Document 5), vinyl ethylene carbonate (for example, see Patent Document 6), and the like have been proposed. Carbonate is widely used because of its great effect.
  • additives are considered to form a stable film called SEI on the surface of the negative electrode, and this film covers the surface of the negative electrode, thereby suppressing the reductive decomposition of the electrolytic solution.
  • silylbenzene-based additives see, for example, Patent Document 8
  • polycarboxylic acid silyl ester-based additives for example, see Patent Document 9
  • electrolyte additives that have been reported so far are electrolyte additives applied to highly crystalline carbon materials such as artificial graphite and natural graphite. It is not described in detail in the literature.
  • Carbon materials with high crystallinity such as graphite have a high potential on the surface of the negative electrode active material, so that they are highly reactive with electrolytes and additives and easily form SEI, whereas carbon materials with low crystallinity are negative electrode active materials Since the surface potential is low, the reactivity with the electrolysis solution is low. Therefore, it is difficult to form SEI that is stable and sufficiently covers the surface. For this reason, until now, sufficient SEI could not be formed on the surface of the active material, and thus the storage characteristics could not be improved.
  • an object of the present invention is to suppress capacity deterioration in a non-aqueous electrolyte secondary battery.
  • the present inventors have found that the above object can be achieved by using a non-aqueous electrolyte containing a negative electrode active material containing a specific carbon material and a polyvalent carboxylic acid ester compound having a specific structure.
  • the headline and the present invention were completed.
  • the present invention provides (A) a negative electrode containing a carbon material having a true specific gravity of 1.60-2.20 g / cm 3 as a negative electrode active material, (B) a positive electrode containing a positive electrode active material, and (C) a lithium salt as an organic solvent.
  • a non-aqueous electrolyte secondary battery comprising a dissolved non-aqueous electrolyte and (D) a separation membrane
  • C A nonaqueous electrolyte secondary battery comprising a compound represented by the following general formula (1) in a nonaqueous electrolyte obtained by dissolving a lithium salt in an organic solvent. .
  • R 1 represents a divalent unsaturated hydrocarbon having 2 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a divalent heterocyclic group having 3 to 12 carbon atoms
  • 2 to R 7 each independently represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms.
  • the nonaqueous electrolytic solution (2) is characterized in that (C) a nonaqueous electrolytic solution obtained by dissolving a lithium salt in an organic solvent contains a compound represented by the following general formula (2).
  • a secondary battery is provided.
  • R 8 to R 15 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group, a benzyl group, or fluorine. Represents a phenyl group, a phenoxy group, or a benzyl group substituted with chlorine, bromine, or an alkyl group having 1 to 6 carbon atoms.
  • FIG. 1 is a longitudinal sectional view schematically showing an example of the structure of a coin-type battery of the nonaqueous electrolyte secondary battery of the present invention.
  • FIG. 2 is a schematic diagram showing a basic configuration of a cylindrical battery of the nonaqueous electrolyte secondary battery of the present invention.
  • FIG. 3 is a perspective view showing the internal structure of the cylindrical battery of the nonaqueous electrolyte secondary battery of the present invention as a cross section.
  • the negative electrode active material for a non-aqueous electrolyte secondary battery of the present invention is a carbon material having a true specific gravity in the range of 1.60 to 2.20 g / cm 3 .
  • the carbon material that gives such true specific gravity can be obtained by calcining coal-based and / or petroleum-based (coal-based, etc.) raw coke, or coal-based calcined coke, alone or mixed.
  • the term “coal-based, etc.” may be “coal-based and / or petroleum-based”, that is, either coal-based or petroleum-based, or a mixture of both. Good thing.)
  • the true specific gravity is less than 1.60 g / cm 3
  • the true specific gravity exceeds 2.20 g / cm 3
  • the input / output characteristics and capacity retention characteristics are degraded when applied to a battery.
  • raw coke such as coal-based coke uses petroleum-based and / or coal-based heavy oil, for example, a coking facility such as a delayed coker, and the maximum temperature reached about 400 ° C. to 700 ° C. for about 24 hours. It means the one obtained by carrying out the decomposition and polycondensation reaction, and the coal-based calcined coke means the one obtained by calcining the coal-based raw coke and the maximum temperature reached 800 ° C. It means petroleum-based and / or coal-based coke calcined at about ⁇ 2000 ° C.
  • a heavy oil such as coal-based heavy oil using a coking facility such as a delayed coker.
  • a coal-based raw coke is obtained by carrying out the thermal decomposition and polycondensation reaction at a temperature of about 400 ° C. to 700 ° C. for about 24 hours. Thereafter, the obtained coal-based raw coke mass is pulverized to a predetermined size.
  • An industrially used pulverizer can be used for the pulverization.
  • pulverization step two or more of these apparatuses may be used for pulverization, or a single apparatus may be used for pulverization a plurality of times.
  • the heavy coal oil used here may be a heavy petroleum oil or a heavy coal oil, but the heavy heavy oil is richer in aromatic properties, Since there are few impurities, such as S, V, and Fe, and there is also little volatile matter, it is more preferable to use a coal-type heavy oil.
  • the negative electrode active material for non-aqueous electrolyte secondary batteries used here is coal-based and / or petroleum-based (coal-based etc.) raw coke, or coal-based calcined coke alone or mixed.
  • a plurality of baking processes and / or a shape control process such as granulation in the process, and / or a process of modifying and coating the surface with different organic and inorganic components And / or through a process of forming different metal components uniformly or dispersed on the surface.
  • the coal-based raw coke obtained as described above is calcined at a maximum temperature of 800 ° C. to 2000 ° C. to produce coal-based calcined coke.
  • equipment such as reed hammer furnace, shuttle furnace, tunnel furnace, rotary kiln, roller hearth kiln or microwave capable of mass heat treatment can be used, but it is particularly limited to these. is not.
  • these baking facilities may be either a continuous type or a batch type.
  • the obtained coal-based calcined coke lump is pulverized to a predetermined size using a pulverizer such as an industrially used atomizer in the same manner as described above.
  • the pulverized coke powder can be sized to a predetermined particle size by cutting fine powder by classification or removing coarse powder with a sieve or the like.
  • the firing temperature is preferably 800 ° C. or more and 2000 ° C. or less at the highest temperature reached.
  • the firing temperature exceeds the upper limit, crystal growth of the coke material is excessively promoted, and it becomes difficult to make the true specific gravity 2.20 g / cm 3 or less. If the true specific gravity exceeds 2.20 g / cm 3 , the crystal structure of the coke is oriented like graphite during firing, and the distance between crystal layers becomes narrow. As described above, the input / output characteristics, capacity retention ratio, etc. Therefore, the characteristic due to the structure will be deteriorated.
  • the crystal structure becomes undeveloped and the true specific gravity is not more than 1.60 g / cm 3, and the functional group derived from the raw material (OH group, COOH group, etc.) is present on the coke surface.
  • the functional group derived from the raw material OH group, COOH group, etc.
  • the true specific gravity is measured by a liquid phase replacement method (also known as a pycnometer method). Specifically, the powder of the negative electrode active material is put into a pycnometer, a solvent liquid such as distilled water is added, and the air and the solvent liquid on the powder surface are replaced by a method such as vacuum degassing to obtain an accurate powder weight and volume. To calculate the true specific gravity value.
  • a liquid phase replacement method also known as a pycnometer method.
  • the powder of the negative electrode active material is put into a pycnometer, a solvent liquid such as distilled water is added, and the air and the solvent liquid on the powder surface are replaced by a method such as vacuum degassing to obtain an accurate powder weight and volume.
  • a method such as vacuum degassing
  • the negative electrode is obtained by mixing a negative electrode active material containing a carbon material having a true specific gravity of 1.60-2.20 g / cm 3 on a current collector (generally copper foil), a conductive material, and a binder. It consists of a composite material layer to be formed. True specific gravity is preferably 1.60-2.20g / cm 3 of the negative electrode active material, 2.05-2.20g / cm 3 is more preferred.
  • a carbon material having a true specific gravity in the range of 1.60 to 2.20 g / cm 3 by the above method may be used as it is.
  • a carbon material having a specific gravity in the range of 1.60 to 2.20 g / cm 3 and a carbon material having a true specific gravity of 2.20 g / cm 3 or more may be mixed.
  • the mass ratio of the carbon material having a true specific gravity in the range of 1.60 to 2.20 g / cm 3 and the carbon material having a true specific gravity of 2.20 g / cm 3 or more by the above method is , Preferably 5 wt% or more, more preferably 10 wt% or more.
  • the binder is a water-soluble adhesive such as fluorine resin powder such as polyvinylidene fluoride (PVDF) or polyimide (PI) resin, styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC).
  • fluorine resin powder such as polyvinylidene fluoride (PVDF) or polyimide (PI) resin, styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC).
  • PVDF polyvinylidene fluoride
  • PI polyimide
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • the amount of the binder used for the negative electrode is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material.
  • Examples of the conductive material for the negative electrode include graphite fine particles, carbon black such as acetylene black and ketjen black, amorphous carbon fine particles such as needle coke, carbon nanofibers, and the like, but are not limited thereto.
  • the amount of the conductive material used for the negative electrode is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material.
  • Formation of the composite material layer on the current collector is performed by preparing a slurry of the negative electrode active material and the binder described above using a solvent, and applying and drying on the current collector (generally copper foil). It can be performed by pressing under any condition.
  • the solvent used is not particularly limited, and N-methylpyrrolidone (NMP), dimethylformamide, water, alcohol, or the like is used.
  • the solvent for the negative electrode is preferably used in combination with a thickener when water is used as the solvent. The amount of the solvent is adjusted so that the viscosity of the paste can be easily applied to the current collector.
  • Examples of the current collector of the negative electrode include stainless steel foil, nickel foil, copper foil, nickel mesh, or copper mesh.
  • a positive electrode active material As in a normal secondary battery, a positive electrode active material, a binder, a conductive material and the like slurryed with an organic solvent or water are applied to a current collector and dried. A sheet is used.
  • the positive electrode active material contains a transition metal and lithium and is preferably a material containing one kind of transition metal and lithium. Examples thereof include a lithium transition metal composite oxide and a lithium-containing transition metal phosphate compound. These may be used in combination.
  • the transition metal of the lithium transition metal composite oxide vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper and the like are preferable.
  • lithium transition metal composite oxide examples include lithium cobalt composite oxide such as LiCoO 2 , lithium nickel composite oxide such as LiNiO 2 , and lithium manganese composite oxide such as LiMnO 2 , LiMn 2 O 4 , and Li 2 MnO 3.
  • lithium cobalt composite oxide such as LiCoO 2
  • lithium nickel composite oxide such as LiNiO 2
  • lithium manganese composite oxide such as LiMnO 2 , LiMn 2 O 4 , and Li 2 MnO 3.
  • Some of the transition metal atoms that are the main components of these lithium transition metal composite oxides are aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, lithium, nickel, copper, zinc, magnesium, gallium, zirconium, etc. The thing substituted with the other metal etc. are mentioned.
  • substituted ones include, for example, LiNi 0.5 Mn 0.5 O 2 , LiNi 0.80 Co 0.17 Al 0.03 O 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiMn 1.8 Al 0.2 O 4 , LiMn 1.5 Ni 0.5 O 4 or the like.
  • transition metal of the lithium-containing transition metal phosphate compound vanadium, titanium, manganese, iron, cobalt, nickel and the like are preferable.
  • iron phosphates such as LiFePO 4 and phosphorus such as LiCoPO 4.
  • Cobalt acids some of the transition metal atoms that are the main components of these lithium transition metal phosphate compounds are aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, lithium, nickel, copper, zinc, magnesium, gallium, zirconium And those substituted with other metals such as niobium.
  • the binder for the positive electrode and the solvent for forming the slurry are the same as those used for the negative electrode.
  • the amount of the binder used for the positive electrode is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and most preferably 0.02 to 8 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • the amount of the solvent used for the positive electrode is preferably 30 to 300 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • Examples of the conductive material for the positive electrode include graphite fine particles, carbon black such as acetylene black and ketjen black, amorphous carbon fine particles such as needle coke, and carbon nanofibers, but are not limited thereto.
  • the amount of the conductive material used for the positive electrode is preferably 0.01 to 20 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • As the current collector for the positive electrode aluminum, stainless steel, nickel-plated steel or the like is usually used.
  • Nonaqueous electrolytic solution in which lithium salt is dissolved in organic solvent A nonaqueous electrolytic solution in which a lithium salt used in the present invention is dissolved in an organic solvent (hereinafter also simply referred to as “nonaqueous electrolytic solution”) will be described.
  • the nonaqueous electrolytic solution contains a compound represented by the general formula (1).
  • the divalent unsaturated hydrocarbon group having 2 to 6 carbon atoms represented by R 1 in the general formula (1) is particularly limited as long as it is a divalent hydrocarbon group containing an unsaturated double bond or triple bond in the group.
  • Suitable examples include vinylene, propenylene, isopropenylene, butenylene, pentenylene, hexenylene, 1-propenylene-2,3-diyl, ethynylene, propynylene, butynylene, pentynylene, hexynylene, and the like.
  • Examples of the arylene group having 6 to 12 include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, etc.
  • Examples of the divalent heterocyclic group having 3 to 12 carbon atoms include the following: The structure of this is mentioned. (In the above structural formulas, X 1 , X 2 , and X 3 each independently represent an oxygen atom or a sulfur atom.
  • R 1 is preferably vinylene, ethynylene, 1,4-phenylene, thiophen-2,5-yl (2,5-thiophenylene), and is preferably vinylene because it can hardly be altered and has a highly durable surface structure. Is most preferred.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 2 to R 7 in the general formula (1) include methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, cyclopentyl, and hexyl.
  • Examples of the alkenyl group having 2 to 6 carbon atoms include vinyl, allyl, 3-butenyl, isobutenyl, 4-pentenyl, 5-hexenyl, etc., and the alkynyl group having 2 to 6 carbon atoms.
  • R 2 to R 7 are preferably methyl, ethyl, propyl, butyl, and vinyl, and most preferably methyl, because a highly durable surface structure that hardly changes in quality can be obtained.
  • Specific examples of the compound represented by the general formula (1) include bis (trimethylsilyl) acetylenedicarboxylate, bis (ethyldimethylsilyl) acetylenedicarboxylate, bis (dimethylpropylsilyl) acetylenedicarboxylate, bis (dimethyl Butylsilyl) acetylenedicarboxylate, bis (dimethylvinylsilyl) acetylenedicarboxylate, bis (trimethylsilyl) fumarate, bis (trimethylsilyl) maleate, bis (trimethylsilyl) phthalate, bis (trimethylsilyl) isophthalate, bis (terephthalate) (Trimethylsilyl), bis (trimethylsilyl) itaconate and the like.
  • the compound represented by the general formula (1) may be used alone or in combination of two or more. Further, in the nonaqueous electrolytic solution of the present invention, when the content of the compound represented by the general formula (1) is too small, a sufficient effect cannot be exhibited, and when the content is too large, the compounding amount is met.
  • the content of the compound represented by the general formula (1) is 0.001 in the non-aqueous electrolyte because not only the increase effect is obtained but also the characteristics of the non-aqueous electrolyte may be adversely affected. Is preferably 10 to 10% by mass, more preferably 0.01 to 8% by mass, and most preferably 0.03 to 5% by mass.
  • the nonaqueous electrolytic solution used in the present invention contains the compound represented by the general formula (2) because the effects of the present invention are remarkably exhibited.
  • the compound represented by the general formula (2) will be described.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 8 to R 15 in the general formula (2) are the same as those exemplified as the alkyl group having 1 to 6 carbon atoms represented by R 2.
  • alkoxy group having 1 to 6 carbon atoms represented by R 8 to R 15 methoxy, ethoxy, propoxy, butoxy, isobutyloxy, s-butyloxy, t-butyloxy, pentoxy, isopentyloxy, cyclopentyloxy, Examples include hexyloxy and cyclohexyloxy.
  • alkyl group having 1 to 6 carbon atoms for substituting the phenyl group, phenoxy group, and benzyl group include the alkyl groups having 1 to 6 carbon atoms listed above.
  • R 8 to R 10 those which are alkyl groups having 1 to 6 carbon atoms are preferable, and among the groups represented by R 11 to R 15 , hydrogen atoms or alkyl groups having 1 to 6 carbon atoms are preferable. Some are preferred.
  • Specific examples of the compound represented by the general formula (2) include trimethylphenylsilane, triethylphenylsilane, 1-trimethylsilyl-4-methylbenzene, ethoxy (methyl) diphenylsilane, monomethyltriphenylsilane and the like.
  • the compound represented by the general formula (2) may be used alone or in combination of two or more.
  • the content of the compound represented by the general formula (2) is preferably 0.001 to 20% by mass in the nonaqueous electrolytic solution, 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is most preferable.
  • the non-aqueous electrolytic solution used in the present invention further includes a fluorosilane compound containing two or more difluorosilyl groups in the molecule, a cyclic carbonate compound having an unsaturated group, a chain carbonate compound, an unsaturated diester compound, and a cyclic sulfate ester.
  • An aromatic silane compound other than the compound represented by the general formula (2) can be added, a cyclic sulfite ester, a sultone, an unsaturated phosphate ester compound, a halogenated cyclic carbonate compound.
  • fluorosilane compounds containing two or more difluorosilyl groups in the molecule include bis (difluoromethylsilyl) methane, 1,2-bis (difluoromethylsilyl) ethane, and 1,3-bis (difluoromethylsilyl).
  • Examples include propane, 1,4-bis (difluoromethylsilyl) butane, 1,4- (bisdifluoromethylsilyl) benzene, tris (difluoromethylsilyl) methane, tetrakis (difluoromethylsilyl) methane, and the like.
  • Bis (difluoromethylsilyl) ethane, 1,3-bis (difluoromethylsilyl) propane, 1,4-bis (difluoromethylsilyl) butane, and tris (difluoromethylsilyl) methane are preferred.
  • the cyclic carbonate compound having an unsaturated group include vinylene carbonate, vinyl ethylene carbonate, propylidene carbonate, ethylene ethylidene carbonate, ethylene isopropylidene carbonate, and vinylene carbonate and vinyl ethylene carbonate are preferable.
  • Examples of the chain carbonate compound include dipropargyl carbonate, propargyl methyl carbonate, ethyl propargyl carbonate, bis (1-methylpropargyl) carbonate, bis (1-dimethylpropargyl) carbonate, and the like.
  • Examples of the unsaturated diester compounds include dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate, diheptyl maleate, dioctyl maleate, dimethyl fumarate, diethyl fumarate, and fumaric acid.
  • Examples of the cyclic sulfate include 1,3,2-dioxathiolane-2,2-dioxide, 1,3-propanediol cyclic sulfate, propane-1,2-cyclic sulfate, and the like.
  • Examples of the cyclic sulfite ester include ethylene sulfite and propylene sulfite.
  • Examples of the sultone include propane sultone, butane sultone, 1,5,2,4-dioxadithiolane-2,2,4,4-tetraoxide and the like.
  • Examples of the unsaturated phosphate compound include tris (2-propynyl) phosphate, diphenyl-2-methacryloyloxyethyl phosphate, and the like.
  • Examples of the halogenated cyclic carbonate compound include chloroethylene carbonate, dichloroethylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, and the like.
  • aromatic silane compounds other than the compound represented by the general formula (2) 1,1,2,2-tetramethyl-1,2-diphenyldisilane, 1,4-bis (trimethylsilyl) benzene, 1, Examples include 2-bis (trimethylsilyl) benzene.
  • additives may be used alone or in combination of two or more.
  • the content of these additives is usually 20% by mass or less in total in the non-aqueous electrolyte, preferably 5% by mass or less, and more preferably 3% by mass or less. .
  • organic solvent used for the non-aqueous electrolyte those usually used for the non-aqueous electrolyte can be used singly or in combination of two or more. Specifically, saturated cyclic carbonate compounds, saturated cyclic ester compounds, sulfoxide compounds, sulfone compounds, amide compounds, saturated chain carbonate compounds, chain ether compounds, cyclic ether compounds, saturated chain ester compounds, phosphorus-containing organic solvents, etc. Is mentioned.
  • saturated cyclic carbonate compounds saturated cyclic ester compounds, sulfoxide compounds, sulfone compounds and amide compounds have a high relative dielectric constant, and thus serve to increase the dielectric constant of non-aqueous electrolytes.
  • Compounds are preferred.
  • saturated cyclic carbonate compounds include ethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 1,1, -dimethylethylene carbonate. Etc.
  • saturated cyclic ester compound examples include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -hexanolactone, and ⁇ -octanolactone.
  • sulfoxide compound examples include dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, thiophene, and the like.
  • sulfone compounds include dimethylsulfone, diethylsulfone, dipropylsulfone, diphenylsulfone, sulfolane (also referred to as tetramethylenesulfone), 3-methylsulfolane, 3,4-dimethylsulfolane, 3,4-diphenimethylsulfolane, sulfolene. , 3-methylsulfolene, 3-ethylsulfolene, 3-bromomethylsulfolene and the like, and sulfolane and tetramethylsulfolane are preferable.
  • amide compound examples include N-methylpyrrolidone, dimethylformamide, dimethylacetamide and the like.
  • saturated chain carbonate compounds, chain ether compounds, cyclic ether compounds and saturated chain ester compounds can lower the viscosity of the non-aqueous electrolyte and increase the mobility of electrolyte ions. Battery characteristics such as output density can be made excellent. Moreover, since it is low-viscosity, the performance of the non-aqueous electrolyte at a low temperature can be enhanced, and among them, a saturated chain carbonate compound is preferable.
  • saturated chain carbonate compounds include dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), ethyl butyl carbonate, methyl-t-butyl carbonate, diisopropyl carbonate, and t-butyl propyl carbonate. Etc.
  • Examples of the chain ether compound or cyclic ether compound include dimethoxyethane (DME), ethoxymethoxyethane, diethoxyethane, tetrahydrofuran, dioxolane, dioxane, 1,2-bis (methoxycarbonyloxy) ethane, 1,2 -Bis (ethoxycarbonyloxy) ethane, 1,2-bis (ethoxycarbonyloxy) propane, ethylene glycol bis (trifluoroethyl) ether, propylene glycol bis (trifluoroethyl) ether, ethylene glycol bis (trifluoromethyl) ether And diethylene glycol bis (trifluoroethyl) ether.
  • DME dimethoxyethane
  • ethoxymethoxyethane diethoxyethane
  • tetrahydrofuran dioxolane
  • dioxane 1,2-bis (methoxycarbonyloxy) ethane
  • the saturated chain ester compound is preferably a monoester compound or a diester compound having a total number of carbon atoms in the molecule of 2 to 8, and specific compounds include methyl formate, ethyl formate, methyl acetate, and ethyl acetate.
  • Examples of the phosphorus-containing organic solvent include phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, and triphenyl phosphate; phosphorous acid esters such as trimethyl phosphite and triethyl phosphite, and triphenyl phosphite.
  • Phosphine oxides such as trimethylphosphine oxide, triethylphosphine oxide, triphenylphosphine oxide, and phosphazenes.
  • acetonitrile acetonitrile, propionitrile, nitromethane and their derivatives can be used as the organic solvent.
  • lithium salt to be dissolved in the organic solvent conventionally known lithium salts are used.
  • the lithium salt can be dissolved in the organic solvent so that the concentration in the non-aqueous electrolyte of the present invention is 0.1 to 3.0 mol / L, particularly 0.5 to 2.0 mol / L. preferable. If the concentration of the lithium salt is less than 0.1 mol / L, a sufficient current density may not be obtained, and if it is more than 3.0 mol / L, the stability of the nonaqueous electrolyte may be impaired.
  • the lithium salt may be used in combination of two or more lithium salts.
  • halogen-based, phosphorus-based and other flame retardants can be appropriately added to the non-aqueous electrolyte in order to impart flame retardancy. If the amount of flame retardant added is too small, sufficient flame retarding effect cannot be exerted.If it is too large, not only an increase effect corresponding to the blending amount can be obtained, but on the other hand, the characteristics of the non-aqueous electrolyte Since it may have an adverse effect, the content is preferably 1 to 50% by mass, more preferably 3 to 10% by mass with respect to the organic solvent constituting the nonaqueous electrolytic solution of the present invention.
  • halogen-based flame retardant examples include di (2,2,2-trifluoroethyl) carbonate, di (2,2,3,3-tetrafluoropropyl) carbonate, di (2,2,3,3, 4,4,5,5-octafluoropentyl) carbonate, 2,2,3,3,3-pentafluoropropyl-1,1,2,2-tetrafluoroethyl ether, etc.
  • Specific examples include trimethyl phosphate and triethyl phosphate.
  • a separation membrane is used between the positive electrode and the negative electrode.
  • a commonly used polymer microporous film can be used without particular limitation. Examples of the film include polyethylene, polypropylene, polyvinylidene fluoride, polyvinylidene chloride, polyacrylonitrile, polyacrylamide, polytetrafluoroethylene, polysulfone, polyethersulfone, polycarbonate, polyamide, polyimide, polyethylene oxide and polypropylene oxide.
  • the microporosity method includes a phase separation method in which a polymer compound and a solvent solution are formed into a film while microphase separation is performed, and the solvent is extracted and removed to make it porous.
  • the film is extruded and then heat treated, the crystals are arranged in one direction, and a “stretching method” or the like is performed by forming a gap between the crystals by stretching, and is appropriately selected depending on the film used.
  • the positive electrode material, the non-aqueous electrolyte, and the separation membrane have a phenol-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant for the purpose of improving safety.
  • Agents, hindered amine compounds and the like may be added.
  • the shape of the non-aqueous electrolyte secondary battery of the present invention having the above configurations (A) to (D) is not particularly limited, and may be various shapes such as a coin shape, a cylindrical shape, and a square shape. Can do.
  • FIG. 1 shows an example of a coin-type battery of the nonaqueous electrolyte secondary battery of the present invention
  • FIGS. 2 and 3 show examples of a cylindrical battery, respectively.
  • 1 includes a positive electrode
  • 1a includes a positive electrode current collector
  • 2 includes a carbon material having a true specific gravity of 1.60-2.20 g / cm 3 as a negative electrode active material.
  • Negative electrode, 2a is a negative electrode current collector
  • 3 is a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent
  • 4 is a stainless steel positive electrode case
  • 5 is a stainless steel negative electrode case
  • 6 is a polypropylene gasket
  • 7 Is a polyethylene separation membrane.
  • 11 is a negative electrode
  • 11 is a negative electrode
  • 12 is a negative current collector
  • 13 is a positive electrode
  • 14 is a positive current collector
  • 15 is a main battery.
  • 16 is a separation membrane
  • 17 is a positive electrode terminal
  • 18 is a negative electrode terminal
  • 19 is a negative electrode plate
  • 20 is a negative electrode lead
  • 21 is a positive electrode plate
  • 22 is a positive electrode lead
  • 23 is a case
  • 24 is an insulating plate
  • 25 are gaskets
  • 26 is a safety valve
  • 27 is a PTC element.
  • nonaqueous electrolyte secondary batteries lithium secondary batteries
  • negative electrode (A2) 94.5 parts by mass of a carbon material having a true specific gravity of 2.14 as an active material, 1.0 part by mass of acetylene black as a conductive material, 3.0 parts by mass of styrene butadiene rubber as a binder, 1.5 parts by mass of carboxymethyl cellulose as a thickener Parts were mixed and dispersed in 50 parts by mass of water to form a slurry. This slurry was applied to a copper negative electrode current collector, dried and press-molded. Thereafter, this negative electrode was cut into a predetermined size to produce a disc-shaped negative electrode A2.
  • Negative Electrode (A′1) 96.0 parts by weight of artificial graphite having a true specific gravity of 2.23 as an active material, 1.0 part by weight of acetylene black as a conductive material, 1.5 parts by weight of styrene butadiene rubber as a binder, and 1.5 parts by weight of carboxymethyl cellulose as a thickener Parts were mixed and dispersed in 120 parts by mass of water to form a slurry. This slurry was applied to a copper negative electrode current collector, dried and press-molded. Then, this negative electrode was cut into a predetermined size to produce a disk-shaped negative electrode A′1.
  • LiPF 6 was dissolved at a concentration of 1 mol / L in a mixed solvent consisting of 30% by volume of ethylene carbonate, 40% by volume of ethyl methyl carbonate, and 30% by volume of dimethyl carbonate to prepare an electrolyte solution A.
  • non-aqueous electrolyte (C) As an electrolytic solution additive, compounds represented by the above general formula (1) (compounds C1-1, C1-2, C1-3 shown below), compounds represented by the above general formula (2) (shown below) Compound C2-1) and compound C′1 shown below were dissolved in the electrolyte solution in the proportions shown in [Table 1] to prepare a nonaqueous electrolyte solution (C).
  • the number in () in [Table 1] represents the concentration (% by mass) in the non-aqueous electrolyte.
  • the capacity loss rate due to battery deterioration was evaluated by the following test method. The results are shown in Table 1. After the preparation of the non-aqueous electrolyte secondary battery, 5 cycles of charging and discharging were performed at 25 ° C., and the discharge capacity for the fifth time was defined as “capacity before storage”. Then, it left still for 2 weeks in a 60 degreeC thermostat in a full charge state. After two weeks, the battery was charged and discharged at 25 ° C. for 5 cycles, and the discharge capacity for the fifth time (the 10th time after battery preparation) was defined as “capacity after storage”.
  • Capacity loss rate (%) [1-[(capacity after storage) / (capacity before storage)]] ⁇ 100
  • the nonaqueous electrolyte secondary battery of the present invention is useful because it can maintain a stable battery capacity over a long period of time.

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Abstract

La présente invention concerne une batterie rechargeable à électrolyte non aqueux qui peut conserver une capacité de batterie stable pendant une longue période de temps par suppression de la détérioration de la capacité de la batterie rechargeable à électrolyte non aqueux. La présente invention concerne plus précisément une batterie rechargeable à électrolyte non aqueux qui comprend : (A) une électrode négative qui contient, comme matériau actif d'électrode négative, un matériau carboné ayant une masse volumique absolue de 1,60 à 2,20 g/cm3 ; (B) une électrode positive contenant un matériau actif d'électrode positive ; (C) une solution électrolytique non aqueuse obtenue par dissolution d'un sel de lithium dans un solvant organique ; et (D) une membrane de séparation. Cette batterie rechargeable à électrolyte non aqueux est configurée de manière que la solution électrolytique non aqueuse (C) obtenue par dissolution d'un sel de lithium dans un solvant organique contienne un composé représenté par la formule générale (1), et de préférence, que la solution électrolytique non aqueuse (C) contienne en outre un composé représenté par la formule générale (2). La formule générale (1) et la formule générale (2) sont définies dans la description.
PCT/JP2015/080745 2014-11-11 2015-10-30 Batterie rechargeable à électrolyte non aqueux WO2016076145A1 (fr)

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WO2018044882A1 (fr) * 2016-08-30 2018-03-08 Wildcat Discovery Technologies, Inc. Préparations d'électrolyte pour cellules électrochimiques contenant une électrode en silicium
WO2019070021A1 (fr) * 2017-10-06 2019-04-11 サイアス株式会社 Procédé de production d'une colonie de lymphocytes t génétiquement diverse dérivée d'une cellule ips
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EP3576206A1 (fr) * 2018-05-29 2019-12-04 Hyundai Motor Company Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium l'incluant
WO2020017378A1 (fr) * 2018-07-19 2020-01-23 株式会社Adeka Batterie secondaire à électrolyte non aqueux

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KR20200114267A (ko) * 2019-03-28 2020-10-07 현대자동차주식회사 리튬 이차전지

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EP3576206A1 (fr) * 2018-05-29 2019-12-04 Hyundai Motor Company Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium l'incluant
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WO2020017378A1 (fr) * 2018-07-19 2020-01-23 株式会社Adeka Batterie secondaire à électrolyte non aqueux

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