WO2020017378A1 - Batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux Download PDF

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WO2020017378A1
WO2020017378A1 PCT/JP2019/026995 JP2019026995W WO2020017378A1 WO 2020017378 A1 WO2020017378 A1 WO 2020017378A1 JP 2019026995 W JP2019026995 W JP 2019026995W WO 2020017378 A1 WO2020017378 A1 WO 2020017378A1
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group
carbon atoms
negative electrode
secondary battery
electrolyte secondary
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PCT/JP2019/026995
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English (en)
Japanese (ja)
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健二 撹上
真梨恵 中西
雄太 野原
洋平 青山
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株式会社Adeka
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Priority to KR1020207033072A priority Critical patent/KR20210031423A/ko
Priority to JP2020531250A priority patent/JPWO2020017378A1/ja
Publication of WO2020017378A1 publication Critical patent/WO2020017378A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
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    • 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
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    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 using a non-aqueous electrolyte containing a specific component.
  • Non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries are small, lightweight, have a high energy density, and can be repeatedly charged and discharged, so they can be used in portable electronic devices such as portable personal computers, handy video cameras, and information terminals. It is widely used as a power source for equipment. Further, from the viewpoint of environmental problems, electric vehicles using non-aqueous electrolyte secondary batteries and hybrid vehicles using electric power as a part of power have been put into practical use. Therefore, in recent years, further improvements in the performance of secondary batteries have been demanded from the viewpoints of the usable time of portable electronic devices, the cruising distance of automobiles, and their safety.
  • Charging / discharging capacity is one of the main performances of secondary batteries.
  • a new material for the positive electrode active material and the negative electrode active material has been studied.
  • a material using sulfur as a positive electrode active material has been proposed (for example, Patent Document 1)
  • a material using silicon, tin, or the like as a negative electrode active material has been proposed (for example, Patent Document 2).
  • an initial charging method for example, Patent Document 1
  • a method of controlling the particle size of the electrode active material Eg, Patent Document 2
  • methods of improving the electrolyte by using an electrolyte additive eg, Patent Documents 3 to 5
  • the technique using an electrolyte additive is an excellent method in that the effect can be easily obtained.
  • a solid electrolyte interface (SEI: Solid Electrolyte Interface) is formed on the surface of the electrode active material during charging and discharging, and a solvent used for the non-aqueous electrolyte is used. Decomposition is suppressed and cycle characteristics are improved. However, the film formed on the electrode active material becomes a resistance component in the charging / discharging process, and the rate characteristic showing high-speed charging / discharging performance is disadvantageous.
  • the rate characteristics were not sufficient.
  • the present invention has been made in view of the above circumstances, and has as its main object to provide a nonaqueous electrolyte secondary battery having improved cycle characteristics and rate characteristics.
  • a non-aqueous electrolyte secondary battery that solves the above problems includes a non-aqueous electrolyte including a positive electrode, a negative electrode containing a silicon atom, and a non-aqueous electrolyte containing a compound represented by the general formula (1) and a lithium salt. It is a secondary battery.
  • R 1 to R 3 each independently represent a hydrocarbon group having 1 to 10 carbon atoms
  • R 4 is an n-valent hydrocarbon group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms
  • a non-aqueous electrolyte secondary battery having improved cycle characteristics and rate characteristics is provided by using a combination of a negative electrode containing a silicon atom and a non-aqueous electrolyte containing a compound having a specific structure. It becomes possible to do.
  • 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.
  • nonaqueous electrolyte secondary battery of the present invention will be described in detail based on preferred embodiments.
  • the positive electrode used in the present invention is not particularly limited, and can be manufactured using a known positive electrode active material and according to a known method.
  • an electrode mixture paste obtained by slurrying a mixture containing a positive electrode active material, a binder and a conductive additive with an organic solvent or water is applied to a current collector and dried to form an electrode mixture on the current collector.
  • a positive electrode having a layer formed thereon can be manufactured.
  • Positive electrode active material includes, for example, lithium transition metal composite oxides, lithium-containing transition metal phosphate compounds, lithium-containing silicate compounds, and lithium-containing transition metal sulfate compounds.
  • the positive electrode active material may be used alone or in combination of two or more.
  • the transition metal of the lithium transition metal composite oxide vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper, and the like are preferable.
  • the lithium transition metal composite oxide include a lithium cobalt composite oxide such as LiCoO 2 , a lithium nickel composite oxide such as LiNiO 2 , and a lithium manganese composite oxide such as LiMnO 2 , LiMn 2 O 4 , and Li 2 MnO 3.
  • lithium transition metal composite oxide in which part of the main transition metal atom is substituted with another metal examples include, for example, Li 1.1 Mn 1.8 Mg 0.1 O 4 and Li 1.1 Mn 1.85.
  • the transition metal of the lithium-containing transition metal phosphate compound vanadium, titanium, manganese, iron, cobalt, nickel and the like are preferable.
  • transition metal atoms that are the main components of these lithium transition metal phosphate compounds, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, lithium, nickel, copper, zinc, magnesium, gallium, zirconium, Examples thereof include those substituted with other metals such as niobium, and vanadium phosphate compounds such as Li 3 V 2 (PO 4 ) 3 .
  • lithium-containing silicate compound examples include Li 2 FeSiO 4 and the like, and examples of the lithium-containing transition metal sulfate compound include LiFeSO 4 and LiFeSO 4 F.
  • sulfur a sulfur-carbon composite, and a sulfur-modified organic compound
  • the positive electrode active material various forms such as powdered sulfur, insoluble sulfur, precipitated sulfur, and colloidal sulfur can be used, but powdered sulfur is preferable in consideration of uniformly dispersing the raw material compound.
  • the sulfur-carbon composite is obtained by mechanically complexing sulfur and carbon, or containing sulfur in the pores of porous carbon, and is capable of absorbing and releasing lithium ions.
  • the sulfur content of the sulfur-carbon composite in which sulfur is supported in the pores of the porous carbon is such that when the content is too small, the charge / discharge capacity does not increase, and when the content is too large, the electron conductivity decreases. It is preferably from 90% by mass to 90% by mass, more preferably from 30% by mass to 70% by mass.
  • porous carbon examples include graphite, carbon, carbon black, Ketjen black, acetylene black, graphite, carbon fiber, activated carbon, and mesoporous carbon produced by a known production method.
  • the shape of the porous carbon may be spherical, fibrous, hollow, cylindrical, or amorphous. Two or more of these can be used.
  • Ketjen black, activated carbon, and mesoporous carbon are preferable because of their large surface area and high electron conductivity.
  • the method for forming a composite of sulfur and porous carbon is not particularly limited, and examples thereof include a method of mechanically mixing with various mills, a liquid phase and / or a gas phase method, or a method combining these methods.
  • a ball mill such as a planetary ball mill, a rolling ball mill, a vibrating ball mill, a vertical roller mill such as a ring roller mill, a high-speed rotation mill such as a hammer mill and a cage mill, and an air current such as a jet mill.
  • a type mill and the like can be mentioned.
  • the non-oxidizing atmosphere is an atmosphere having an oxygen concentration of less than 5% by volume, preferably less than 2% by volume, more preferably an atmosphere containing substantially no oxygen, that is, an inert gas atmosphere such as nitrogen, helium, or argon, It is a sulfur gas atmosphere.
  • the average particle diameter (D50) of the positive electrode active material in the present invention is preferably 0.5 ⁇ m to 100 ⁇ m, and more preferably 1 ⁇ m to 50 ⁇ m, from the viewpoint of obtaining a uniform and smooth electrode mixture layer and the handleability in the slurrying step. More preferably, it is more preferably from 1 ⁇ m to 30 ⁇ m.
  • the average particle diameter (D50) refers to a 50% particle diameter measured by a laser diffraction light scattering method. The particle diameter is a volume-based diameter, and the diameter of the secondary particles is measured by the laser diffraction light scattering method.
  • the positive electrode active material can have a desired particle size by a method such as pulverization.
  • the pulverization may be dry pulverization performed in a gas or wet pulverization performed in a liquid such as water.
  • Examples of the industrial pulverization method include a ball mill, a roller mill, a turbo mill, a jet mill, a cyclone mill, a hammer mill, a pin mill, a rotary mill, a vibration mill, a planetary mill, an attritor, and a bead mill.
  • binder binders
  • binders can be used as the binder.
  • conductive assistant those known as conductive assistants for electrodes can be used. Specifically, for example, natural graphite, artificial graphite, coal tar pitch, carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, roller black, disk black, carbon nanotube, gas phase Carbon materials such as carbon fiber (Vapor Carbon Carbon Fiber: VGCF), graphene, fullerene, and needle coke; metal powders such as aluminum powder, nickel powder, and titanium powder; conductive metal oxides such as zinc oxide and titanium oxide; Sulfides such as La 2 S 3 , Sm 2 S 3 , Ce 2 S 3 , and TiS 2 are exemplified.
  • the particle size of the conductive additive is preferably from 0.0001 ⁇ m to 100 ⁇ m, more preferably from 0.01 ⁇ m to 50 ⁇ m.
  • the content of the conductive additive is usually 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the electrode active material.
  • solvent examples include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetonitrile, and acetonitrile.
  • the amount of the solvent used may be adjusted according to the method selected when coating the slurry.For example, in the case of application by the doctor blade method, the total amount of the positive electrode active material, the binder and the conductive additive is 100 parts by mass. On the other hand, the amount is preferably from 15 to 300 parts by mass, more preferably from 30 to 200 parts by mass.
  • the electrode mixture paste contains, in addition to the above components, other components such as a viscosity adjuster, a reinforcing material, an antioxidant, a pH adjuster, and a dispersant, in a range that does not impair the effects of the present invention. It does not matter.
  • known components can be used in known mixing ratios.
  • Electrode mixture paste manufacturing process In the production of the electrode mixture paste, when dispersing or dissolving the positive electrode active material, the binder and the conductive auxiliary in a solvent, all can be added to the solvent at once and subjected to dispersion treatment, and separately added and dispersed. You can also. It is preferable to sequentially add a binder, a conductive auxiliary agent, and an active material to a solvent in the order of the dispersion treatment, since these can be uniformly dispersed in the solvent. When the electrode mixture paste contains other components, the other components can be added at once and subjected to a dispersion treatment. However, it is preferable to perform the dispersion treatment every time one kind is added.
  • the method of the dispersion treatment is not particularly limited, but as an industrial method, for example, a normal ball mill, a sand mill, a bead mill, a cyclone mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a rotation / revolution mixer, A planetary mixer, a fill mix, a jet paster, or the like can be used.
  • a conductive material such as titanium, a titanium alloy, aluminum, an aluminum alloy, nickel, stainless steel, nickel-plated steel, and carbon is used.
  • the shape of the current collector include a foil shape, a plate shape, a net shape, a foamed shape, and a nonwoven fabric shape.
  • the current collector may be either porous or non-porous.
  • these conductive materials may be subjected to a surface treatment in order to improve adhesion and electrical characteristics.
  • aluminum is preferred from the viewpoint of conductivity and price, and aluminum foil is particularly preferred.
  • the thickness of the current collector is not particularly limited, but is usually 5 to 30 ⁇ m.
  • the method of applying the electrode mixture paste to the current collector is not particularly limited.
  • a die coater method, a comma coater method, a curtain coater method, a spray coater method, a gravure coater method, a flexo coater method, a knife coater method, a doctor coater method Each method such as a blade method, a reverse roll method, a brush coating method, and a dip method can be used.
  • a die coater method, a knife coater method, a doctor blade method, and a comma coater method are preferable in that a good coating layer surface state can be obtained in accordance with the viscosity and drying properties of the electrode mixture paste.
  • the application of the electrode mixture paste to the current collector may be performed on only one side of the current collector, or may be performed on both sides.
  • the current collector can be applied one by one successively, or both surfaces can be applied simultaneously. Further, it can be applied continuously to the surface of the current collector, can be applied intermittently, or can be applied in a stripe shape.
  • the thickness, length and width of the coating layer can be appropriately determined according to the size of the battery and the like.
  • lithium can be doped in advance.
  • the method of doping the material may be a known method. For example, assembling a half-cell using metallic lithium as the counter electrode and inserting lithium by an electrolytic doping method of electrochemically doping lithium, or attaching a metallic lithium foil to the electrode and leaving it in the electrolytic solution There is a method of inserting lithium by a sticking doping method of doping using diffusion of lithium to the electrode, a mechanical doping method of mechanically colliding an active material with lithium metal and inserting lithium, and the like. It is not limited.
  • the negative electrode containing a silicon atom used in the present invention is not particularly limited, and can be produced according to a known method using a negative electrode active material containing a silicon atom.
  • a negative electrode active material containing a silicon atom, an electrode mixture paste obtained by slurrying a composition containing a binder and a conductive auxiliary agent with an organic solvent or water, by coating and drying the current collector, the current collector A negative electrode having an electrode mixture layer formed thereon can be manufactured.
  • the negative electrode active material containing a silicon atom examples include simple substance silicon, silicon nitride, an alloy containing silicon, SiO, SiO x , SiO 2 , and a Si-containing material coated with a carbon material, or a mixture of a Si-containing material and carbon.
  • a composite material of a Si-containing material and a carbon material in which the material is composited is exemplified.
  • the Si-containing material examples include simple silicon, silicon nitride, an alloy containing silicon, SiO, SiO x , and SiO.
  • the negative electrode active material containing a silicon atom may be carbon-coated. As the negative electrode active material containing a silicon atom, only one type may be used, or two or more types may be used in combination.
  • the silicon nitride may have an ⁇ -phase or ⁇ -phase crystal phase.
  • the alloy containing silicon for example, as the second constituent element other than silicon, lithium, aluminum, tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, and antimony And at least one of the group consisting of chromium.
  • X of the SiO x is usually 0.01 or more and less than 2.
  • x is preferably 0.5 to 1.6, and more preferably 0.8 to 1.3.
  • SiO x can be formed using, for example, a reaction between Si and SiO 2 or a disproportionation reaction of silicon monoxide (SiO).
  • a SiO, heat treated in the presence of polymers such as polyvinyl alcohol, by forming a Si and SiO 2 can be prepared SiO x, it is not limited thereto .
  • the heat treatment can be performed, for example, at a temperature of 900 ° C. or higher, preferably 1000 ° C. or higher in an atmosphere containing an organic substance gas and / or steam after pulverizing and mixing SiO and a polymer.
  • the method of compounding when producing a compound of the Si-containing material and the carbon material is not particularly limited.
  • benzene, toluene, xylene, alkane, or the like is decomposed in a gas phase with a carbon source, and CVD method of chemical vapor deposition, method of applying thermoplastic resin such as pitch, tar or furfuryl alcohol on the surface of particles and then firing, or applying mechanical energy between particles and carbon material to composite
  • CVD method A method using a mechanochemical reaction that forms Among them, it is preferable to use the CVD method because the carbon material can be uniformly coated.
  • the negative electrode containing a silicon atom used in the present invention may further contain a carbon material as a negative electrode active material.
  • a carbon material that can be contained as the negative electrode active material a known material from which lithium ions can be inserted and removed can be used.
  • Examples of the carbon material that can be used as the negative electrode active material include natural graphite, artificial graphite, non-graphitizable carbon, graphitizable carbon, and the like.
  • the negative electrode containing a silicon atom used in the present invention may further contain a lithium-transition metal composite oxide (eg, Li 4 Ti 5 O 12 ), tin, or the like as a negative electrode active material.
  • the content of silicon atoms in the negative electrode is not particularly limited, but a small content has a small effect of improving capacity, and a large content increases the rate of change in volume of the negative electrode active material due to charge and discharge and increases the durability of the electrode. And the cycle characteristics of the non-aqueous electrolyte secondary battery decrease. Therefore, the content of silicon atoms in the electrode mixture layer is preferably 1% by mass to 98% by mass, more preferably 2% by mass to 95% by mass, still more preferably 5% by mass to 90% by mass, and 5% by mass. The content is more preferably from 80 to 80% by mass, and most preferably from 5 to 70% by mass.
  • This amount is based on silicon atoms and can be measured by, for example, an inductively coupled plasma emission spectrometer (ICP-AES), an electron beam microanalyzer (EPMA), an energy dispersive X-ray analyzer (EDX), or the like.
  • ICP-AES inductively coupled plasma emission spectrometer
  • EPMA electron beam microanalyzer
  • EDX energy dispersive X-ray analyzer
  • the shape of the negative electrode active material is not particularly limited, but may be, for example, spherical, polyhedral, fibrous, rod-like, plate-like, scale-like, or amorphous, and may be hollow. Among these shapes, a spherical or polyhedral shape is preferable because the electrode mixture layer is formed uniformly.
  • the average particle diameter (D50) of the silicon-containing negative electrode active material in the present invention is preferably 0.01 ⁇ m to 50 ⁇ m, more preferably 0.05 ⁇ m to 30 ⁇ m, and further preferably 0.1 ⁇ m to 20 ⁇ m.
  • the average particle diameter of the negative electrode active material containing the carbon material is in the same range as the preferable range described above for the average particle diameter of the negative electrode active material containing silicon atoms. It may be.
  • the negative electrode active material can have a desired particle size by a method such as pulverization.
  • the pulverization may be dry pulverization performed in a gas or wet pulverization performed in a liquid such as water.
  • Examples of the industrial pulverization method include a ball mill, a roller mill, a turbo mill, a jet mill, a cyclone mill, a hammer mill, a pin mill, a rotary mill, a vibration mill, a planetary mill, an attritor, and a bead mill.
  • the negative electrode active materials may be pulverized for each material and then mixed, or may be mixed and pulverized.
  • binder binder
  • binders can be used as the binder. Specific examples of the binder include, for example, those similar to the binder used for the positive electrode. Only one binder may be used, or two or more binders may be used in combination.
  • the content of the binder is preferably from 1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the negative electrode active material.
  • conductive assistant those known as conductive assistants for electrodes can be used. Specifically, the same as the conductive additive used for the positive electrode can be used.
  • the particle size of the conductive additive is preferably from 0.0001 ⁇ m to 100 ⁇ m, more preferably from 0.01 ⁇ m to 50 ⁇ m.
  • the content of the conductive additive is usually 0 to 50 parts by mass, preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the negative electrode active material.
  • solvent examples of the solvent for preparing the electrode mixture paste include the same solvents as those used for preparing the positive electrode mixture paste.
  • the amount of the solvent used can be adjusted according to the method selected when coating the slurry. For example, in the case of application by the doctor blade method, the total amount of the negative electrode active material, the binder and the conductive auxiliary agent is 100 parts by mass. Is preferably 15 to 300 parts by mass, more preferably 30 to 200 parts by mass.
  • a viscosity modifier for example, a viscosity modifier, a reinforcing material, an antioxidant, a pH adjuster, and other components such as a dispersant are contained. No problem.
  • known components can be used in known mixing ratios.
  • Electrode mixture paste manufacturing process Except for using the negative electrode active material instead of the positive electrode active material in the production of the electrode mixture paste, it can be blended, dispersed and produced in the same process as the production process of the positive electrode mixture paste.
  • the negative electrode used in the present invention may be used after being doped with lithium in advance.
  • the doping method may be in accordance with a known method. For example, assembling a half-cell using metallic lithium as the counter electrode and inserting lithium by electrolytic doping method of electrochemically doping lithium, or attaching a metallic lithium foil to the electrode and leaving it in the electrolytic solution Doping using the diffusion of lithium into the electrode, a method of inserting lithium by a sticking doping method, a mechanical doping method of mechanically colliding an active material with lithium metal and inserting lithium, and the like.
  • the present invention is not limited to this.
  • the negative electrode active material or the negative electrode used in the present invention may have a film formed on its surface with a material having a siloxane bond.
  • a material having a siloxane bond and a method of forming a film may be in accordance with a known method.
  • the non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery of the present invention contains a compound represented by the following general formula (1).
  • the cycle characteristics and the rate characteristics of the nonaqueous electrolyte secondary battery using the negative electrode containing a silicon atom are improved. Can be.
  • Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R 1 to R 3 in the compound represented by the general formula (1) include, for example, a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group. And aromatic hydrocarbon groups.
  • Hydrocarbon group phenyl group, methylphenyl group, ethylphenyl group, t-butylphenyl group, phenylmethyl group Phenylethyl group, and aromatic hydrocarbon groups such as a naphthyl group.
  • the saturated aliphatic hydrocarbon group and the unsaturated aliphatic hydrocarbon group may have a linear structure or a branched structure.
  • the hydrocarbon group having 1 to 10 carbon atoms representing R 1 to R 3 is preferably a hydrocarbon group having 1 to 4 carbon atoms because both the cycle characteristics and the rate characteristics are improved and the production process is simple.
  • An aliphatic hydrocarbon group or an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferable, a methyl group, an ethyl group, a butyl group, a vinyl group or a phenyl group is more preferable, and a methyl group, an ethyl group, a vinyl group or a phenyl group is more preferable. Even more preferred is a methyl group.
  • the content of the compound represented by the general formula (1) is preferably 0.01% by mass to 20% by mass, more preferably 0.05% by mass to 10% by mass, and more preferably 0.1% by mass in the nonaqueous electrolyte. -7% by mass is more preferable, and 0.1-5% by mass is most preferable.
  • the content is 0.01% by mass or more, the cycle characteristics and the rate characteristics are sufficiently improved.
  • the content is 20% by mass or less, the effect of improving the cycle characteristics and the rate characteristics commensurate with the added amount. There is expected.
  • R 1 to R 3 are saturated hydrocarbon groups
  • R 4 is a group in which two methylene groups are connected by a sulfur atom.
  • No. 1-1 to No. 1-29 but is not limited thereto.
  • Compound No. A notation such as 1-28 indicates that the position of the substituent is arbitrary.
  • any one of n R 1 to R 3 is an unsaturated hydrocarbon group, and R 4 is a group in which two methylene groups are connected by a sulfur atom.
  • R 4 is a group in which two methylene groups are connected by a sulfur atom.
  • any one of n R 1 to R 3 is an aromatic hydrocarbon group, and R 4 is a group in which two methylene groups are connected by a sulfur atom.
  • R 4 is a group in which two methylene groups are connected by a sulfur atom.
  • R 4 in the general formula (1) is an n-valent hydrocarbon group having 1 to 10 carbon atoms, an n-valent group in which a hydrocarbon group having 1 to 10 carbon atoms is connected by an oxygen atom or a sulfur atom, or Represents an n-valent heterocyclic group containing an oxygen atom or a sulfur atom, and n represents an integer of 1 to 6.
  • the compound represented by the general formula (1) is a compound represented by the following general formula: This corresponds to a compound substituted with a group represented by the formula (1a).
  • Examples of the hydrocarbons having 1 to 10 carbon atoms in which n hydrogen atoms are substituted by the general formula (1a) include saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, and aromatic hydrocarbons. Specifically, for example, methane, ethane, propane, n-butane, 2-methylpropane, n-pentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane And saturated aliphatic hydrocarbons such as n-adamantane, ethene, ethyne, propene, propyne, 1-butene, 2-butene, 1,3-butadiene, 1-pentene, 2-pentene, 1,3-pentadiene, 1- Hexene, 3-hexene, 1,3,5-hexatriene,
  • R 4 in the general formula (1) is an n-valent group in which a hydrocarbon group having 1 to 10 carbon atoms is connected by an oxygen atom or a sulfur atom
  • the compound represented by the general formula (1) is The compound corresponds to a compound in which a hydrocarbon group having 1 to 10 carbon atoms is connected by an oxygen atom or a sulfur atom, wherein n hydrogen atoms are substituted by a group represented by the general formula (1a).
  • Examples of the compound in which a hydrocarbon group having 1 to 10 carbon atoms is linked by an oxygen atom or a sulfur atom include a compound in which a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group is linked by an oxygen atom or a sulfur atom.
  • the linked saturated aliphatic hydrocarbon groups or unsaturated aliphatic hydrocarbon groups may be the same or different.
  • the saturated aliphatic hydrocarbon group or unsaturated aliphatic hydrocarbon group is the same as the saturated aliphatic hydrocarbon group or unsaturated aliphatic hydrocarbon group represented by R 1 to R 3 in the general formula (1). No.
  • connection includes not only a case where the connection is made with one oxygen atom or a sulfur atom but also a case where the connection is made with two or more oxygen atoms or oxygen atoms.
  • the latter case includes, for example, a case where they are linked by -SS-, and a case where they are represented by -S-RS- or the like (R is an alkylene group having 1 or 2 carbon atoms).
  • R 1 to R 3 are methyl groups, for example, the following compound No. 1a-29 to No. 1 1a-58, but not limited thereto.
  • R 1 to R 3 are methyl groups, for example, the following compound No. 1a-59 to No. 1 1a-66, but is not limited thereto.
  • No. A bond extending over a plurality of rings described in 1a-66 means that a bond can be bonded to any position of these rings.
  • R 4 is preferably an n-valent aliphatic hydrocarbon group having 2 to 10 carbon atoms, because of improved cycle characteristics and rate characteristics, a simple production process, and easy availability.
  • Preferred are an n-valent group in which 1 to 10 hydrocarbon groups are connected by a sulfur atom, and an n-valent heterocyclic group having 3 to 6 carbon atoms containing a sulfur atom.
  • the aliphatic hydrocarbon group represented by R 4 an aliphatic hydrocarbon group having 2 to 6 carbon atoms is more preferable, and an unsaturated aliphatic hydrocarbon group having 2 to 4 carbon atoms is most preferable.
  • n-valent group in which a hydrocarbon group having 1 to 10 carbon atoms represented by R 4 is linked by a sulfur atom an aliphatic hydrocarbon group having 1 to 6 carbon atoms is linked to a sulfur atom A group is preferable, and a group in which an aliphatic hydrocarbon group having 1 to 4 carbon atoms is connected to one sulfur atom or the above-mentioned —S—R—S— group is particularly preferable.
  • sulfur-containing n-valent heterocyclic group having 3 to 6 carbon atoms represented by R 4 an aromatic heterocyclic ring having 3 to 8 carbon atoms including a sulfur atom is particularly preferable, and thiophene is most preferable.
  • R 4 is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms in addition to the above groups.
  • n is preferably 2 to 6, more preferably 2 to 4, and most preferably 2, because the cycle characteristics and rate characteristics of the nonaqueous electrolyte secondary battery are good.
  • the compound No. 1 can be used because the cycle characteristics and the rate characteristics are both improved and the production process is simple.
  • 1-1, No. 1a-1, No. 1; 1a-2, No. 1 1a-29, no. 1a-35, no. 1a-59, no. 1a-68, no. 1a-77, no. 1a-82 and No. 1 No. 1a-92 is preferable.
  • 1-1, No. 1a-1, No. 1; 1a-29, no. Nos. 1a-82 and No. 1 1a-94 is more preferred.
  • the non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery of the present invention contains a lithium salt.
  • a liquid electrolyte obtained by dissolving a lithium salt in a solvent a polymer gel obtained by dissolving or dispersing a lithium salt in a polymer gel gelled with a polymer compound dissolved in a solvent, A pure polymer electrolyte obtained by using a polymer compound as a dispersion medium and dissolving or dispersing a lithium salt can be used.
  • lithium salt used for the pure polymer electrolyte examples include LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (SO 2 F) 2 , and LiC (CF 3 SO 2 ) 3. , LiB (CF 3 SO 3 ) 4 , LiB (C 2 O 4 ) 2 and the like.
  • the concentration of the lithium salt in the nonaqueous electrolyte is too low, a sufficient current density may not be obtained, and if the concentration is too high, the stability of the liquid nonaqueous electrolyte may be impaired.
  • L is preferable, and 0.8 to 1.8 mol / L is more preferable.
  • an organic solvent usually used for a non-aqueous electrolyte of a non-aqueous electrolyte secondary battery can be used.
  • the organic solvent usually used for the non-aqueous electrolyte of the non-aqueous electrolyte secondary battery include, for example, a saturated cyclic carbonate compound, a saturated cyclic ester compound, a sulfoxide compound, a sulfone compound, an amide compound, a saturated chain carbonate compound, and a chain ether.
  • the saturated cyclic carbonate compound, the saturated cyclic ester compound, the sulfoxide compound, the sulfone compound and the amide compound have a high relative dielectric constant, and thus play a role of increasing the dielectric constant of the liquid composition, and in particular, the saturated cyclic carbonate compound. Is preferred.
  • saturated cyclic carbonate compound examples include ethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 1,1-dimethylethylene carbonate and the like.
  • saturated cyclic ester compound examples include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -hexanolactone, ⁇ -octanolactone, and the like.
  • sulfoxide compound examples include dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, and thiophene.
  • sulfone compound examples include dimethyl sulfone, diethyl sulfone, dipropyl sulfone, diphenyl sulfone, sulfolane (also referred to as tetramethylene sulfone), 3-methyl sulfolane, 3,4-dimethyl sulfolane, 3,4-diphenyl sulfolane, sulfolene, Examples include 3-methylsulfolene, 3-ethylsulfolene, and 3-bromomethylsulfolene. Sulfolane and tetramethylsulfolane are preferred.
  • Amide compounds include N-methylpyrrolidone, dimethylformamide, dimethylacetamide and the like.
  • the saturated chain carbonate compound, the chain ether compound, the cyclic ether compound and the saturated chain ester compound can lower the viscosity of the liquid composition and increase the mobility of electrolyte ions.
  • the battery characteristics such as the output density can be improved.
  • the viscosity is low, the performance of the non-aqueous electrolyte at a low temperature can be enhanced, and a saturated chain carbonate compound is particularly preferable.
  • saturated chain carbonate compound examples include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl butyl carbonate, methyl-t-butyl carbonate, diisopropyl carbonate, t-butyl propyl carbonate and the like.
  • chain ether compound or cyclic ether compound examples include dimethoxyethane, ethoxymethoxyethane, diethoxyethane, tetrahydrofuran, dioxolan, dioxane, 1,2-bis (methoxycarbonyloxy) ethane, and 1,2-bis (ethoxycarbonyl).
  • the saturated chain ester compound a monoester compound and a diester compound having a total of 2 to 8 carbon atoms in the molecule are preferable, and specific compounds include, for example, methyl formate, ethyl formate, methyl acetate, acetic acid and the like.
  • organic solvent used for preparing the liquid electrolyte for example, acetonitrile, propionitrile, nitromethane, derivatives thereof, and various ionic liquids can be used.
  • Examples of the polymer used for the polymer gel electrolyte include polyethylene oxide, polypropylene oxide, polyvinyl chloride, polyacrylonitrile, polymethyl methacrylate, polyethylene, polyvinylidene fluoride, and polyhexafluoropropylene.
  • Examples of the polymer used for the pure polymer electrolyte include polyethylene oxide, polypropylene oxide, and polystyrene sulfonic acid.
  • the non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery of the present invention may further contain a compound represented by the general formula (2) because battery characteristics such as cycle characteristics and safety are improved.
  • R 5 to R 9 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a heterocyclic group having 4 to 6 carbon atoms, and at least one hydrogen atom Represents a hydrocarbon group having 1 to 6 carbon atoms substituted by a fluorine atom, or a heterocyclic group having 4 to 6 carbon atoms substituted by one or more hydrogen atoms by a fluorine atom, and R 10 to R 12 are Each independently represents a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • examples of the halogen atom represented by R 5 to R 9 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • examples of the hydrocarbon group having 1 to 6 carbon atoms include a linear or cyclic saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, and an aromatic hydrocarbon group.
  • heterocyclic group having 4 to 6 carbon atoms examples include a thienyl group, a furanyl group, a pyridyl group, a tetrahydrothienyl group, a tetrahydrofuranyl group, and a piperidyl group.
  • Examples of the hydrocarbon group having 1 to 6 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom include a linear saturated aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a fluorine atom, An unsaturated aliphatic hydrocarbon group in which at least one hydrogen atom has been replaced with a fluorine atom, a cyclic saturated aliphatic hydrocarbon group having at least one hydrogen atom replaced with a fluorine atom, and at least one hydrogen atom having a fluorine atom; And a substituted phenyl group.
  • Examples of the chain saturated aliphatic hydrocarbon group, unsaturated aliphatic hydrocarbon group and cyclic saturated aliphatic hydrocarbon group include the above-mentioned chain saturated aliphatic hydrocarbon group, unsaturated aliphatic hydrocarbon group, and cyclic saturated aliphatic group. And a hydrocarbon group.
  • Examples of the chain saturated aliphatic hydrocarbon group in which one or more hydrogen atoms have been substituted with a fluorine atom include, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 1-fluoroethyl group, 2-fluoroethyl Group, 1-fluoroisopropyl group, 2-fluoroisopropyl group, 1-fluorobutyl group, 2-fluorobutyl group, 3-fluorobutyl group, 1-fluoroisobutyl group, 2-fluoroisobutyl group, 2-fluoro-t- Examples thereof include a butyl group, a 1-fluoropentyl group, a 2-fluoropentyl group, a 3-fluoropentyl group, a 4-fluoropentyl group, and a 1-fluorohexyl group.
  • Examples of the cyclic saturated aliphatic hydrocarbon group in which one or more hydrogen atoms have been substituted with fluorine atoms include a fluorocyclopentyl group and a fluorocyclohexyl group.
  • Examples of the aromatic hydrocarbon group in which one or more hydrogen atoms have been replaced by fluorine atoms include a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, and the like.
  • heterocyclic group in which one or more hydrogen atoms are substituted with a fluorine atom examples include a fluorothienyl group, a fluorofuranyl group, a fluoropyridyl group, a fluorothiolanyl group, a fluorooxanyl group, a fluoropiperidyl group, and the like.
  • halogen atom represented by R 10 to R 12 and the hydrocarbon group having 1 to 6 carbon atoms in the compound represented by the general formula (2) those similar to R 5 to R 9 can be mentioned.
  • alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a butoxy group, a pentoxy group, a hexyloxy group and a cyclohexyloxy group.
  • compounds in which R 5 to R 9 are a hydrogen atom or a halogen atom and R 10 to R 12 are a methyl group include, for example, the following compound Nos. 2-1 to No. 2-6.
  • any one of R 5 to R 9 is a saturated aliphatic hydrocarbon group and R 10 to R 12 is a methyl group. 2-7 to No. 2-23.
  • any of R 5 to R 9 is an unsaturated aliphatic hydrocarbon group and R 10 to R 12 is a methyl group, for example, the following compound No. . 2-24 to No. 2-32.
  • compounds in which any of R 5 to R 9 is a cyclic aliphatic hydrocarbon group or a phenyl group and R 10 to R 12 are a methyl group include, for example, Compound No. 2-33-No. 2-35.
  • any of R 5 to R 9 is a heterocyclic group, and R 10 to R 12 are methyl groups. 2-36-No. 2-41.
  • any of R 5 to R 9 is a hydrocarbon group having 1 to 6 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom,
  • 10 to R 12 are a methyl group, for example, the following compound No. 2-42 to No. 2-54.
  • any of R 5 to R 9 is a heterocyclic group in which one or more hydrogen atoms are substituted with a fluorine atom, and R 10 to R 12 are a methyl group.
  • R 5 to R 9 is a heterocyclic group in which one or more hydrogen atoms are substituted with a fluorine atom
  • R 10 to R 12 are a methyl group.
  • R 5 to R 9 of the compound represented by the general formula (2) have excellent cycle characteristics and rate characteristics, and are easily available as raw materials. It is preferably a hydrogen group, more preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. In addition, a hydrogen atom, a fluorine atom, a methyl group, or a vinyl group is also preferable because excellent battery characteristics are obtained, raw materials are easily available, and synthesis is simple. From these points, it is most preferable that R 5 to R 9 be a hydrogen atom.
  • R 10 to R 12 of the compound represented by the general formula (2) an aliphatic hydrocarbon group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms is preferable because of excellent cycle characteristics and rate characteristics. It is preferred that Further, as R 10 to R 12 , a methyl group, a vinyl group or a phenyl group is preferable, and a methyl group is more preferable, because excellent battery characteristics are obtained, raw materials are easily available, and synthesis is simple. .
  • the content of the compound represented by the general formula (2) is preferably from 0.1% by mass to 20% by mass, more preferably from 0.1% by mass to 10% by mass, and more preferably from 0.1% by mass to 10% by mass based on the whole nonaqueous electrolyte. It is more preferably from 5% by mass to 7.0% by mass, most preferably from 1% by mass to 5% by mass.
  • the content is 0.1% by mass or more, a sufficient effect can be exhibited, and when the content is 20% by mass or less, an effect of increasing the amount commensurate with the addition amount is observed, and the battery performance due to an excessive amount of the compound is obtained. Can be prevented more reliably.
  • the non-aqueous electrolyte secondary battery of the present invention can be manufactured by interposing a non-aqueous electrolyte containing the compound represented by the general formula (1) and the lithium salt between the positive electrode and the negative electrode.
  • a separator between the positive electrode and the negative electrode it is preferable to use a separator between the positive electrode and the negative electrode.
  • the separator As the separator, a commonly used polymer film can be used without particular limitation.
  • the polymer film include, for example, polyethylene, polypropylene, polyvinylidene fluoride, polyvinylidene chloride, polyacrylonitrile, polyacrylamide, polytetrafluoroethylene, polysulfone, polyethersulfone, polycarbonate, polyamide, polyimide, polyethylene oxide, polypropylene oxide, and the like. It is composed of polyethers, various celluloses such as carboxymethylcellulose and hydroxypropylcellulose, polymer compounds mainly composed of poly (meth) acrylic acid and various esters thereof, derivatives thereof, and copolymers and mixtures thereof. Films and the like can be mentioned.
  • the shape of the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, and may be various shapes such as a coin shape, a cylindrical shape, a square shape, and a laminate type.
  • 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.
  • 1 is a positive electrode capable of releasing lithium ions
  • 1a is a positive electrode current collector
  • 2 is a negative electrode capable of absorbing and releasing lithium ions released from the positive electrode
  • 2a is A negative electrode current collector
  • 3 is a non-aqueous electrolyte
  • 4 is a positive electrode case made of stainless steel
  • 5 is a negative electrode case made of stainless steel
  • 6 is a gasket made of polypropylene
  • 7 is a separator made of polyethylene.
  • 11 is a negative electrode
  • 12 is a negative electrode current collector
  • 13 is a positive electrode
  • 14 is a positive electrode current collector
  • 15 is a non-aqueous electrolyte
  • 16 is a separator
  • 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 is a gasket
  • 26 is a safety valve.
  • 27 are PTC elements.
  • the external packaging member a laminated film or a metal container can be used.
  • the thickness of the packaging member is usually 0.5 mm or less, preferably 0.3 mm or less.
  • Examples of the shape of the packaging member include a flat type (thin type), a square type, a cylindrical type, a coin type, and a button type.
  • the laminate film may be a multilayer film having a metal layer between resin films.
  • the metal layer is preferably an aluminum foil or an aluminum alloy foil for weight reduction.
  • As the resin film for example, a polymer material such as polypropylene, polyethylene, nylon, or polyethylene terephthalate can be used.
  • the laminate film can be formed into a shape of an exterior member by performing sealing by heat fusion.
  • the electrode mixture paste was applied to a current collector made of aluminum foil (thickness: 20 ⁇ m) by a doctor blade method, and allowed to stand at 90 ° C. for 3 hours and dried. Further, press molding was performed. Thereafter, the electrode was cut into a predetermined size, and further dried under vacuum at 150 ° C. for 2 hours immediately before use to produce a positive electrode.
  • the negative electrode A was prepared by dissolving 1.0 mol / L of LiPF 6 in a mixed solvent of 30% by volume of ethylene carbonate, 30% by volume of dimethyl carbonate, and 40% by volume of ethyl methyl carbonate, using lithium metal as a counter electrode. A half-cell was assembled as an electrolyte, and an electrochemically doped lithium was used.
  • Example 2 A coin-type non-aqueous electrolyte secondary battery of Example 2 was produced in the same manner as in Example 1, except that Compound No. 1-1 was dissolved in the mixed solvent at a concentration of 1.0% by mass.
  • Example 3 A coin-type nonaqueous electrolyte secondary battery of Example 3 was produced in the same manner as in Example 1, except that Compound No. 1-1 was dissolved in the mixed solvent at a concentration of 2.0% by mass.
  • Example 4 A coin-type nonaqueous electrolyte secondary battery of Example 4 was produced in the same manner as in Example 1, except that Compound No. 1a-29 was dissolved in the above-mentioned mixed solvent at a concentration of 0.5% by mass.
  • Example 5 A coin-type nonaqueous electrolyte secondary battery of Example 5 was produced in the same manner as in Example 1, except that Compound No. 1a-29 was dissolved in the above mixed solvent at a concentration of 1.0% by mass.
  • Example 6 A coin-type nonaqueous electrolyte secondary battery of Example 6 was produced in the same manner as in Example 1, except that Compound No. 1a-29 was dissolved in the mixed solvent at a concentration of 2.0% by mass.
  • Example 7 A coin-type nonaqueous electrolyte secondary battery of Example 7 was produced in the same manner as in Example 1, except that Compound No. 1a-92 was dissolved in the above mixed solvent at a concentration of 0.5% by mass.
  • Example 9 A coin-type nonaqueous electrolyte secondary battery of Example 9 was produced in the same manner as in Example 1, except that Compound No. 1a-92 was dissolved in the above mixed solvent at a concentration of 2.0% by mass.
  • Example 10 Compound No. 1-1 was added at a concentration of 1.0% by mass, and Compound No. 1-1 was used.
  • a coin-type non-aqueous electrolyte secondary battery of Example 10 was produced in the same manner as in Example 1, except that 2-1 was dissolved in the mixed solvent at a concentration of 1.0% by mass.
  • Example 11 Compound No. 1a-29 was added at a concentration of 1.0% by mass and Compound No. 1a-29 was added.
  • a coin-type non-aqueous electrolyte secondary battery of Example 11 was produced in the same manner as in Example 1, except that 2-1 was dissolved in the mixed solvent at a concentration of 1.0% by mass.
  • Example 12 Compound No. 1a-92 was added at a concentration of 1.0% by mass and Compound No. 1a-92 was added.
  • a coin-type nonaqueous electrolyte secondary battery of Example 12 was produced in the same manner as in Example 1, except that 2-1 was dissolved in the above-mentioned mixed solvent at a concentration of 1.0% by mass.
  • Example 13 Further, a coin-type non-aqueous electrolyte secondary battery of Example 13 was produced in the same manner as in Example 1, except that vinylene carbonate was dissolved in the mixed solvent at a concentration of 0.5% by mass.
  • Example 14 Further, a coin-type nonaqueous electrolyte secondary battery of Example 14 was produced in the same manner as in Example 4, except that vinylene carbonate was dissolved in the mixed solvent at a concentration of 0.5% by mass.
  • Example 15 Further, a coin-type non-aqueous electrolyte secondary battery of Example 15 was produced in the same manner as in Example 7, except that vinylene carbonate was dissolved in the mixed solvent at a concentration of 0.5% by mass.
  • CMCNa manufactured by Daicel Finechem
  • Example 16 A coin-type non-aqueous electrolyte secondary battery of Example 16 was produced in the same manner as in Example 2, except that the negative electrode B was used instead of the negative electrode A.
  • Example 17 A coin-type non-aqueous electrolyte secondary battery of Example 17 was produced in the same manner as in Example 5, except that the negative electrode B was used instead of the negative electrode A.
  • Example 18 A coin-type nonaqueous electrolyte secondary battery of Example 18 was produced in the same manner as in Example 8, except that the negative electrode B was used instead of the negative electrode A.
  • the electrode mixture paste was applied to a current collector made of copper foil (thickness: 10 ⁇ m) by a doctor blade method, and allowed to stand at 90 ° C. for 3 hours and dried. Thereafter, the electrode was cut into a predetermined size, and further dried immediately before use at 150 ° C. for 2 hours under vacuum to produce a negative electrode C.
  • Example 20 A coin-type non-aqueous electrolyte secondary battery of Example 20 was produced in the same manner as in Example 2, except that the negative electrode C was used instead of the negative electrode A.
  • Example 21 A coin-type nonaqueous electrolyte secondary battery of Example 21 was produced in the same manner as in Example 3, except that the negative electrode C was used instead of the negative electrode A.
  • Example 25 A coin-type nonaqueous electrolyte secondary battery of Example 25 was made in the same manner as in Example 7, except that the negative electrode C was used instead of the negative electrode A.
  • Example 28 A coin-type nonaqueous electrolyte secondary battery of Example 28 was produced in the same manner as in Example 10, except that the negative electrode C was used instead of the negative electrode A.
  • Example 33 A coin-type nonaqueous electrolyte secondary battery of Example 33 was made in the same manner as Example 15 except that the negative electrode C was used instead of the negative electrode A.
  • CMCNa sodium carboxymethyl cellulose
  • Example 34 A coin-type nonaqueous electrolyte secondary battery of Example 34 was produced in the same manner as in Example 2, except that the negative electrode A was used instead of the negative electrode A.
  • Example 35 A coin-type nonaqueous electrolyte secondary battery of Example 35 was produced in the same manner as in Example 5, except that the negative electrode D was used instead of the negative electrode A.
  • Example 36 A coin-type nonaqueous electrolyte secondary battery of Example 36 was made in the same manner as in Example 8, except that the negative electrode A was used instead of the negative electrode A.
  • the nonaqueous electrolyte secondary batteries of Examples 1 to 36 have higher capacity retention ratios and superior cycle characteristics than the nonaqueous electrolyte secondary batteries of Comparative Examples 1 to 12.
  • the non-aqueous electrolyte secondary battery had a high capacity retention rate even when the charge / discharge rate was high and had excellent rate characteristics.

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Abstract

La présente invention concerne une batterie secondaire à électrolyte non aqueux comprenant : une électrode positive ; une électrode négative contenant des atomes de silicium ; et un électrolyte non aqueux qui contient un sel de lithium et un composé représenté par la formule générale (1) (dans la formule, R1-R3 représentent chacun indépendamment un groupe hydrocarboné ayant de 1 à 10 atomes de carbone, R4 représente un groupe hydrocarboné à valence n ayant de 1 à 10 atomes de carbone, un groupe à valence n dans lequel un groupe hydrocarboné ayant de 1 à 10 atomes de carbone est couplé à un atome d'oxygène ou à un atome de soufre, ou un groupe hétérocyclique à valence n qui a de 3 à 6 atomes de carbone et qui comprend un atome d'oxygène ou un atome de soufre, et n représente un nombre entier de 1 à 6).
PCT/JP2019/026995 2018-07-19 2019-07-08 Batterie secondaire à électrolyte non aqueux WO2020017378A1 (fr)

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CN115149104A (zh) * 2022-08-16 2022-10-04 昆明理工大学 一种含添加剂的电池电解液及其在锂硫电池中的应用

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CN115149104A (zh) * 2022-08-16 2022-10-04 昆明理工大学 一种含添加剂的电池电解液及其在锂硫电池中的应用
CN115149104B (zh) * 2022-08-16 2024-02-27 昆明理工大学 一种含添加剂的电池电解液及其在锂硫电池中的应用

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