WO2017013827A1 - Accumulateur lithium-ion - Google Patents

Accumulateur lithium-ion Download PDF

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WO2017013827A1
WO2017013827A1 PCT/JP2016/002784 JP2016002784W WO2017013827A1 WO 2017013827 A1 WO2017013827 A1 WO 2017013827A1 JP 2016002784 W JP2016002784 W JP 2016002784W WO 2017013827 A1 WO2017013827 A1 WO 2017013827A1
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active material
negative electrode
electrode active
positive electrode
ion secondary
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Japanese (ja)
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達哉 江口
三好　学
斉藤　淳志
孝二 岩田
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Toyota Industries Corp
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Toyota Industries Corp
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • 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
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/134—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
    • H01M4/38—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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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 lithium ion secondary battery.
  • non-aqueous electrolyte secondary batteries are recognized as essential for portable devices such as mobile phones and laptop computers.
  • non-aqueous electrolyte secondary batteries lithium ion secondary batteries are widely used because of their small size and large capacity. Lithium ion secondary batteries are also used in aircraft and automobiles.
  • lithium ion secondary batteries As negative electrode active materials for lithium ion secondary batteries, silicon-based materials such as silicon, silicon alloys, and silicon oxides having charge / discharge capacities far exceeding the theoretical capacity of carbon materials have been studied.
  • Patent Document 1 International Publication No. 2014/080608
  • CaSi 2 and an acid are reacted to synthesize a layered silicon compound containing layered polysilane as a main component, and the layered silicon compound is heated at 300 ° C. or higher.
  • a silicon material is manufactured by heating, and a lithium ion secondary battery including the silicon material as an active material.
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-157854
  • Japanese Patent Laid-Open No. 2003-157854 describes a lithium ion secondary battery that did not ignite even when a nail penetration test was performed.
  • the electrode is divided into sheets having a specific shape.
  • the area and shape of the sheet into which the electrode is divided and the distance between the positive electrode current collector and the negative electrode current collector are defined by a certain relational expression, and the lithium ion secondary battery Multiple restrictions were imposed on the components.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2008-198591 discloses lithium ions in which an insulating member is interspersed at the interface between the current collector and the electrode mixture layer to increase the resistance between the positive electrode and the negative electrode. According to the secondary battery, it is disclosed that smoke does not occur even when a nail penetration test is performed. However, with the technique disclosed in Patent Document 3, there is a concern that the resistance as a battery increases and the output characteristics deteriorate.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a lithium ion secondary battery having high safety when an internal short circuit occurs.
  • a positive electrode active material containing a lithium nickel cobalt manganese composite oxide and a lithium iron phosphate compound and a silicon material having a structure in which a plate-like silicon body is laminated in the thickness direction It has been found that a lithium ion secondary battery having a negative electrode active material containing can withstand a nail penetration test and has high safety even during an internal short circuit.
  • the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte
  • the positive electrode has a positive electrode active material layer including a positive electrode active material
  • the positive electrode active material is represented by the following formula ( 1) comprising a lithium nickel cobalt manganese composite oxide represented by the following formula and a lithium iron phosphate compound represented by the following formula (2), Li a Ni b Co c Mn (1-bcd) M 1 d O (2-e) (1)
  • M 1 represents at least one selected from the group consisting of Mg, Al, B, Ti, V, Cr, Fe, Cu, Zn, Zr, Mo, Sn, Ca, Sr and W.
  • A, b, c, d and e are 0.8 ⁇ a ⁇ 1.2, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.5, 0 ⁇ d ⁇ 0.5, b + c + d ⁇ 1 , -0.1 ⁇ e ⁇ 0.2.)
  • Li p Fe q M 2 (1-q) PO 4 (2) (In the formula (2), M 2 is at least one of the group consisting of Co, Mn, Ni, Mg, Al, B, Ti, V, Nb, Cu, Zn, Mo, Ca, Sr, W and Zr.
  • the negative electrode has a negative electrode active material layer containing a negative electrode active material, and the negative electrode active material contains a silicon material having a structure in which plate-like silicon bodies are laminated in the thickness direction.
  • the density of the positive electrode active material layer is preferably 2.5 g / cm 3 or more and 3.5 g / cm 3 or less, and the density of the negative electrode active material layer is preferably 0.5 g / cm 3 or more and 2 g / cm 3 or less. .
  • the content of the silicon material is preferably 30 parts by mass or more and 80 parts by mass or less when the negative electrode active material layer is 100 parts by mass.
  • the content of the lithium nickel cobalt manganese composite oxide is preferably 50 parts by mass or more and 80 parts by mass or less when the positive electrode active material layer is 100 parts by mass, and the content of the lithium iron phosphate compound is positive electrode When the active material layer is 100 parts by mass, it is preferably 20 parts by mass or more and 40 parts by mass or less.
  • the separator preferably includes a porous film made of synthetic resin.
  • the non-aqueous electrolyte includes an electrolyte salt and a non-aqueous solvent
  • the electrolyte salt includes lithium hexafluorophosphate
  • the non-aqueous solvent includes fluoroethylene carbonate, ethylene carbonate, ethyl methyl carbonate, and dimethyl carbonate. preferable.
  • the synergistic effect by using the specific negative electrode active material and the specific positive electrode active material a good result is obtained in the nail penetration test, and an excessive temperature rise at the time of short circuit is achieved. Can be suppressed.
  • FIG. 6 is a graph showing the relationship between the cell surface temperature, which is the nail penetration test result of the laminated lithium ion secondary batteries of Examples 1 to 7, and the mass part of the silicon material of each negative electrode.
  • the numerical range “a to b” described in this specification includes the lower limit “a” and the upper limit “b”.
  • the numerical range can be configured by arbitrarily combining these upper limit value and lower limit value and the numerical values listed in the examples.
  • numerical values arbitrarily selected from the numerical value range can be used as upper and lower numerical values.
  • the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte.
  • the positive electrode has a positive electrode active material layer containing a positive electrode active material.
  • the positive electrode active material layer is disposed on the surface of the current collector.
  • a current collector refers to a chemically inert electronic high conductor that keeps a current flowing through an electrode during discharge or charging of a lithium ion secondary battery.
  • the current collector material include metal materials such as stainless steel, titanium, nickel, aluminum, and copper, or conductive resins.
  • the material for the current collector is preferably aluminum or copper.
  • the current collector can take the form of a foil, a sheet, a film, a linear shape, a rod shape, a mesh, or the like.
  • a metal foil such as a copper foil, a nickel foil, an aluminum foil, or a stainless steel foil can be suitably used.
  • the thickness of the current collector is preferably 10 ⁇ m to 50 ⁇ m.
  • the thickness of the current collector is particularly preferably 12 ⁇ m to 30 ⁇ m from the viewpoint of increasing battery capacity while maintaining high strength in the current collector.
  • the positive electrode active material layer has a positive electrode active material.
  • the positive electrode active material layer may include a binder and a conductive additive as necessary.
  • the positive electrode active material contains a lithium nickel cobalt manganese composite oxide represented by the following formula (1) and a lithium iron phosphate compound represented by the following formula (2).
  • M 1 represents at least one selected from the group consisting of Mg, Al, B, Ti, V, Cr, Fe, Cu, Zn, Zr, Mo, Sn, Ca, Sr and W.
  • A, b, c, d and e are 0.8 ⁇ a ⁇ 1.2, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.5, 0 ⁇ d ⁇ 0.5, b + c + d ⁇ 1 , -0.1 ⁇ e ⁇ 0.2.
  • M 2 is at least one of the group consisting of Co, Mn, Ni, Mg, Al, B, Ti, V, Nb, Cu, Zn, Mo, Ca, Sr, W and Zr.
  • P is a value in the range of 0.9 ⁇ p ⁇ 1.1
  • q is a value in the range of 0 ⁇ q ⁇ 1)
  • lithium nickel cobalt manganese composite oxide represented by the formula (1) examples include LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0. .5 Co 0.2 Mn 0.3 O 2 and the like.
  • the lithium iron phosphate compound represented by the formula (2) include LiFePO 4.
  • the lithium ion secondary battery can obtain a higher energy density.
  • the lithium ion secondary battery is expected to be highly safe because the positive electrode active material contains a lithium iron phosphate compound represented by the formula (2).
  • the lithium iron phosphate compound represented by the formula (2) has an olivine type structure.
  • the olivine structure is based on hexagonal close-packing of oxygen, and phosphorus is located at the tetrahedral site and lithium and iron are located at the octahedral site.
  • a lithium iron phosphate compound having an olivine structure is less likely to release oxygen even at high temperatures because phosphorus and oxygen are covalently bonded.
  • the safety of the lithium ion secondary battery can be improved by using a lithium iron phosphate compound having an olivine type structure as the positive electrode active material of the lithium ion secondary battery.
  • the lithium iron phosphate compound represented by the formula (2) is preferably a carbon-coated surface.
  • the lithium ion secondary battery is higher. Energy density can be obtained and safety can be improved.
  • the content of the lithium nickel cobalt manganese composite oxide is preferably 50 parts by mass or more and 80 parts by mass or less, and 58 parts by mass or more and 78 parts by mass when the positive electrode active material layer is 100 parts by mass. More preferably, it is 65 parts by mass or more and 75 parts by mass or less, and the content of the lithium iron phosphate compound is 20 parts by mass when the positive electrode active material layer is 100 parts by mass. It is preferably no less than 40 parts by mass and no greater than 40 parts by mass, more preferably no less than 22 parts by mass and no greater than 35 parts by mass, and even more preferably no less than 24 parts by mass and no greater than 30 parts by mass.
  • the positive electrode active material layer may further include other lithium-containing oxides, other metal oxides, and other positive electrode active materials.
  • the positive electrode active material is preferably in the form of a powder having an average particle diameter D 50 of 1 ⁇ m to 20 ⁇ m.
  • the average particle diameter D 50 of the positive electrode active material is small, the specific surface area of the positive electrode active material is increased. Therefore, the average particle diameter D 50 of the positive electrode active material is too small, will be the reaction area of the cathode active material and an electrolytic solution is excessively increased, resulting in promoted decomposition of the electrolytic solution, the lithium ion secondary The cycle characteristics of the secondary battery may be deteriorated.
  • the average particle diameter D 50 of the positive electrode active material is too large, resistance of the lithium ion secondary battery increases, there is a possibility that the output characteristics of the lithium ion secondary battery decreases.
  • the average particle diameter D 50 refers to the particle size cumulative value of the volume distribution in the particle size distribution measurement by laser diffraction method is equivalent to 50%. That is, the average particle diameter D 50 means the median size measured by volume.
  • the binder plays a role of connecting the positive electrode active material to the current collector.
  • the binder for example, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer (abbreviation FEP), fluorine-containing resin such as fluoro rubber, polypropylene, thermoplastic resin such as polyethylene, polyimide, Examples thereof include imide resins such as polyamide imide, acrylic resins such as poly (meth) acrylic acid, alkoxysilyl group-containing resins, styrene / butadiene rubber, carboxymethyl cellulose, polyethylene glycol, and polyacrylonitrile.
  • Positive electrode active material: binding agent 1: 0.005 to 1: 0.2 is more preferable, and 1: 0.01 to 1: 0.15 is further preferable. If the amount of the binder is too small, the moldability of the electrode may be lowered, and if the amount of the binder is too large, the energy density of the electrode may be lowered.
  • the conductive additive is added to the positive electrode active material layer as necessary in order to increase the conductivity of the electrode.
  • Carbon black, graphite, acetylene black (abbreviated as AB), ketjen black (registered trademark) (abbreviated as KB), vapor-grown carbon fiber (abbreviated as VGCF), etc., which are carbonaceous fine particles, are used alone or in combination as conductive aids. These can be used in combination.
  • the amount of the conductive aid used is not particularly limited, but can be, for example, about 1 to 30 parts by mass with respect to 100 parts by mass of the active material contained in the electrode.
  • a positive electrode active material layer-forming composition containing a positive electrode active material, a binder, and, if necessary, a conductive additive is prepared.
  • An appropriate solvent may be added to the product to form a paste, which may be applied to the surface of the current collector and then dried.
  • a coating method of the composition for forming a positive electrode active material layer conventionally known methods such as a roll coating method, a dip coating method, a doctor blade method, a spray coating method, a curtain coating method, a lip coating method, a comma coating method, and a die coating method are known. A method may be used.
  • solvent for adjusting the viscosity water, N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone and the like can be used.
  • the density of the positive electrode active material layer is preferably 2.5 g / cm 3 or more and 3.5 g / cm 3 or less, more preferably 2.6 g / cm 3 or more and 3.2 g / cm 3 or less. particularly preferably .8g / cm 3 or more 3.0 g / cm 3 or less.
  • the negative electrode has a negative electrode active material layer containing a negative electrode active material.
  • the negative electrode active material layer is disposed on the surface of the current collector.
  • the current collector is the same as that described for the positive electrode.
  • the negative electrode active material layer has a negative electrode active material.
  • the negative electrode active material layer may contain a binder and a conductive additive as necessary.
  • the binder and the conductive assistant are the same as those described for the positive electrode.
  • the negative electrode active material includes a silicon material having a structure in which plate-like silicon bodies are laminated in the thickness direction.
  • the structure of a silicon material having a structure in which plate-like silicon bodies are laminated in the thickness direction can be confirmed by observation with a scanning electron microscope or the like.
  • the plate-like silicon body has a thickness in the range of 10 nm to 100 nm for efficient insertion and removal of lithium ions. Are preferred, and those in the range of 20 nm to 50 nm are more preferred.
  • the length of the plate-like silicon body in the major axis direction is preferably in the range of 0.1 ⁇ m to 50 ⁇ m.
  • the plate-like silicon body preferably has a (length in the long axis direction) / (thickness) range of 2 to 1000.
  • the silicon material may be pulverized or classified to form particles having a certain particle size distribution.
  • D 50 can be exemplified within a range of 1 ⁇ m to 30 ⁇ m when measured by a general laser diffraction type particle size distribution measuring apparatus.
  • the silicon crystallite size is preferably nano-sized. Specifically, the silicon crystallite size is preferably in the range of 0.5 nm to 300 nm, more preferably in the range of 1 nm to 100 nm, further preferably in the range of 1 nm to 50 nm, and particularly in the range of 1 nm to 10 nm. preferable.
  • the silicon material can be manufactured by the following manufacturing process.
  • the production process includes a process of producing a layered silicon compound mainly composed of layered polysilane by reacting CaSi 2 and an acid, and a process of producing a silicon material by heating the layered silicon compound at 300 ° C. or higher.
  • CaSi 2 generally has a structure in which a Ca layer and a Si layer are laminated.
  • CaSi 2 may be synthesized by a known production method, or a commercially available one may be adopted.
  • CaSi 2 used for producing the layered silicon compound is preferably pulverized in advance.
  • Acids include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, methanesulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluoroarsenic acid, fluoro Examples include antimonic acid, hexafluorosilicic acid, hexafluorogermanic acid, hexafluorotin (IV) acid, trifluoroacetic acid, hexafluorotitanic acid, hexafluorozirconic acid, trifluoromethanesulfonic acid, and fluorosulfonic acid. These acids may be used alone or in combination.
  • the acid is used as an aqueous solution from the viewpoint of easy work and safety, and removal of by-products.
  • Acid may be used in an amount capable of providing 2 or more equivalents of protons relative CaSi 2. Therefore, if a monovalent acid, the acid may be used in two moles or more relative to CaSi 2 1 mol.
  • the reaction conditions are preferably a reduced pressure condition such as vacuum or an inert gas atmosphere, and a temperature condition of room temperature or lower such as an ice bath. What is necessary is just to set reaction time suitably.
  • Si 6 H 6 which is polysilane corresponds to an ideal layered silicon compound. This reaction can also be considered to form a Si—H bond while Ca in the layered CaSi 2 is substituted with 2H.
  • the layered silicon compound has a layer shape because the basic skeleton of the Si layer in the raw material CaSi 2 is maintained.
  • the acid is preferably used as an aqueous solution in the reaction step of reacting CaSi 2 with the acid.
  • Si 6 H 6 can react with water, the layered silicon compound is rarely obtained only with a compound of Si 6 H 6 , and contains an element derived from oxygen or an acid.
  • ⁇ Heat is released from the layered silicon compound at 300 ° C. or higher to obtain a silicon material.
  • the process of heating the layered silicon compound at 300 ° C. or higher is sometimes referred to as a silicon material manufacturing process.
  • the silicon material manufacturing process is shown as an ideal reaction formula as follows.
  • the layered silicon compound actually used in the silicon material manufacturing process contains oxygen and acid-derived elements and also contains inevitable impurities
  • the actually obtained silicon material also contains oxygen and acid-derived elements. Further, inevitable impurities are also contained.
  • the molar amount of silicon when the molar amount of silicon is 100, the molar amount of oxygen element is preferably 50 or less, and particularly preferably 40 or less.
  • the molar amount of silicon when the molar amount of silicon is 100, the molar amount of the acid-derived element is preferably 8 or less, and particularly preferably 5 or less.
  • the silicon material production process is preferably performed in a non-oxidizing atmosphere having a lower oxygen content than in normal air.
  • the non-oxidizing atmosphere include a reduced pressure atmosphere including a vacuum and an inert gas atmosphere.
  • the heating temperature is preferably in the range of 350 ° C. to 1200 ° C., more preferably in the range of 400 ° C. to 1200 ° C. If the heating temperature is too low, hydrogen may not be released sufficiently, while if the heating temperature is too high, energy is wasted. What is necessary is just to set a heating time suitably according to heating temperature, and it is also preferable to determine a heating time, measuring the quantity of hydrogen etc. which escapes out of a reaction system.
  • the ratio of amorphous silicon and silicon crystallites contained in the silicon material to be manufactured, and the size of the silicon crystallites can also be adjusted, and further manufactured.
  • the shape and size of a nano-level layer containing amorphous silicon and silicon crystallites contained in the silicon material can also be prepared.
  • the silicon material covered with carbon may be only amorphous carbon, may be crystalline carbon, or may be a mixture of amorphous carbon and crystalline carbon.
  • the method for coating the silicon material with carbon is not particularly limited.
  • Carbon coating methods include mixing carbon powder and silicon material (for example, mechanical milling), heating the mixture obtained from the composite of resin and silicon material, and carbonizing the resin, and non-oxidizing silicon material. Examples thereof include a method (thermal CVD method) in which the organic gas is carbonized by being brought into contact with the organic gas in an atmosphere and heated.
  • the content of the silicon material in the negative electrode active material layer is preferably 30 parts by mass or more and 85 parts by mass or less, and preferably 40 parts by mass or more and 80 parts by mass or less when the negative electrode active material layer is 100 parts by mass. Is more preferable, and it is further more preferable that it is 50 to 75 mass parts.
  • the negative electrode active material layer may contain other negative electrode active materials in addition to the silicon material.
  • a carbon-based material capable of inserting and extracting lithium, an element capable of being alloyed with lithium, a compound having an element capable of being alloyed with lithium, a polymer material, or the like can be used.
  • the carbon-based material examples include graphite, non-graphitizable carbon, cokes, graphites, glassy carbons, organic polymer compound fired bodies, carbon fibers, activated carbon, and carbon blacks.
  • the organic polymer compound fired body refers to a material obtained by firing and carbonizing a polymer material such as phenols and furans at an appropriate temperature.
  • Elements that can be alloyed with lithium are Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si, Ge, Sn. , Pb, Sb, Bi.
  • Examples of the compound having an element that can be alloyed with lithium include ZnLiAl, AlSb, SiB 4 , SiB 6 , Mg 2 Si, Mg 2 Sn, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , and CaSi. 2, CrSi 2, Cu 5 Si , FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2, ZnSi 2, SiC, Si 3 N 4, Si 2 N 2 O, SiO v (0 ⁇ v ⁇ 2), SnO w (0 ⁇ w ⁇ 2), SnSiO 3 , LiSiO or LiSnO can be used.
  • polyacetylene polypyrrole, or the like can be used as the polymer material.
  • the other negative electrode active material is preferably a carbon-based material.
  • the negative electrode active material is preferably in powder form.
  • the average particle diameter D 50 of the negative electrode active material is preferably 0.5 ⁇ m or more and 30 ⁇ m or less, and more preferably 1 ⁇ m or more and 20 ⁇ m or less.
  • the average particle diameter D 50 of the negative electrode active material is too small, the specific surface area of the powder of the negative electrode active material is increased, it increases the contact area of the powder of the anode active material and the electrolyte solution, proceed decomposition of the electrolyte solution Therefore, the cycle characteristics of the lithium ion secondary battery may be deteriorated.
  • the average particle diameter D 50 of the negative electrode active material is too large, conductivity of the whole electrode becomes uneven, charging and discharging characteristics may deteriorate.
  • the negative electrode active material layer can be disposed on the surface of the current collector in the same manner as the positive electrode active material layer is disposed on the surface of the current collector.
  • the density of the negative electrode active material layer is preferably 0.5 g / cm 3 or more and 2 g / cm 3 or less, more preferably 0.8 g / cm 3 or more and 1.5 g / cm 3 or less, and 1.0 g / Cm 3 or more and 1.3 g / cm 3 or less is particularly preferable.
  • the separator separates the positive electrode and the negative electrode and allows lithium ions to pass while preventing a short circuit of current due to contact between the two electrodes.
  • the separator include a porous film made of synthetic resin such as polytetrafluoroethylene, polypropylene, polyethylene, polyester, and polyamide, or a porous film made of ceramics.
  • the separator preferably includes a porous film made of a synthetic resin so that it can easily follow expansion and contraction due to charging and discharging of the negative electrode including the silicon material.
  • the separator made of synthetic resin may have a single layer structure using a single synthetic resin or a laminated structure in which a plurality of synthetic resin layers are stacked.
  • the thickness of the separator is not particularly limited, but is preferably in the range of 5 ⁇ m to 100 ⁇ m, more preferably in the range of 10 ⁇ m to 50 ⁇ m, and particularly preferably in the range of 15 ⁇ m to 30 ⁇ m.
  • Non-aqueous electrolyte The nonaqueous electrolytic solution contains a nonaqueous solvent and an electrolyte dissolved in the nonaqueous solvent.
  • non-aqueous solvent examples include cyclic esters, chain esters, and ethers.
  • cyclic esters include ethylene carbonate, propylene carbonate, butylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone, and gamma valerolactone.
  • chain esters include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, ethyl methyl carbonate, propionic acid alkyl ester, malonic acid dialkyl ester, and acetic acid alkyl ester.
  • ethers examples include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane.
  • the non-aqueous solvent a compound in which part or all of hydrogen in the chemical structure of the specific non-aqueous solvent is substituted with fluorine may be employed.
  • the compound in which part or all of hydrogen in the chemical structure of the non-aqueous solvent is fluorine-substituted include, for example, fluoroethylene carbonate and difluoroethylene carbonate.
  • a lithium salt such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (FSO 2 ) 2 is used.
  • a lithium salt such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (FSO 2 ) 2 is used.
  • non-aqueous electrolyte for example, a lithium salt such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (FSO 2 ) 2 is added to a solvent such as ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate.
  • a solution dissolved at a concentration of about 5 mol / l to 1.7 mol / l can be used.
  • a separator is sandwiched between the positive electrode and the negative electrode to form an electrode body.
  • the electrode body may be any of a stacked type in which a positive electrode, a separator and a negative electrode are stacked, or a wound type in which a positive electrode, a separator and a negative electrode are sandwiched.
  • a non-aqueous electrolyte is added to the electrode body and lithium is added. It is preferable to use an ion secondary battery.
  • the lithium ion secondary battery of this invention should just be charged / discharged in the voltage range suitable for the kind of active material contained in an electrode.
  • the shape of the lithium ion secondary battery is not particularly limited, and various shapes such as a cylindrical shape, a square shape, a coin shape, and a laminate shape can be adopted.
  • the lithium ion secondary battery can be mounted on a vehicle. Since the lithium ion secondary battery has high safety, a vehicle equipped with the lithium ion secondary battery has high safety.
  • the vehicle may be a vehicle that uses electric energy from a battery as a whole or a part of a power source.
  • a vehicle that uses electric energy from a battery as a whole or a part of a power source.
  • an electric vehicle a hybrid vehicle, a plug-in hybrid vehicle, a hybrid railway vehicle, an electric forklift, an electric wheelchair, and an electric assist.
  • Bicycles and electric motorcycles are examples.
  • LiNi 0.5 Co 0.2 Mn 0.3 O 2 having an average particle diameter D 50 of 6 ⁇ m as a positive electrode active material
  • LiFePO 4 having an average particle diameter D 50 of 1.5 ⁇ m having a carbon coating on the surface as a positive electrode active material
  • Acetylene black as a conductive additive and polyvinylidene fluoride (hereinafter referred to as PVDF) as a binder were mixed in a ratio of 67 parts by mass, 27 parts by mass, 3 parts by mass, and 3 parts by mass, respectively.
  • NMP N-methyl-2-pyrrolidone
  • An aluminum foil having a thickness of 15 ⁇ m was prepared as a current collector.
  • the positive electrode active material layer slurry was placed on the current collector, and the positive electrode active material layer slurry was applied in a film form using a comma coater.
  • the current collector coated with the positive electrode active material layer slurry was dried at 90 ° C. for 5 minutes and then dried at 120 ° C. for 5 minutes to volatilize and remove NMP. Thereafter, the current collector and the coated material on the current collector were firmly bonded by a roll press. At this time, the basis weight of the positive electrode active material layer was set to 27.0 mg / cm 2 .
  • the basis weight of the positive electrode active material layer was calculated from the equation: mass of positive electrode active material layer (g) ⁇ area of positive electrode active material layer (cm 2 ).
  • the bonded product was heated in a vacuum dryer at 120 ° C. for 6 hours.
  • the bonded product after heating was cut into a predetermined shape (rectangular shape of 40 mm ⁇ 80 mm) to obtain a positive electrode A.
  • the thickness of the positive electrode active material layer of the positive electrode A was about 90 ⁇ m.
  • the density of the positive electrode active material layer of the positive electrode A was 2.9 g / cm 3 .
  • (Positive electrode B) 94 parts by mass of LiNi 0.5 Co 0.2 Mn 0.3 O 2 having an average particle diameter D 50 of 6 ⁇ m as a positive electrode active material, acetylene black as a conductive additive, and PVDF as a binder,
  • a positive electrode B was prepared in the same manner as the positive electrode A, except that the mixture was mixed at a ratio of 3 parts by mass and the mixture was dispersed in an appropriate amount of NMP to prepare a positive electrode active material layer slurry.
  • the thickness of the positive electrode active material layer of the positive electrode B was about 80 ⁇ m.
  • the density of the positive electrode active material layer of the positive electrode B was 2.9 g / cm 3 .
  • acetylene black as a conductive assistant and PVDF as a binder are mixed in a ratio of 69 parts by mass, 25 parts by mass, 3 parts by mass, and 3 parts by mass, respectively, and this mixture is dispersed in an appropriate amount of NMP.
  • a positive electrode C was prepared in the same manner as the positive electrode A, except that the positive electrode active material layer slurry was prepared.
  • the thickness of the positive electrode active material layer of the positive electrode C was about 89 ⁇ m.
  • the density of the positive electrode active material layer of the positive electrode C was 2.9 g / cm 3 .
  • a silicon material coated with carbon was prepared as follows.
  • a mixed solution of 7 ml of an aqueous HF solution having a concentration of 46% by mass and 56 ml of an aqueous HCl solution having a concentration of 36% by mass was brought to 0 ° C. in an ice bath, and 3.3 g of CaSi 2 was added thereto in an argon gas stream. Stir. After confirming the completion of foaming, the mixed solution was warmed to room temperature, stirred for another 2 hours at room temperature, then added with 20 ml of distilled water, and further stirred for 10 minutes. At this time, yellow powder floated.
  • the obtained mixed solution was filtered, and the obtained residue was washed with 10 ml of distilled water and then with 10 ml of ethanol. The residue after washing was vacuum dried to obtain 2.5 g of layered polysilane.
  • the obtained silicon material was put into a rotary kiln type reactor and subjected to a carbonization process by thermal CVD under a condition of 850 ° C. and a residence time of 5 minutes under a flow of propane gas to obtain a silicon material coated with carbon. .
  • a carbonization process by thermal CVD under a condition of 850 ° C. and a residence time of 5 minutes under a flow of propane gas to obtain a silicon material coated with carbon.
  • the rotation speed of the reactor was 1 rpm.
  • the average particle diameter D 50 of the silicon material coated with this carbon was 5 [mu] m.
  • NiO having an average particle diameter D 50 of 4 ⁇ m and natural graphite having an average particle diameter D 50 of 15 ⁇ m were prepared.
  • a polyamide-imide resin was prepared as a binder resin.
  • Acetylene black was prepared as a conductive aid.
  • An appropriate amount of NMP was added as a solvent to the above mixture to prepare a negative electrode active material layer slurry.
  • a 20 ⁇ m copper foil was prepared as a negative electrode current collector.
  • the said slurry for negative electrode active material layers was apply
  • the copper foil coated with the negative electrode active material layer slurry was dried at 80 ° C. for 5 minutes to volatilize and remove NMP. Thereafter, the current collector and the coated material on the current collector were firmly bonded by a roll press.
  • the basis weight of the negative electrode active material layer was set to 7.5 mg / cm 2 .
  • the basis weight of the negative electrode active material layer was calculated from the equation: mass of negative electrode active material layer (g) ⁇ area of negative electrode active material layer (cm 2 ).
  • the joined product was heated in a vacuum dryer at 200 ° C. for 2 hours, and then cut into a predetermined shape (rectangular shape having a negative electrode active material layer area of 44 mm ⁇ 84 mm) to form a negative electrode A.
  • the thickness of the negative electrode active material layer of the negative electrode A was about 47 ⁇ m.
  • the density of the negative electrode active material layer of the negative electrode A was 1.6 g / cm 3 .
  • a negative electrode C was produced in the same manner as the negative electrode A, except that this negative electrode active material layer slurry was used and the basis weight of the negative electrode active material layer was 5.5 mg / cm 2 .
  • the thickness of the negative electrode active material layer of the negative electrode C was about 50 ⁇ m.
  • the density of the negative electrode active material layer of the negative electrode C was 1.1 g / cm 3 .
  • a negative electrode D was produced in the same manner as the negative electrode C, except that the density of the negative electrode active material layer was 1.2 g / cm 3 .
  • the thickness of the negative electrode active material layer of the negative electrode D was about 46 ⁇ m.
  • the basis weight of the negative electrode active material layer of the negative electrode D was 5.5 mg / cm 2 .
  • a negative electrode F was produced in the same manner as the negative electrode E, except that the density of the negative electrode active material layer was 1.2 g / cm 3 .
  • the thickness of the negative electrode active material layer of the negative electrode F was about 41 ⁇ m.
  • the basis weight of the negative electrode active material layer of the negative electrode F was 4.9 mg / cm 2 .
  • the negative electrode active material used in the negative electrode B, the conductive auxiliary agent used in the negative electrode A, and the binder resin are coated with carbon.
  • Silicon material: graphite: conductive auxiliary agent: binder resin 70: 15: 5: 10 Mixed.
  • An appropriate amount of NMP was added as a solvent to the above mixture to prepare a negative electrode active material layer slurry.
  • a negative electrode G was produced in the same manner as the negative electrode A, except that the basis weight of the negative electrode active material layer was 4.0 mg / cm 2 .
  • the thickness of the negative electrode active material layer of the negative electrode G was about 36 ⁇ m. Further, the density of the negative electrode active material layer of the negative electrode G was 1.1 g / cm 3 .
  • a negative electrode H was produced in the same manner as the negative electrode G, except that the density of the negative electrode active material layer was 1.2 g / cm 3 .
  • the thickness of the negative electrode active material layer of the negative electrode H was about 33 ⁇ m.
  • the basis weight of the negative electrode active material layer of the negative electrode H was 4.0 mg / cm 2 .
  • a negative electrode I was produced in the same manner as the negative electrode F, except that this negative electrode active material layer slurry was used and the density of the negative electrode active material layer was 1.1 g / cm 3 .
  • the thickness of the negative electrode active material layer of the negative electrode I was about 52 ⁇ m.
  • the basis weight of the negative electrode active material layer was 5.7 mg / cm 2 .
  • Example 1 The laminated lithium ion secondary battery of Example 1 was produced as follows.
  • a laminate type lithium ion secondary battery was manufactured using 30 positive electrodes A and 31 negative electrodes B. Specifically, a rectangular sheet (48 mm ⁇ 88 mm, thickness 25 ⁇ m) made of a porous polyethylene film as a separator was sandwiched between each positive electrode and each negative electrode, and laminated to form an electrode plate group. The electrode plate group was covered with a set of two laminated films, and the three sides were sealed, and then an electrolyte solution was injected into the bag-like laminated film. The amount of electrolyte injected was 3.4 ml / Ah with respect to the battery capacity.
  • FEC fluoroethylene carbonate
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • the positive electrode and the negative electrode have a tab portion that can be electrically connected to the outside, and a part of the tab portion extends to the outside of the laminated lithium ion secondary battery.
  • the laminated lithium ion secondary battery of Example 1 was produced through the above steps.
  • Example 2 A laminated lithium ion secondary battery of Example 2 was produced in the same manner as in Example 1 except that the negative electrode C was used instead of the negative electrode B in Example 1.
  • Example 3 A laminated lithium ion secondary battery of Example 3 was produced in the same manner as in Example 1 except that the negative electrode D was used instead of the negative electrode B in Example 1.
  • Example 4 A laminated lithium ion secondary battery of Example 4 was produced in the same manner as in Example 1 except that the negative electrode E was used instead of the negative electrode B in Example 1.
  • Example 5 A laminated lithium ion secondary battery of Example 5 was produced in the same manner as in Example 1 except that the negative electrode F was used instead of the negative electrode B in Example 1.
  • Example 6 A laminated lithium ion secondary battery of Example 6 was produced in the same manner as in Example 1 except that the negative electrode G was used instead of the negative electrode B in Example 1.
  • Example 7 A laminated lithium ion secondary battery of Example 7 was produced in the same manner as in Example 1 except that the negative electrode H was used instead of the negative electrode B in Example 1.
  • Example 8 The laminated lithium ion secondary battery of Example 8 was the same as Example 5 except that the amount of electrolyte injected in Example 5 was 1.7 ml / Ah with respect to the battery capacity. Produced.
  • Example 9 A laminated lithium ion secondary battery of Example 9 was produced in the same manner as in Example 5 except that the positive electrode C was used instead of the positive electrode A in Example 5.
  • Example 10 A laminated lithium ion secondary battery of Example 10 was produced in the same manner as in Example 9, except that the negative electrode I was used instead of the negative electrode F in Example 9.
  • Comparative Example 1 A laminated lithium ion secondary battery of Comparative Example 1 was prepared in the same manner as in Example 1 except that the positive electrode B was used instead of the positive electrode A in Example 1, and the negative electrode F was used instead of the negative electrode B in Example 1. Produced.
  • Comparative Example 2 Comparative Example as in Example 1, except that the negative electrode A was used instead of the negative electrode B in Example 1, and the amount of electrolyte injected was 4.1 ml / Ah with respect to the battery capacity. 2 laminate type lithium ion secondary battery was produced.
  • Comparative Example 3 A laminate type lithium ion secondary battery of Comparative Example 3 was produced in the same manner as Comparative Example 2, except that the amount of electrolyte injected was 2.8 ml / Ah with respect to the battery capacity.
  • each laminated lithium ion secondary battery was charged with a constant current (CC) until it reached 4.5 V at a current value of 3.0 A. Thereafter, charging was continued so as to maintain the voltage within 4.5 V ⁇ 0.02 V, and the charging was stopped when the total charging time reached 5 hours.
  • the capacity of each laminated lithium ion secondary battery is 7.5 Ah for the laminated lithium ion secondary batteries of Examples 1 to 10, and 7.5 Ah for the laminated lithium ion secondary battery of Comparative Example 1.
  • the laminate type lithium ion secondary batteries of Comparative Examples 2 and 3 were 7.0 Ah.
  • Each laminated lithium ion secondary battery subjected to the above-described charging treatment was placed on a restraining plate having a hole with a diameter of 20 mm.
  • a restraint plate was placed on a press machine with a nail attached to the top. The nail was moved from the top to the bottom at a speed of 20 mm / sec until the nail penetrated the laminated lithium ion secondary battery on the restraint plate and the tip of the nail was positioned inside the hole of the restraint plate.
  • a temperature measuring device capable of measuring the surface temperature was attached to the laminate type lithium ion secondary battery.
  • the nail was made of stainless steel (S45C defined by JIS G 4051), had a diameter of 8 mm, and a nail tip angle of 60 °.
  • the nail penetration test was performed while measuring the surface temperature of the laminated lithium ion secondary battery at room temperature and in the air. By this nail penetration test, the positive electrode and the negative electrode of the laminated lithium ion secondary battery were short-circuited.
  • the surface temperature of the laminated lithium ion secondary battery at the time of an internal short circuit was measured, and the state of the battery was observed. After the nail penetration, the surface temperature of each battery once increased and then gradually decreased.
  • Table 1 shows the cell surface temperatures observed in the nail penetration test of the laminated lithium ion secondary batteries of Examples 1 to 7 and Comparative Examples 1 and 2. As the cell surface temperature, the maximum temperature among the surface temperatures of each laminated lithium ion secondary battery is described.
  • FIG. 1 is a graph showing the relationship between the cell surface temperature, which is a nail penetration test result of the laminated lithium ion secondary batteries of Examples 1 to 7, and the mass part of the silicon material of each negative electrode.
  • a lithium ion secondary battery having a negative electrode including a silicon material and a positive electrode including NCM and LFP has an excessive increase in the cell surface temperature even when the positive electrode and the negative electrode are short-circuited by a nail penetration test. It turns out that does not happen.
  • the cell surface temperature during the nail penetration test of the laminated lithium ion secondary batteries of Examples 1 to 7 was compared, as shown in FIG. 1 and Table 1, the mass part of the silicon material in the negative electrode active material layer It was found that the greater the amount, the lower the cell surface temperature during the nail penetration test.
  • the density of the negative electrode active material layer was 1.2 g / cm 3.
  • the laminated lithium ion secondary batteries of Nos. 5 and 7 have a nail penetration test rather than the laminated type lithium ion secondary batteries of Examples 2, 4, and 6 in which the density of the negative electrode active material layer is 1.1 g / cm 3.
  • the cell surface temperature was found to be low.
  • the electrolyte solution is removed by nail penetration and the resistance increases, so that the amount of heat generation increases and the cell surface temperature rises.
  • the heat generation of the cell is suppressed by the heat of vaporization of the electrolyte. Therefore, from the viewpoint of safety, it is preferable that the amount of electrolyte contained in the laminated lithium ion secondary battery is larger. For example, 20 to 30% of the total volume of cells of a lithium ion secondary battery is preferably occupied by the electrolyte.
  • Table 2 shows the cell surface temperatures observed in the nail penetration test of the laminated lithium ion secondary batteries of Example 5, Example 8, Comparative Example 2 and Comparative Example 3.
  • the laminate type lithium ion secondary battery of Comparative Example 3 has a smaller amount of electrolyte than the laminate type lithium ion secondary battery of Comparative Example 2. Comparing the cell surface temperature during the nail penetration test of the laminate type lithium ion secondary battery of Comparative Example 2 and Comparative Example 3 in Table 2, the cell surface during the nail penetration test of the laminate type lithium ion secondary battery of Comparative Example 3 The temperature rose significantly compared to the cell surface temperature during the nail penetration test of the laminated lithium ion secondary battery of Comparative Example 2.
  • the laminate type lithium ion secondary battery of Example 8 has a smaller amount of electrolyte than the laminate type lithium ion secondary battery of Example 5, but the laminate type lithium ion of Examples 5 and 8 Comparing the cell surface temperature during the nail penetration test of the secondary battery, the laminate type lithium ion secondary battery of Example 8 and the laminate type lithium ion secondary battery of Example 5 have the cell surface temperature during the nail penetration test, There was little difference. In other words, it was found that the surface temperature of the cell during the nail penetration test does not increase excessively regardless of the amount of the electrolyte by including the silicon material in the negative electrode.
  • a lithium ion secondary battery having a negative electrode containing a silicon material and a positive electrode containing NCM and LFP has a cell surface at the time of a short circuit between the positive electrode and the negative electrode by a nail penetration test even when the amount of the electrolyte is small. It has been found that the effect that the temperature does not increase excessively is effectively exhibited.
  • Table 3 shows the cell surface temperatures observed in the nail penetration test of the laminated lithium ion secondary batteries of Example 5, Example 9, and Example 10.
  • the content ratios of NCM and LFP are different in each positive electrode.
  • the cell surface temperatures during the nail penetration test of the laminated lithium ion secondary batteries of Example 5 and Example 9 in Table 3 were compared, there was almost no difference. From this, in the positive electrode active material layer, if the content ratio of NCM is 50 parts by mass or more and 80 parts by mass or less and the content ratio of LFP is in the range of 20 parts by mass or more and 40 parts by mass or less, NCM and LFP It was found that the cell surface temperature did not increase excessively during the nail penetration test even when the content ratio changed.
  • the negative electrode of the laminated lithium ion secondary battery of Example 9 contains silicon material and graphite
  • the laminated lithium ion secondary of Example 10 The negative electrode of the battery contains a silicon material but does not contain graphite.

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Abstract

L'invention concerne un accumulateur lithium-ion qui présente une sécurité élevée lors d'un court-circuit interne. Cet accumulateur lithium-ion comprend une électrode positive, une électrode négative, un séparateur et une solution d'électrolyte non aqueux, et est caractérisé : en ce que l'électrode positive est pourvue d'une couche de matériau actif d'électrode positive contenant un matériau actif d'électrode positive ; en ce que le matériau actif d'électrode positive contient un oxyde composite de lithium, de nickel, de cobalt et de manganèse et un composé de phosphate de fer et de lithium ; en ce que l'électrode négative est pourvue d'une couche de matériau actif d'électrode négative contenant un matériau actif d'électrode négative ; et en ce que le matériau actif d'électrode négative contient un matériau de silicium dans la structure duquel des corps de silicium en forme de plaque sont stratifiés dans la direction de l'épaisseur.
PCT/JP2016/002784 2015-07-22 2016-06-08 Accumulateur lithium-ion Ceased WO2017013827A1 (fr)

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WO2018143273A1 (fr) * 2017-01-31 2018-08-09 日本電気株式会社 Oxyde composite à base de lithium et de manganèse ainsi que procédé de fabrication de celui-ci, matériau d'électrode positive mettant en œuvre celui-ci, électrode positive, et batterie secondaire au lithium-ion
CN111164817A (zh) * 2017-10-13 2020-05-15 远景Aesc能源元器件有限公司 锂离子二次电池
JP2020169270A (ja) * 2019-04-03 2020-10-15 信越化学工業株式会社 生体電極組成物、生体電極、及び生体電極の製造方法
CN112447972A (zh) * 2019-08-27 2021-03-05 株式会社丰田自动织机 含有硅包合物ii的负极活性物质
JP2022013562A (ja) * 2020-06-30 2022-01-18 ニンボ チュンシン マイクロ－エレクトロニクス カンパニー リミテッド フォトカプラ装置
WO2022033584A1 (fr) * 2020-08-14 2022-02-17 比亚迪股份有限公司 Matériau d'électrode positive mixte, plaque d'électrode positive et son procédé de fabrication, et batterie
WO2022035531A3 (fr) * 2020-07-14 2022-03-24 Celgard, Llc Batterie secondaire avec séparateur de batterie amélioré
JP2023526562A (ja) * 2020-06-14 2023-06-21 クレイトン ハンセン ジョージ 電池の抵抗低減及び電池材料
WO2023149685A1 (fr) * 2022-02-03 2023-08-10 주식회사 엘지에너지솔루션 Batterie secondaire au lithium
JP2023538720A (ja) * 2021-07-30 2023-09-11 寧徳時代新能源科技股▲分▼有限公司 二次電池及びこの二次電池を含む電池モジュール、電池パックと電力消費装置
WO2023224071A1 (fr) * 2022-05-20 2023-11-23 株式会社Ｇｓユアサ Élément de stockage d'énergie à électrolyte non aqueux
JP2024539298A (ja) * 2021-10-25 2024-10-28 寧徳新能源科技有限公司 電気化学装置及びそれを含む電子装置
WO2024246719A1 (fr) * 2023-06-02 2024-12-05 株式会社半導体エネルギー研究所 Batterie secondaire, appareil électronique et véhicule
JP2025528470A (ja) * 2023-02-06 2025-08-28 香港時代新能源科技有限公司 二次電池と電力消費装置
WO2026032057A1 (fr) * 2024-08-08 2026-02-12 宁德时代新能源科技股份有限公司 Élément de batterie, dispositif de batterie et dispositif électrique
WO2026086032A1 (fr) * 2024-10-24 2026-04-30 湖北亿纬动力有限公司 Matériau d'électrode positive, son procédé de préparation, feuille d'électrode positive et batterie

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JP7097540B2 (ja) 2017-01-31 2022-07-08 日本電気株式会社 リチウムイオン二次電池用リチウムマンガン系複合酸化物及びその製造方法、並びにそれを用いた正極材料、正極及びリチウムイオン二次電池
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WO2018143273A1 (fr) * 2017-01-31 2018-08-09 日本電気株式会社 Oxyde composite à base de lithium et de manganèse ainsi que procédé de fabrication de celui-ci, matériau d'électrode positive mettant en œuvre celui-ci, électrode positive, et batterie secondaire au lithium-ion
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CN111164817B (zh) * 2017-10-13 2023-09-01 株式会社Aesc 日本 锂离子二次电池
CN111164817A (zh) * 2017-10-13 2020-05-15 远景Aesc能源元器件有限公司 锂离子二次电池
JP2020169270A (ja) * 2019-04-03 2020-10-15 信越化学工業株式会社 生体電極組成物、生体電極、及び生体電極の製造方法
JP7082082B2 (ja) 2019-04-03 2022-06-07 信越化学工業株式会社 生体電極組成物、生体電極、及び生体電極の製造方法
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JP7609898B2 (ja) 2020-06-14 2025-01-07 バッテリー エレクトロン トランスポート アソシエーツ，インコーポレイティド 電池の抵抗低減及び電池材料
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JP2022013562A (ja) * 2020-06-30 2022-01-18 ニンボ チュンシン マイクロ－エレクトロニクス カンパニー リミテッド フォトカプラ装置
WO2022035531A3 (fr) * 2020-07-14 2022-03-24 Celgard, Llc Batterie secondaire avec séparateur de batterie amélioré
CN114079046A (zh) * 2020-08-14 2022-02-22 比亚迪股份有限公司 混合正极材料、正极极片及其制作方法、电池
WO2022033584A1 (fr) * 2020-08-14 2022-02-17 比亚迪股份有限公司 Matériau d'électrode positive mixte, plaque d'électrode positive et son procédé de fabrication, et batterie
CN114079046B (zh) * 2020-08-14 2024-01-09 比亚迪股份有限公司 混合正极材料、正极极片及其制作方法、电池
JP2023538720A (ja) * 2021-07-30 2023-09-11 寧徳時代新能源科技股▲分▼有限公司 二次電池及びこの二次電池を含む電池モジュール、電池パックと電力消費装置
JP7574397B2 (ja) 2021-07-30 2024-10-28 香港時代新能源科技有限公司 二次電池及びこの二次電池を含む電池モジュール、電池パックと電力消費装置
JP2024539298A (ja) * 2021-10-25 2024-10-28 寧徳新能源科技有限公司 電気化学装置及びそれを含む電子装置
JP7815430B2 (ja) 2021-10-25 2026-02-17 寧徳新能源科技有限公司 電気化学装置及びそれを含む電子装置
JP2024528099A (ja) * 2022-02-03 2024-07-26 エルジー エナジー ソリューション リミテッド リチウム二次電池
WO2023149685A1 (fr) * 2022-02-03 2023-08-10 주식회사 엘지에너지솔루션 Batterie secondaire au lithium
WO2023224071A1 (fr) * 2022-05-20 2023-11-23 株式会社Ｇｓユアサ Élément de stockage d'énergie à électrolyte non aqueux
JP2025528470A (ja) * 2023-02-06 2025-08-28 香港時代新能源科技有限公司 二次電池と電力消費装置
WO2024246719A1 (fr) * 2023-06-02 2024-12-05 株式会社半導体エネルギー研究所 Batterie secondaire, appareil électronique et véhicule
WO2026032057A1 (fr) * 2024-08-08 2026-02-12 宁德时代新能源科技股份有限公司 Élément de batterie, dispositif de batterie et dispositif électrique
WO2026086032A1 (fr) * 2024-10-24 2026-04-30 湖北亿纬动力有限公司 Matériau d'électrode positive, son procédé de préparation, feuille d'électrode positive et batterie

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