WO2013024639A1 - Matériau actif d'électrode négative et électrode négative pour batterie secondaire lithium-ion, et batterie secondaire lithium-ion - Google Patents

Matériau actif d'électrode négative et électrode négative pour batterie secondaire lithium-ion, et batterie secondaire lithium-ion Download PDF

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WO2013024639A1
WO2013024639A1 PCT/JP2012/066984 JP2012066984W WO2013024639A1 WO 2013024639 A1 WO2013024639 A1 WO 2013024639A1 JP 2012066984 W JP2012066984 W JP 2012066984W WO 2013024639 A1 WO2013024639 A1 WO 2013024639A1
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negative electrode
active material
electrode active
ion secondary
secondary battery
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PCT/JP2012/066984
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English (en)
Japanese (ja)
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須黒　雅博
緑 志村
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日本電気株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a negative electrode active material and a negative electrode for lithium ion secondary batteries, and a lithium ion secondary battery.
  • Lithium ion secondary batteries have already been put into practical use as batteries for electronic devices such as notebook computers and mobile phones due to advantages such as high energy density, small self-discharge, and excellent long-term reliability.
  • electronic devices have been enhanced in functionality and used in electric vehicles, and development of lithium ion secondary batteries with higher energy density has been demanded. Therefore, the secondary battery using the graphite-based negative electrode material cannot satisfy the required performance.
  • Patent Document 1 describes that silicon oxide or silicate is used as a negative electrode active material of a secondary battery.
  • Patent Document 2 discloses a negative electrode for a secondary battery including an active material layer including carbon material particles capable of inserting and extracting lithium ions, metal particles capable of being alloyed with lithium, and oxide particles capable of inserting and extracting lithium ions. Is described.
  • Patent Document 3 describes a negative electrode material for a secondary battery in which the surface of particles having a structure in which silicon microcrystals are dispersed in a silicon compound is coated with carbon.
  • Patent Document 4 describes a negative electrode for a lithium secondary battery using active material particles containing silicon and / or silicon alloy having a specific average particle size and particle size distribution, and polyimide as a binder.
  • Patent Document 5 describes a negative electrode for a non-aqueous electrolyte secondary battery including an active material containing Si, polyimide and polyacrylic acid as a binder, and a carbon material as a conductive material.
  • Patent Document 6 describes that surface-modified silicon particles having an organic silane layer formed by treating the surface of silicon particles with a silane coupling agent are used as a negative electrode active material.
  • Patent Document 7 describes a negative electrode active material obtained by surface-modifying silicon particles or silicon oxide particles with terminal hydrolyzable modified silicone.
  • a lithium ion secondary battery using a metal that can be alloyed with lithium (for example, silicon) or a metal oxide that can occlude and release lithium (for example, silicon oxide) as a negative electrode active material the cycle characteristics in a high-temperature environment are reduced. It becomes a problem.
  • an object of the present invention is to provide a secondary battery having good high-temperature cycle characteristics, and to provide a negative electrode active material and a negative electrode suitable for such a secondary battery.
  • the negative electrode active material according to an aspect of the present invention is a negative electrode active material for a lithium ion secondary battery, including a metal (a) that can be alloyed with lithium, Following formula (1):
  • R 1 and R 2 each independently represent an alkoxy group
  • R 3 and R 4 each independently represent an alkyl group or a hydrogen atom
  • n and m each independently represent 0, 1 or 2
  • X represents a divalent group containing an oxyalkylene group in the main chain.
  • a negative electrode for a lithium ion secondary battery according to another embodiment of the present invention includes the negative electrode active material described above.
  • a lithium ion secondary battery according to another aspect of the present invention includes the above negative electrode.
  • An assembled battery according to another aspect of the present invention includes a plurality of the above lithium ion secondary batteries.
  • a vehicle according to another aspect of the present invention has the above-described lithium ion secondary battery or the above assembled battery mounted as a motor driving power source.
  • a method for producing a negative electrode active material for a lithium ion secondary battery in which a negative electrode active material containing a metal (a) that can be alloyed with lithium is treated with a silane compound represented by the above formula (1). Processing step.
  • a method of manufacturing a lithium ion secondary battery according to another aspect of the present invention includes: Surface treatment of the negative electrode active material by the above method, Forming a negative electrode using the negative electrode active material surface-treated; Forming the electrode pair by disposing the negative electrode and the positive electrode opposite to each other with a separator interposed therebetween; Covering the electrode pair with a laminate film.
  • the present invention it is possible to provide a secondary battery with good high-temperature cycle characteristics, and to provide a negative electrode active material and a negative electrode suitable for such a secondary battery.
  • FIG. 1 is a schematic cross-sectional view for explaining the structure of a laminated laminate type secondary battery according to an embodiment of the present invention.
  • the negative electrode active material according to the embodiment of the present invention includes a metal (a) that can be alloyed with lithium and is surface-treated with a silane compound represented by the formula (1).
  • a negative electrode formed using this negative electrode active material is suitable for a lithium ion secondary battery.
  • a lithium ion secondary battery includes a positive electrode, a separator, an electrode laminate including the negative electrode disposed to face the positive electrode with the separator interposed therebetween, an electrolytic solution, and an outer package including them. including.
  • the electrode laminate can include one or two or more electrode pairs of a positive electrode and a negative electrode.
  • the secondary battery according to the present embodiment may have a laminated laminate type structure in which such an electrode laminate is packaged with a laminate film. According to this embodiment, it is possible to provide a lithium ion secondary battery in which gas generation during operation is suppressed and cycle characteristics under a high temperature environment are good.
  • FIG. 1 is a schematic cross-sectional view showing an example of an electrode laminated body of such a laminated laminate type secondary battery.
  • the exterior body is omitted.
  • the positive electrode 3 and the negative electrode 1 are alternately stacked via the separator 2.
  • the positive electrode current collector 5 of each positive electrode 3 is welded to and electrically connected to each other at an end portion not covered with the positive electrode active material, and the positive electrode terminal 6 is welded to the welded portion.
  • a negative electrode current collector 4 included in each negative electrode 1 is welded to and electrically connected to each other at an end portion not covered with the negative electrode active material, and a negative electrode terminal 7 is welded to the welded portion.
  • This electrode laminate is accommodated in a container formed of a laminate film as an exterior body, and an electrolyte is injected and sealed.
  • a laminated battery (laminated laminated battery) having such a planar laminated structure has a smaller R (for example, a wound core with a wound structure) than a battery having a wound structure (winded battery). Therefore, there is an advantage that it is difficult to be adversely affected by the volume change of the electrode accompanying charging / discharging.
  • the electrode since the electrode is curved in the wound type battery, the structure is easily distorted when a volume change occurs in the electrode. Such distortion is particularly noticeable when a negative electrode active material having a large volume change accompanying charge / discharge, such as a silicon-based active material, is used.
  • a laminated laminate battery is suitable when an active material having a large volume change associated with charge / discharge is used.
  • planar laminated structure means that each laminated electrode is a sheet-like material, and each electrode is laminated in a planar shape (the outer peripheral edge of the sheet-like material is at the peripheral edge of the laminated structure) It is distinguished from a structure in which the electrode stack is bent or a structure in which the electrode stack is wound.
  • such a laminated laminate type battery has a problem that when the gas is generated between the electrodes, the generated gas tends to stay between the electrodes. This is because the winding type battery has tension acting on the electrodes and thus the distance between the electrodes is difficult to widen, whereas in the laminated battery, the distance between the electrodes is likely to be widened. This problem is particularly noticeable when the outer package is an aluminum laminate film. Furthermore, this problem becomes more prominent when the electrolytic solution contains a carbonate ester or a carboxylic acid ester.
  • the negative electrode active material according to the present embodiment contains a metal (a) that can be alloyed with lithium and is surface-treated with a specific silane compound.
  • the negative electrode in the present embodiment includes a current collector and an active material layer on the current collector, and the active material layer includes a binder and the above-described negative electrode active material.
  • the binder binds between the active material particles and between the active material particles and the current collector.
  • the negative electrode active material only needs to contain the metal (a), but preferably contains both the metal (a) and the metal oxide (b).
  • the negative electrode active material preferably further contains a carbon material (c).
  • the negative electrode active material may have a carbon film.
  • the metal (a) Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, or an alloy containing two or more of these is used. it can.
  • silicon (Si) or a silicon-containing metal is preferable as the metal (a), and silicon is more preferable.
  • the content of the metal (a) in the negative electrode active material is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more from the viewpoint of obtaining a sufficient addition effect (such as charge / discharge capacity). From the viewpoint of sufficiently obtaining the effect of adding other components, etc., it is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 80% by mass or less, and can also be 50% by mass or less.
  • silicon oxide, aluminum oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, or a composite oxide containing two or more of these can be used.
  • silicon oxide is preferably included as the metal oxide (b). This is because silicon oxide is relatively stable and does not easily react with other compounds.
  • one or more elements selected from nitrogen, boron and sulfur may be added to the metal oxide (b), for example, 0.1 to 5% by mass. By carrying out like this, the electrical conductivity of a metal oxide (b) can be improved.
  • the content of the metal oxide (b) in the negative electrode active material may be 0% by mass, but is preferably 5% by mass or more and 15% by mass from the viewpoint of obtaining a sufficient addition effect (such as charge / discharge cycle characteristics).
  • the above is more preferable, 40% by mass or more is further preferable, and 50% by mass or more can also be achieved.
  • 90 mass% or less is preferable from the point which fully obtains the addition effect of another component, etc., 80 mass% or less is more preferable, and 70 mass% or less is further more preferable.
  • the metal oxide (b) preferably has an amorphous structure in whole or in part.
  • the metal oxide (b) having an amorphous structure can suppress the volume expansion of the carbon material (c) and the metal (a), which are other negative electrode active material components, and can suppress the decomposition of the electrolytic solution.
  • the metal oxide (b) has an amorphous structure, which has some influence on the film formation at the interface between the carbon material (c) and the electrolytic solution.
  • the amorphous structure is considered to have relatively few elements due to non-uniformity such as crystal grain boundaries and defects.
  • the metal (a) is entirely or partially dispersed in the metal oxide (b).
  • the metal oxide (b) By dispersing at least a part of the metal (a) in the metal oxide (b), volume expansion as the whole negative electrode can be further suppressed, and decomposition of the electrolytic solution can also be suppressed.
  • all or part of the metal (a) is dispersed in the metal oxide (b) because of observation with a transmission electron microscope (general TEM observation) and energy dispersive X-ray spectroscopy (general). This can be confirmed by using a combination of a standard EDX measurement. Specifically, the cross section of the sample containing the metal (a) is observed, the oxygen concentration of the particles dispersed in the metal oxide (b) is measured, and the metal (a) constituting the particles is It can be confirmed that it is not an oxide.
  • the metal oxide (b) is preferably an oxide of a metal constituting the metal (a). More preferably, the metal (a) is simple silicon and the metal oxide (b) is silicon oxide.
  • the mass ratio (a / b) of the metal (a) and the metal oxide (b) in the negative electrode active material is not particularly limited. Can be set in the range of 5/95 to 90/10, can be set in the range of 10/90 to 80/20, and can be set in the range of 30/70 to 60/40. it can.
  • carbon material (c) graphite, amorphous carbon, diamond-like carbon, carbon nanotube, or a composite containing two or more of these can be used.
  • graphite with high crystallinity has high electrical conductivity, and is excellent in adhesiveness and voltage flatness with a positive electrode current collector made of a metal such as copper.
  • amorphous carbon having low crystallinity has a relatively small volume expansion, it has a high effect of relaxing the volume expansion of the entire negative electrode, and deterioration due to non-uniformity such as crystal grain boundaries and defects hardly occurs.
  • the content of the carbon material (c) in the negative electrode active material may be 0% by mass, but is preferably 1% by mass or more, more preferably 2% by mass or more from the viewpoint of obtaining a sufficient addition effect, and other components. From the viewpoint of sufficiently obtaining the addition effect, etc., 50% by mass or less is preferable, and 30% by mass or less is more preferable.
  • the ratio of the metal (a), the metal oxide (b), and the carbon material (c) is not particularly limited. However, it can be set according to the range of the above content rate.
  • the content ratio of the metal (a) is, for example, preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass with respect to the total of the metal (a), the metal oxide (b), and the carbon material (c). % Or more is more preferable, 90 mass% or less is preferable, 80 mass% or less is more preferable, and it can also be set to 50 mass% or less.
  • the content ratio of the metal oxide (b) is preferably, for example, 5% by mass or more, more preferably 15% by mass or more, with respect to the total of the metal (a), the metal oxide (b), and the carbon material (c). It can also be set to 40% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and can also be set to 70% by mass or less.
  • the content ratio of the carbon material (c) is, for example, preferably 1% by mass or more, more preferably 2% by mass or more, with respect to the total of the metal (a), the metal oxide (b), and the carbon material (c). 50 mass% or less is preferable and 30 mass% mass% or less is more preferable.
  • the shape of the metal (a), the metal oxide (b), and the carbon material (c) is not particularly limited, but may be particulate.
  • the average particle diameter of the metal (a) is preferably smaller than the average particle diameter of the carbon material (c) and the average particle diameter of the metal oxide (b).
  • the metal (a) having a large volume change during charging and discharging has a relatively small particle size, and the metal oxide (b) and the carbon material (c) having a relatively small volume change are relatively large. Due to the particle size, dendrite formation and alloy pulverization are more effectively suppressed. In addition, during the charge / discharge process, large particles and small particles can alternately occlude and release lithium, thereby suppressing the occurrence of residual stress and residual strain.
  • the average particle diameter of the metal (a) can be, for example, 20 ⁇ m or less, preferably 15 ⁇ m or less, and can also be 10 ⁇ m or less.
  • the average particle diameter is a 50% cumulative diameter D 50 (median diameter) obtained by particle size distribution measurement by a laser diffraction scattering method.
  • the average particle diameter of the metal oxide (b) is preferably 1 ⁇ 2 or less of the average particle diameter of the carbon material (c). Moreover, it is preferable that the average particle diameter of a metal (a) is 1/2 or less of the average particle diameter of a metal oxide (b). Furthermore, the average particle diameter of the metal oxide (b) is 1 ⁇ 2 or less of the average particle diameter of the carbon material (c), and the average particle diameter of the metal (a) is the average particle diameter of the metal oxide (b). It is more preferable that it is 1/2 or less.
  • the average particle diameter of silicon oxide (b) is set to be 1 ⁇ 2 or less of the average particle diameter of graphite (c), and the average particle diameter of silicon (a) is equal to the average particle diameter of silicon oxide (b). It is preferable to make it 1/2 or less.
  • the average particle diameter of silicon (a) can be set to, for example, 20 ⁇ m or less, preferably 15 ⁇ m or less, and can also be set to 10 ⁇ m or less.
  • the negative electrode active material containing metal (a) and metal oxide (b) can be obtained, for example, by sintering metal (a) and metal oxide (b) under high temperature and reduced pressure. Or it can obtain by mixing a metal (a) and a metal oxide (b) by mechanical milling.
  • the active material thus formed can be coated with carbon. For example, there are a method of mixing and baking this active material and an organic compound, and a method of introducing this active material into a gas atmosphere of an organic compound such as methane and performing thermal CVD.
  • the negative electrode active material containing the metal (a), the metal oxide (b), and the carbon material (c) all or part of the metal oxide (b) has an amorphous structure, and all or part of the metal (a) A part of which is dispersed in the metal oxide (b) can be used.
  • a negative electrode active material can be produced, for example, by the method described in Patent Document 3 (Japanese Patent Laid-Open No. 2004-47404).
  • the metal oxide (b) is disproportionated at 900 to 1400 ° C. in an atmosphere containing an organic compound gas such as methane, and a thermal CVD process is performed.
  • the metal element in metal oxide (b) can be clustered as a metal (a), and the composite body by which the surface was coat
  • the negative electrode active material containing the metal (a), the metal oxide (b), and the carbon material (c) can also be produced by mixing by mechanical milling.
  • the specific surface area of the negative electrode active material is preferably 0.2 m 2 / g or more, more preferably 1.0 m 2 / g or more, still more preferably 2.0 m 2 / g or more, while 9.0 m 2 / g or less.
  • 8.0 m 2 / g or less is more preferable, and 7.0 m 2 / g or less is more preferable.
  • the specific surface area is obtained by an ordinary BET specific surface area measurement method.
  • the average particle diameter of the negative electrode active material is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, further preferably 0.2 ⁇ m or more, and on the other hand, 30 ⁇ m or less is more preferable, and 20 ⁇ m or less is more preferable.
  • the average particle diameter is 50% cumulative diameter D 50 (median diameter), and is obtained by particle size distribution measurement by a laser diffraction scattering method.
  • binder for the negative electrode examples include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene-butadiene copolymer rubber, polytetrafluoroethylene, polypropylene, polyethylene, Polyimide, polyamideimide, or the like can be used. Of these, polyimide or polyamideimide is preferred because of its high binding properties.
  • the amount of the binder for negative electrode to be used is preferably 5 to 25 parts by mass with respect to 100 parts by mass of the negative electrode active material, from the viewpoints of binding force and high energy density which are in a trade-off relationship.
  • the negative electrode current collector aluminum, nickel, copper, silver, and alloys thereof are preferable in view of electrochemical stability.
  • the shape include foil, flat plate, and mesh.
  • a copper foil can be used.
  • the negative electrode can be produced, for example, by forming a negative electrode active material layer containing a negative electrode active material and a negative electrode binder on a negative electrode current collector.
  • a negative electrode can be produced by preparing a slurry containing a negative electrode active material, a binder, and a solvent, applying the slurry onto a negative electrode current collector, and drying the slurry.
  • the slurry application method include a doctor blade method, a die coater method, and a dip coating method.
  • a metal thin film may be formed by a method such as vapor deposition or sputtering, and this metal thin film may be used as the negative electrode current collector.
  • the silane compound used for the surface treatment of the negative electrode active material in the present embodiment is a compound represented by the above formula (1).
  • R 1 and R 2 each independently represents an alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, such as a methoxy group, an ethoxy group, or n-propoxy Group, i-propoxy group is preferable, and methoxy group and ethoxy group are more preferable.
  • R 3 and R 4 each independently represents an alkyl group or a hydrogen atom.
  • the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, Group and ethyl group are more preferred.
  • X represents a divalent group containing an oxyalkylene group in the main chain.
  • the oxyalkylene group an oxyethylene group and an oxypropylene group are preferable, and an oxyethylene group is more preferable.
  • the number of oxyalkylene groups in the main chain of the divalent group X is one or more, and preferably the divalent group X has a polyoxyalkylene chain containing two or more oxyalkylene groups in the main chain. preferable.
  • the number of oxyalkylene groups in the polyoxyalkylene chain is preferably in the range of 2 to 10, more preferably in the range of 2 to 5.
  • the atom bonded to the Si atom of the divalent group X may be a carbon atom or an oxygen atom.
  • Such a divalent group X is preferably an organic chain containing an oxyalkylene group or a polyoxyalkylene group in the main chain, and each terminal of the oxyalkylene group or polyoxyalkylene group is an alkylene group (for example, a carbon number). 1 to 3) or can be bonded to the silicon atom via an oxygen atom.
  • Examples of the silane compound represented by the formula (1) include organosilicon compounds represented by the following formulas (2) to (43).
  • the method of surface treatment using a silane compound is not particularly limited, and for example, a method of surface treating Si-based inorganic particles with a normal silane coupling agent can be applied.
  • a solution in which a silane compound is dissolved in a solvent is prepared, and active material particles (or a mixture of active material particles and a solvent) are added to the solution and mixed.
  • a silane compound solution may be added and mixed in a solvent in which the active material particles are dispersed. Thereafter, filtration and drying can be performed to obtain surface-treated active material particles.
  • the solvent include lower alcohols such as methanol and ethanol, and water.
  • the mixing ratio between the silane compound and the active material particles is not particularly limited as long as the particle surface is sufficiently processed.
  • a surface treatment is performed using, for example, a 1% by mass solution of a silane compound, and this amount can be appropriately increased or decreased so as to obtain a desired effect. Determining the minimum coverage of the silane compound (m 2 / g), based on the product of the mass (g) and specific surface area of the particles of the active material particles (m 2 / g) to a value obtained by dividing this minimum coverage silane You may set the addition amount of a compound.
  • the treatment temperature can be set, for example, in the range of 10 to 40 ° C.
  • the treatment time can be set, for example, in the range of 1 to 24 hours.
  • the amount of silane compound bonded to the active material particles is such that, for example, the mass reduction rate when heated to 600 ° C. at 20 ° C./min in an air atmosphere is in the range of 0.01 to 5% by mass. Can be set.
  • the mass reduction rate is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. If this mass reduction rate is too large (that is, if the coating amount is too large), the charge transfer resistance may increase, and therefore it is preferably 5% by mass or less, more preferably 3% by mass or less.
  • This mass reduction rate can be measured using a thermal analyzer such as TGA. This mass reduction rate is the ratio (%) of the mass reduction amount when heated at 600 ° C. with respect to the mass of the sample before heating.
  • Positive electrode for example, a positive electrode having a positive electrode active material layer containing a positive electrode active material and a positive electrode binder on a positive electrode current collector can be used.
  • lithium manganate having a layered structure or spinel structure such as LiMnO 2 or Li x Mn 2 O 4 (0 ⁇ x ⁇ 2); a part of Mn of lithium manganate was replaced with another metal Lithium metal oxide; LiCoO 2 , LiNiO 2 , lithium metal oxide in which a part of these transition metals (Co, Ni) is replaced with another metal; LiNi 1/3 Co 1/3 Mn 1/3 O 2, etc. Lithium transition metal oxides whose specific transition metals do not exceed half of the total number of transition metals (atomic ratio); in these lithium transition metal oxides, mention may be made of lithium metal oxides containing Li in excess of the stoichiometric composition It is done.
  • ⁇ ⁇ 0.1 and ⁇ ⁇ 0.01 can be set.
  • a positive electrode active material can be used individually by 1 type or in combination of 2 or more types.
  • the positive electrode binder the same negative electrode binder as that used for normal negative electrodes can be used.
  • polyvinylidene fluoride is preferable from the viewpoint of versatility and low cost.
  • the amount of the positive electrode binder used is preferably 2 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material, from the viewpoints of binding force and energy density which are in a trade-off relationship.
  • the positive electrode current collector can be selected from the same conductive materials as the negative electrode current collector, and can be electrochemically stable.
  • Examples of the shape include foil, flat plate, and mesh. In particular, an aluminum foil can be suitably used.
  • a conductive auxiliary material may be added to the positive electrode active material layer containing the positive electrode active material for the purpose of reducing impedance.
  • the conductive auxiliary material include carbonaceous fine particles such as graphite, carbon black, and acetylene black.
  • the positive electrode is prepared by, for example, preparing a slurry containing a positive electrode active material, a binder, and a solvent (and, if necessary, a conductive auxiliary material), applying the slurry onto the negative electrode current collector, and drying the slurry.
  • a positive electrode active material layer can be produced by forming a positive electrode active material layer.
  • Electrolytic Solution As the electrolytic solution used in the present embodiment, a nonaqueous electrolytic solution that is stable at the operating potential of the battery can be used.
  • a non-aqueous electrolyte an electrolyte containing a lithium salt (supporting salt) and a non-aqueous solvent that dissolves the lithium salt can be used.
  • an aprotic organic solvent such as carbonate ester (chain or cyclic carbonate) or carboxylic acid ester (chain or cyclic carboxylic acid ester) can be used.
  • Examples of the carbonate ester include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC); dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate ( EMC), chain carbonates such as dipropyl carbonate (DPC); and propylene carbonate derivatives.
  • Examples of the carboxylic acid ester include aliphatic carboxylic acid esters such as methyl formate, methyl acetate, and ethyl propionate.
  • Non-aqueous solvents can be used alone or in combination of two or more.
  • the non-aqueous electrolyte preferably further contains a fluorinated ether compound.
  • the fluorinated ether compound has a high affinity with the Si-based active material (particularly Si), and can improve cycle characteristics (particularly capacity retention rate).
  • the fluorinated ether compound may be a fluorinated chain ether compound obtained by substituting a part of hydrogen of a non-fluorinated chain ether compound with fluorine, or a part of hydrogen of a non-fluorinated cyclic ether compound with fluorine. It may be a substituted fluorinated cyclic ether compound.
  • fluorinated chain ether compound examples include fluorinated products of non-fluorinated chain ether compounds exemplified below.
  • non-fluorinated chain ether compounds include dimethyl ether, methyl ethyl ether, diethyl ether, methyl propyl ether, ethyl propyl ether, dipropyl ether, methyl butyl ether, ethyl butyl ether, propyl butyl ether, dibutyl ether, methyl pentyl ether, ethyl pentyl.
  • Chain monoether compounds such as ether, propylpentyl ether, butylpentyl ether, dipentyl ether; 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxymethoxyethane (EME), 1, 2-dipropoxyethane, propoxyethoxyethane, propoxymethoxyethane, 1,2-dibutoxyethane, butoxypropoxyethane, butoxyethoxyethane, butoxy Methoxy ethane, 1,2-pentoxy ethane, pentoxy butoxy ethane, pent propoxy ethane, pentoxy ethoxy ethane, chain diether compounds such as pentoxifylline methoxy ethane.
  • DME 1,2-dimethoxyethane
  • DEE 1,2-diethoxyethane
  • EME ethoxymethoxyethane
  • 1, 2-dipropoxyethane propoxye
  • fluorinated cyclic ether compound examples include fluorinated products of non-fluorinated cyclic ether compounds exemplified below.
  • non-fluorinated cyclic ether compound examples include ethylene oxide, propylene oxide, oxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, tetrahydropyran, 2-methyltetrahydropyran, 3-methyltetrahydropyran, 4-methyltetrahydropyran, etc.
  • a fluorinated chain ether compound having good stability is preferable, and such a fluorinated chain ether compound has the following formula: H- (CX 1 X 2 -CX 3 X 4 ) n -CH 2 O-CX 5 X 6 -CX 7 X 8 -H (In the formula, n is 1, 2, 3 or 4, and X 1 to X 8 are each independently a fluorine atom or a hydrogen atom, provided that at least one of X 1 to X 4 is a fluorine atom, At least one of X 5 to X 8 is a fluorine atom, and the atomic ratio of fluorine atoms to hydrogen atoms bonded to the fluorinated chain ether compound (total number of fluorine atoms / total number of hydrogen atoms ⁇ 1).
  • the content of such a fluorinated ether compound is preferably 10 vol% or more, more preferably 15 vol% or more based on the total amount of the nonaqueous solvent (100 vol%) from the viewpoint of obtaining a sufficient addition effect within the range not impairing the battery characteristics. More preferably, it is 75 vol% or less, more preferably 70 vol% or less, and further preferably 50 vol% or less.
  • Examples of the supporting salt include LiPF 6 , LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , Li (CF 3 SO 2 ) 2 , LiN (CF 3 SO 2 ) A lithium salt such as 2 .
  • the supporting salt can be used alone or in combination of two or more.
  • separator As the separator, a polyolefin film such as polypropylene or polyethylene, a porous film or a nonwoven fabric made of a fluororesin, or the like can be used. Moreover, what laminated
  • Exterior Body As the exterior body, a laminate film that is stable in an electrolytic solution and has a sufficient water vapor barrier property can be used.
  • a laminate film made of polypropylene, polyethylene or the like coated with aluminum, silica, or alumina can be used as such an exterior body.
  • a change in the volume of the battery and distortion of the electrode due to the generation of gas are more likely to occur than in a secondary battery using a metal can as the exterior body. This is because the laminate film is more easily deformed by the internal pressure of the secondary battery than the metal can.
  • the internal pressure of the battery is usually lower than atmospheric pressure, and there is no extra space inside, so when gas is generated in the battery Immediately leads to battery volume change and electrode deformation.
  • the secondary battery according to the present embodiment can suppress the occurrence of such a problem. Thereby, a laminated laminate type lithium ion secondary battery having excellent high-temperature cycle characteristics can be provided.
  • an assembled battery in which a plurality of the secondary batteries (single cells) described above are electrically connected and packed with a tube or a case.
  • the cells in the assembled battery can be connected in series, in parallel, or both.
  • the capacity and voltage can be adjusted according to the number of cells and the connection method.
  • a plurality of the assembled batteries can be connected in series or in parallel.
  • the above-mentioned secondary battery or assembled battery can be used as a power source for driving a vehicle, and can provide a vehicle with a long life and high reliability.
  • the vehicle can be applied to a hybrid vehicle, an electric vehicle, an electric motorcycle, an electric assist bicycle, and the like. It is not limited to a four-wheel vehicle or a two-wheel vehicle, and a three-wheel vehicle is also included, and the number of wheels is not limited. Furthermore, it can be applied to various power sources for moving / transporting media such as trains.
  • Example 1 Silicon particles (metal (a)) having an average particle diameter of 5 ⁇ m are immersed in a 1 wt% ethanol solution of the silane compound represented by the above formula (3) for 1 hour at room temperature, and then water is added so that the water concentration becomes 5 wt%. And stirred for 1 hour. Next, filtration was performed, and the obtained silicon particles were heated at 100 ° C. for 1 hour to obtain silicon particles surface-treated with a silane compound.
  • silicon particles and graphite (carbon material (c)) having an average particle diameter of 30 ⁇ m are weighed at a mass ratio of 90:10 (silicon: graphite) and mixed by so-called mechanical milling for 24 hours to obtain a negative electrode active material. Obtained.
  • This negative electrode slurry was applied to a copper foil having a thickness of 10 ⁇ m, dried, and further subjected to a heat treatment in a nitrogen atmosphere at 300 ° C. to obtain a negative electrode.
  • 3 layers of the obtained positive electrode and 4 layers of the negative electrode were alternately stacked via a polypropylene porous film as a separator.
  • the electrode laminate was wrapped with an aluminum laminate film as an outer package, and an electrolytic solution was injected therein, and then sealed while reducing pressure to 0.1 atm to obtain a secondary battery.
  • Example 2 to 25 A secondary battery was fabricated in the same manner as in Example 1 except that the silane compound shown in Table 1 was used instead of the silane compound of the formula (3).
  • Example 26 Polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Pyromax (registered trademark)) is used instead of polyimide (PI) as the binder for the negative electrode, and the mass of the negative electrode active material and the polyamideimide is 85:15.
  • a secondary battery was fabricated in the same manner as in Example 1 except that the ratio was reduced and the mixture was mixed with n-methylpyrrolidone to obtain a negative electrode slurry.
  • Example 27 to 50 A secondary battery was made in the same manner as in Example 26 except that the silane compound shown in Table 2 was used instead of the silane compound of the formula (3).
  • Example 51 Silicon having an average particle size of 5 ⁇ m as metal (a), amorphous silicon oxide (SiOx, 0 ⁇ x ⁇ 2) having an average particle size of 13 ⁇ m as metal oxide (b), and carbon material (c) Graphite with an average particle size of 30 ⁇ m was weighed at a mass ratio of 29:61:10 and mixed for 24 hours by so-called mechanical milling to obtain a negative electrode active material.
  • a secondary battery was fabricated in the same manner as in Example 1.
  • Example 52 to 75 A secondary battery was made in the same manner as in Example 51 except that the silane compound shown in Table 3 was used instead of the silane compound of the formula (3).
  • Example 76 Polyamideimide (PAI, manufactured by Toyobo Co., Ltd., trade name: Pyromax (registered trademark)) is used instead of polyimide (PI) as a binder for the negative electrode, and the mass of the negative electrode active material and the polyamideimide is 85:15.
  • a secondary battery was fabricated in the same manner as in Example 51 except that they were reduced in weight and mixed with n-methylpyrrolidone to obtain a negative electrode slurry.
  • Example 77 to 100 A secondary battery was made in the same manner as in Example 76 except that the silane compound shown in Table 4 was used instead of the silane compound of the formula (3).
  • a secondary battery was fabricated in the same manner, and H—CF 2 CF 2 —CH 2 O—CF 2 CF 2 —H was used as the fluorinated ether compound.
  • Example 102 to 104 A secondary battery was fabricated in the same manner as in Example 101 except that the silane compound shown in Table 5 was used instead of the silane compound of the formula (3).
  • a secondary battery was fabricated in the same manner as described above.
  • As the fluorinated ether compound H—CF 2 CF 2 —CH 2 O—CF 2 CF 2 —H was used.
  • Example 106 to 108 A secondary battery was fabricated in the same manner as in Example 105 except that the silane compound shown in Table 5 was used instead of the silane compound of the formula (3).
  • a secondary battery was fabricated in the same manner as described above.
  • As the fluorinated ether compound H—CF 2 CF 2 —CH 2 O—CF 2 CF 2 —H was used.
  • Example 110 to 112 A secondary battery was made in the same manner as Example 109 except that the silane compound shown in Table 5 was used instead of the silane compound of formula (3).
  • a secondary battery was fabricated in the same manner as described above.
  • As the fluorinated ether compound H—CF 2 CF 2 —CH 2 O—CF 2 CF 2 —H was used.
  • Example 114 to 116 A secondary battery was made in the same manner as in Example 113 except that the silane compound shown in Table 5 was used instead of the silane compound of the formula (3).
  • the swelling rate was determined to be “AA” for less than 5%, “A” for 5% or more and less than 10%, “B” for 10% or more but less than 20%, and “C” for 20% or more.
  • the swelling rate of the secondary batteries of the examples at 60 ° C. is smaller than that of the secondary batteries of Comparative Examples 1 to 4, and 60% of the secondary batteries of the examples. It can be seen that the capacity retention rate at 0 ° C. is higher than that of the secondary batteries of Comparative Examples 1 to 4, and a secondary battery with good high-temperature cycle characteristics can be obtained.
  • This embodiment can be used in all industrial fields that require a power source and in industrial fields related to the transport, storage, and supply of electrical energy.
  • power sources for mobile devices such as mobile phones and laptop computers
  • power sources for electric vehicles such as electric cars, hybrid cars, electric motorcycles, electric assist bicycles, and trains
  • power sources for mobile and transport media such as satellites and submarines
  • a backup power source such as a UPS (uninterruptible power supply); a power storage facility for storing power generated by solar power generation, wind power generation, or the like.
  • UPS uninterruptible power supply

Abstract

L'invention concerne un matériau actif d'électrode négative pour une batterie secondaire lithium-ion contenant un métal pouvant former un alliage avec le lithium, le matériau actif d'électrode négative étant traité en surface avec un composé silane représenté par la formule (1) R1 3-nR3 nSi-X-SiR2 3-mR4 m (1) (R1 et R2 représentant chacun indépendamment un groupe alcoxy; R3 et R4 représentant chacun indépendamment un groupe alkyle ou un atome d'hydrogène; n et m représentant chacun indépendamment 0, 1 ou 2; et X représentant un groupe divalent contenant un groupe oxyalkylène dans la chaîne principale).
PCT/JP2012/066984 2011-08-17 2012-07-03 Matériau actif d'électrode négative et électrode négative pour batterie secondaire lithium-ion, et batterie secondaire lithium-ion WO2013024639A1 (fr)

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WO2016152716A1 (fr) * 2015-03-24 2016-09-29 日本電気株式会社 Électrode négative pour batterie rechargeable au lithium-ion, et batterie rechargeable
JP2017112010A (ja) * 2015-12-17 2017-06-22 日本電気株式会社 リチウムイオン二次電池
JP2021501168A (ja) * 2017-11-01 2021-01-14 クローダ，インコーポレイティド パーソナルケア及び化粧品用途に適した化合物
WO2021172443A1 (fr) * 2020-02-28 2021-09-02 パナソニックＩｐマネジメント株式会社 Électrode négative de batterie secondaire, son procédé de fabrication, et batterie secondaire
CN113801155A (zh) * 2020-06-15 2021-12-17 中国石油化工股份有限公司 适用于制备石英砂防吸附亲水涂层的化学剂及其制备和应用
WO2022092212A1 (fr) * 2020-10-30 2022-05-05 パナソニックＩｐマネジメント株式会社 Composé alcoxysilyle et additif pour solution électrolytique non aqueuse le contenant, et solution électrolytique non aqueuse et batterie secondaire à solution électrolytique non aqueuse contenant ledit additif
WO2023032592A1 (fr) * 2021-08-31 2023-03-09 パナソニックＩｐマネジメント株式会社 Matériau actif d'électrode négative pour une batterie rechargeable à électrolyte non aqueux, batterie rechargeable à électrolyte non aqueux utilisant celui-ci, et procédé de fabrication d'un matériau actif d'électrode négative pour une batterie rechargeable à électrolyte non aqueux

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Publication number Priority date Publication date Assignee Title
JP2015185446A (ja) * 2014-03-25 2015-10-22 三菱化学株式会社 非水系二次電池負極用複合黒鉛粒子、及びそれを用いた非水系二次電池
WO2016152716A1 (fr) * 2015-03-24 2016-09-29 日本電気株式会社 Électrode négative pour batterie rechargeable au lithium-ion, et batterie rechargeable
CN107431184A (zh) * 2015-03-24 2017-12-01 日本电气株式会社 锂离子二次电池用负极和二次电池
JP2017112010A (ja) * 2015-12-17 2017-06-22 日本電気株式会社 リチウムイオン二次電池
JP2021501168A (ja) * 2017-11-01 2021-01-14 クローダ，インコーポレイティド パーソナルケア及び化粧品用途に適した化合物
JP7301826B2 (ja) 2017-11-01 2023-07-03 クローダ，インコーポレイティド パーソナルケア及び化粧品用途に適した化合物
WO2021172443A1 (fr) * 2020-02-28 2021-09-02 パナソニックＩｐマネジメント株式会社 Électrode négative de batterie secondaire, son procédé de fabrication, et batterie secondaire
CN113801155A (zh) * 2020-06-15 2021-12-17 中国石油化工股份有限公司 适用于制备石英砂防吸附亲水涂层的化学剂及其制备和应用
CN113801155B (zh) * 2020-06-15 2023-10-31 中国石油化工股份有限公司 适用于制备石英砂防吸附亲水涂层的化学剂及其制备和应用
WO2022092212A1 (fr) * 2020-10-30 2022-05-05 パナソニックＩｐマネジメント株式会社 Composé alcoxysilyle et additif pour solution électrolytique non aqueuse le contenant, et solution électrolytique non aqueuse et batterie secondaire à solution électrolytique non aqueuse contenant ledit additif
WO2023032592A1 (fr) * 2021-08-31 2023-03-09 パナソニックＩｐマネジメント株式会社 Matériau actif d'électrode négative pour une batterie rechargeable à électrolyte non aqueux, batterie rechargeable à électrolyte non aqueux utilisant celui-ci, et procédé de fabrication d'un matériau actif d'électrode négative pour une batterie rechargeable à électrolyte non aqueux

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