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WO2014069117A1 - Matériau actif d'anode pour batterie secondaire non aqueuse et batterie secondaire non aqueuse - Google Patents

Matériau actif d'anode pour batterie secondaire non aqueuse et batterie secondaire non aqueuse Download PDF

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Publication number
WO2014069117A1
WO2014069117A1 PCT/JP2013/074969 JP2013074969W WO2014069117A1 WO 2014069117 A1 WO2014069117 A1 WO 2014069117A1 JP 2013074969 W JP2013074969 W JP 2013074969W WO 2014069117 A1 WO2014069117 A1 WO 2014069117A1
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Prior art keywords
secondary battery
negative electrode
aqueous secondary
active material
electrode active
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Japanese (ja)
Inventor
章 稲葉
春樹 上剃
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Maxell Ltd
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Hitachi Maxell Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous secondary battery having a high capacity and good storage characteristics, and a negative electrode active material for constituting the non-aqueous secondary battery.
  • Non-aqueous secondary batteries such as lithium ion secondary batteries are widely used as power sources for various portable devices because of their high voltage and high capacity.
  • medium- and large-sized power tools such as electric tools, electric vehicles, and electric bicycles has been spreading.
  • the SiO x utilization rate is limited to suppress volume expansion / contraction due to charge / discharge reactions, or halogen-substituted cyclic carbonates (for example, 4-fluoro-1,3-dioxolane-2- Technologies that improve the charge / discharge cycle characteristics of the battery or suppress the expansion of the battery can due to gas generation have been proposed by using a non-aqueous electrolyte solution to which a gas etc. is added (patent document) 3).
  • Patent Document 4 discloses a composite in which SiO x is used as a core and the surface thereof is coated with carbon, and the degree of carbon coating in the composite and the crystalline state of Si in SiO x are specified. A technique that achieves this improvement is disclosed.
  • an object of the present invention is to provide a non-aqueous secondary battery having a high capacity and good storage characteristics, and a negative electrode active material for constituting the non-aqueous secondary battery.
  • the negative electrode active material for a non-aqueous secondary battery of the present invention contains a material containing Si and O as constituent elements, has an average particle diameter D 50% of 6 to 10 ⁇ m determined by a laser diffraction scattering method, and CuK ⁇
  • the full width at half maximum of the (220) diffraction peak of Si obtained by X-ray diffraction using a line is 0.6 to 1.0 °.
  • the non-aqueous secondary battery of the present invention is a non-aqueous secondary battery having a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, a separator and a non-aqueous electrolyte.
  • the negative electrode active material for a non-aqueous secondary battery of the present invention and a graphitic carbon material are used.
  • non-aqueous secondary battery having a high capacity and good storage characteristics, and a negative electrode active material for constituting the non-aqueous secondary battery.
  • FIG. 1 It is a figure which represents typically an example of the non-aqueous secondary battery of this invention, (a) is the top view, (b) is the partial longitudinal cross-sectional view. It is a perspective view of the non-aqueous secondary battery represented in FIG.
  • the present inventors have studied the technique described in Patent Document 4 in order to further improve the storage characteristics of the nonaqueous secondary battery.
  • the half width of the (220) diffraction peak of Si obtained by the X-ray diffraction method is within a specific range.
  • the average particle diameter of the material takes a specific value, it has been found that the storage characteristics of the non-aqueous secondary battery can be enhanced to a high degree, and the present invention has been completed.
  • the present invention will be described in detail.
  • the negative electrode active material for a non-aqueous secondary battery of the present invention contains a material containing Si and O as constituent elements. If it is a negative electrode active material containing such a material, a high capacity
  • the negative electrode active material for a non-aqueous secondary battery of the present invention has an average particle diameter D 50% obtained by a laser diffraction scattering method of 6 to 10 ⁇ m, and is obtained by an X-ray diffraction method using CuK ⁇ rays.
  • the full width at half maximum of the (220) diffraction peak is 0.6 to 1.0 °.
  • the average particle diameter D is 50%
  • the half width of the (220) diffraction peak of Si is By making it become a value, in a non-aqueous secondary battery using this, it is possible to suppress a decrease in capacity when stored in a charged state while maintaining a high capacity, and to ensure high storage characteristics. .
  • the average particle diameter D 50% of the negative electrode active material for a non-aqueous secondary battery is too small, the capacity tends to decrease when a non-aqueous secondary battery using this is stored in a charged state. Further, if the average particle diameter D 50% of the negative electrode active material for a non-aqueous secondary battery is too large, the vicinity of the center of the negative electrode active material particles becomes difficult to participate in the charge / discharge reaction of the battery. The capacity of the secondary battery itself becomes small.
  • the capacity itself of the non-aqueous secondary battery using this will be small.
  • the half width of the (220) diffraction peak of Si in the negative electrode active material for a non-aqueous secondary battery is too large, when the non-aqueous secondary battery using this is stored in a charged state, the capacity is likely to decrease. Become.
  • the (111) diffraction peak is known as the main Si-derived peak observed during the measurement by the X-ray diffraction method, but the (220) diffraction peak is ( For example, the half-value width is easier to obtain than the 111) diffraction peak because it is not affected by a broad peak derived from SiO 2 . Therefore, in the present invention, the negative electrode active material for a non-aqueous secondary battery has a half value width of the (220) diffraction peak of Si as a specific value.
  • the average particle diameter D 50% of the negative electrode active material for a non-aqueous secondary battery in the present specification is a value determined by the laser diffraction scattering method. More specifically, the laser scattering particle size distribution meter (For example, “LA-920” manufactured by HORIBA, Ltd.), and the particle size at 50% of the volume-based integrated fraction measured by dispersing the negative electrode active material in a medium that does not dissolve.
  • the negative electrode active material for nonaqueous secondary battery of the present invention D 10 from the viewpoint of enhancing the storage characteristics of the non-aqueous secondary battery using the better is determined by the average particle diameter D 50% in the same way % (Particle diameter at 10% of the volume-based integrated fraction) is preferably 4 ⁇ m or more.
  • the negative electrode active material for a non-aqueous secondary battery of the present invention is a non-aqueous secondary battery using the same, from the viewpoint of improving the reliability by suppressing the damage of the separator due to the negative electrode active material. It is preferable that D 90% (particle diameter at 90% of the volume-based integrated fraction) obtained by the same method as the particle diameter D 50% is 14 ⁇ m or less.
  • the material containing Si and O as constituent elements may be a composite oxide of Si and another metal in addition to an Si oxide, and may contain a microcrystalline or amorphous phase of Si or another metal. You may go out.
  • a material having a structure in which minute Si phases are dispersed in an amorphous SiO 2 matrix is particularly preferable.
  • This material is represented by the general composition formula SiO x (where 0.5 ⁇ x ⁇ 1.5).
  • SiO x where 0.5 ⁇ x ⁇ 1.5
  • the composition formula is expressed as SiO.
  • SiO x is preferably a composite that is combined with a carbon material.
  • the surface of SiO x is preferably coated with the carbon material. Since SiO x has poor conductivity, when it is used as a negative electrode active material, a conductive aid such as a carbon material is required from the viewpoint of securing good battery characteristics. If complexes complexed with carbon material SiO x, for example, simply than with a material obtained by mixing a conductive assistant such as SiO x and the carbon material, good conductive network in the negative electrode The load characteristics of the battery can be enhanced.
  • the composite in which the surface of SiO x is coated with a carbon material is further combined with a conductive material (carbon material or the like), a better conductive network can be formed in the negative electrode.
  • a non-aqueous secondary battery with higher capacity and better battery characteristics (for example, charge / discharge cycle characteristics).
  • the complex of the SiO x and the carbon material coated with a carbon material for example, like granules the mixture was further granulated with SiO x and the carbon material coated with a carbon material.
  • SiO x whose surface is coated with a carbon material
  • the surface of a composite (for example, a granulated body) of SiO x and a carbon material having a smaller specific resistance value is further coated with a carbon material.
  • a carbon material for example, a granulated body
  • Those can also be preferably used.
  • the non-aqueous secondary battery having a negative electrode containing SiO x as a negative electrode active material it is possible to form a better conductive network when SiO x and the carbon material are dispersed inside the granule. Battery characteristics such as load discharge characteristics can be further improved.
  • Preferred examples of the carbon material that can be used to form a composite with SiO x include carbon materials such as low crystalline carbon, carbon nanotubes, and vapor grown carbon fibers.
  • the details of the carbon material include at least one selected from the group consisting of fibrous or coiled carbon materials, carbon black (including acetylene black and ketjen black), artificial graphite, graphitizable carbon, and non-graphitizable carbon.
  • a seed material is preferred.
  • a fibrous or coiled carbon material is preferable in that it easily forms a conductive network and has a large surface area.
  • Carbon black (including acetylene black and ketjen black), graphitizable carbon, and non-graphitizable carbon have high electrical conductivity and high liquid retention, and even if SiO x particles expand and contract. This is preferable in that it has a property of easily maintaining contact with the particles.
  • graphitic carbon material is also used as a negative electrode active material, the graphite carbon material, and SiO x It can also be used as a carbon material related to a composite with a carbon material.
  • Graphite carbon materials like carbon black, have high electrical conductivity and high liquid retention properties, and even when SiO x particles expand and contract, they easily maintain contact with the particles. Therefore, it can be preferably used for forming a complex with SiO x .
  • a fibrous carbon material is particularly preferable for use when the composite with SiO x is a granulated body. Fibrous carbon material can follow the expansion and contraction of SiO x with the charging and discharging of the battery due to the high shape is thin threadlike flexibility, also because bulk density is large, many and SiO x particles It is because it can have a junction.
  • the fibrous carbon include polyacrylonitrile (PAN) -based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, and carbon nanotube, and any of these may be used.
  • the fibrous carbon material can also be formed on the surface of the SiO x particles by, for example, a vapor phase method.
  • the specific resistance value of SiO x is usually 10 3 to 10 7 k ⁇ cm, whereas the specific resistance value of the above-described carbon material is usually 10 ⁇ 5 to 10 k ⁇ cm.
  • the composite of SiO x and the carbon material may further have a material layer (a material layer containing non-graphitizable carbon) that covers the carbon material coating layer on the particle surface.
  • SiO x relative to 100 parts by mass, a carbon material
  • the amount is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more.
  • SiO x relative to 100 parts by weight, the carbon material, and more preferably preferably not more than 50 parts by weight, more than 40 parts by weight.
  • SiO x can be obtained, for example, by the following method.
  • SiO x can be obtained by a method in which a mixture of Si and SiO 2 is heated, and the generated silicon oxide gas is cooled and deposited.
  • D 50% can be said a value of 10% and D 90% D.
  • the classification may be performed after the CVD process described later.
  • the half width of the (220) diffraction peak of Si can be controlled to the above value.
  • the heat treatment temperature is preferably 900 to 1400 ° C.
  • the heat treatment time is preferably 0.1 to 10 hours.
  • the intensity I a of the diffraction peak derived from Si in which 2 ⁇ is found at a position of 28.4 ° and 2 ⁇ are
  • the ratio I a / I b of the diffraction peak intensity I b derived from SiO 2 observed at a position near 21.2 ° is preferably 2.7 to 3.9. It can be seen that if I a / I b is SiO x satisfying the above values, the SiO 2 molecules are arranged better as the Si particles grow. That is, if I a / I b is SiO x satisfying the above values, it is heat-treated well, and the effect of improving storage characteristics of a non-aqueous secondary battery using this is improved.
  • the intensity I a of diffraction peaks derived from Si to 2 [Theta] in this specification is found at the position of 28.4 ° is the peak height at a position where the peak top of the diffraction peak is present, also, 2 [Theta] is
  • the intensity I b of the diffraction peak derived from SiO 2 observed at a position near 21.2 ° means the peak height at the position where the peak top of the diffraction peak exists.
  • a complex with said SiO x and the carbon material can be obtained, for example, by the following method.
  • a dispersion liquid in which SiO x is dispersed in a dispersion medium is prepared, and sprayed and dried to produce composite particles including a plurality of particles.
  • a dispersion medium for example, ethanol or the like can be used as the dispersion medium. It is appropriate to spray the dispersion liquid in an atmosphere of 50 to 300 ° C.
  • similar composite particles can be produced also by a granulation method by a mechanical method using a vibration type or planetary type ball mill or rod mill.
  • the SiO x in the case of manufacturing a granulated body with small carbon material resistivity value than SiO x is adding the carbon material in the dispersion liquid of SiO x are dispersed in a dispersion medium, the dispersion by using a liquid, by a similar method to the case of composite of SiO x may be a composite particle (granule). Further, by granulation process according to the similar mechanical method, it is possible to produce a granular material of the SiO x and the carbon material.
  • SiO x particles SiO x composite particles or a granulated body of SiO x and a carbon material
  • a carbon material for example, the SiO x particles and the hydrocarbon-based material
  • the gas is heated in the gas phase, and carbon generated by pyrolysis of the hydrocarbon-based gas is deposited on the surface of the particles.
  • the hydrocarbon-based gas spreads to every corner of the composite particle, and the surface of the particle and the pores in the surface are thin and contain a conductive carbon material. Since a uniform film (carbon material coating layer) can be formed, the SiO x particles can be imparted with good conductivity with a small amount of carbon material.
  • the processing temperature (atmosphere temperature) of the vapor deposition (CVD) method varies depending on the type of hydrocarbon gas, but usually 600 to 1200 ° C. is appropriate. Among these, the temperature is preferably 700 ° C. or higher, and more preferably 800 ° C. or higher. This is because the higher the treatment temperature, the less the remaining impurities, and the formation of a coating layer containing carbon having high conductivity.
  • the processing temperature in the CVD method is preferably 900 ° C. or higher.
  • toluene As the liquid source of the hydrocarbon-based gas, toluene, benzene, xylene, mesitylene and the like can be used, but toluene that is easy to handle is particularly preferable.
  • a hydrocarbon-based gas can be obtained by vaporizing them (for example, bubbling with nitrogen gas).
  • methane gas, acetylene gas, etc. can also be used.
  • SiO x particles SiO x composite particles or a granulated body of SiO x and a carbon material
  • a carbon material by a vapor deposition (CVD) method
  • a petroleum-based pitch or a coal-based pitch is used.
  • At least one organic compound selected from the group consisting of a thermosetting resin and a condensate of naphthalene sulfonate and aldehydes is attached to a coating layer containing a carbon material, and then the organic compound is attached.
  • the obtained particles may be fired.
  • a dispersion liquid in which a SiO x particle (SiO x composite particle or a granulated body of SiO x and a carbon material) coated with a carbon material and the organic compound are dispersed in a dispersion medium is prepared, The dispersion is sprayed and dried to form particles coated with the organic compound, and the particles coated with the organic compound are fired.
  • Isotropic pitch can be used as the pitch, and phenol resin, furan resin, furfural resin, or the like can be used as the thermosetting resin.
  • phenol resin, furan resin, furfural resin, or the like can be used as the thermosetting resin.
  • condensate of naphthalene sulfonate and aldehydes naphthalene sulfonic acid formaldehyde condensate can be used.
  • a dispersion medium for dispersing the SiO x particles coated with the carbon material and the organic compound for example, water or alcohols (ethanol or the like) can be used. It is appropriate to spray the dispersion liquid in an atmosphere of 50 to 300 ° C.
  • the firing temperature is usually 600 to 1200 ° C., preferably 700 ° C. or higher, and more preferably 800 ° C. or higher. This is because the higher the processing temperature, the less the remaining impurities, and the formation of a coating layer containing a high-quality carbon material with high conductivity. However, the processing temperature needs to be lower than the melting point of SiO x .
  • a composite of SiO x and a carbon material is 510 cm ⁇ derived from Si in a Raman spectrum obtained by Raman spectroscopic analysis using a measurement laser having a wavelength of 532 nm.
  • the intensity I 510 of the first peak, the ratio I 510 / I 1343 of the peak intensity I 1343 of 1343cm -1, which derived from the carbon is preferably 0.25 or less.
  • I 510 / I 1343 is a microscopic Raman spectroscopy, mapping measurement (80 ⁇ 80 ⁇ m range, 2 ⁇ m step) of the complex, and averaging all spectra within the measurement range to obtain the peak of Si each intensity of peak (1343Cm around -1) of (510 cm around -1) and carbon (C) was measured, determined by calculating these ratios.
  • I 510 / I 1343 is of a complex between SiO x and the carbon material which satisfies the values of the, of the SiO x particle surface is exposed locations (SiO x particulate surface that is not coated with the carbon material Therefore, the effect of improving conductivity by combining SiO x and the carbon material is more remarkably exhibited. Therefore, in the manufacture of the composite of SiO x and carbon material, the conditions (for example, in the case of the CVD method, the processing temperature and the processing time are set so that I 510 / I 1343 satisfies the above value. It is desirable to adjust the liquid source concentration of the carbon material in the processing environment.
  • the non-aqueous secondary battery of the present invention has a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, a separator, and a non-aqueous electrolyte.
  • the non-aqueous secondary battery of the present invention is used as a negative electrode active material.
  • the negative electrode active material and the graphitic carbon material are used, there is no particular limitation on the other configurations and structures, and various configurations and configurations adopted in conventionally known non-aqueous secondary batteries Structure can be applied.
  • a negative electrode mixture layer containing a negative electrode active material and a binder is used on one side or both sides of a current collector.
  • the negative electrode active material of the present invention is used in combination with the negative electrode active material for a non-aqueous secondary battery and a graphitic carbon material.
  • the negative electrode active material for a non-aqueous secondary battery of the present invention has a higher capacity than a carbon material widely used as a negative electrode active material for a non-aqueous secondary battery.
  • the negative electrode (negative electrode mixture layer) is formed by repeated charge and discharge. There is a risk that the volume is greatly changed to deteriorate, and the capacity is reduced (that is, the charge / discharge cycle characteristics are reduced).
  • Graphite carbon material is widely used as a negative electrode active material for non-aqueous secondary batteries, and has a relatively large capacity.
  • the amount of volume change accompanying charging / discharging of the battery is negative electrode active materials for non-aqueous secondary batteries of the present invention. Smaller than the substance. Therefore, by using the negative electrode active material for non-aqueous secondary battery of the present invention and the graphitic carbon material in combination with the negative electrode active material, the amount of the negative electrode active material for non-aqueous secondary battery of the present invention is reduced. Since it is possible to satisfactorily suppress the deterioration of the charge / discharge cycle characteristics of the battery while suppressing the decrease in the capacity improvement effect of the battery as much as possible, the capacity is higher and the charge / discharge cycle characteristics are excellent. A water secondary battery can be obtained.
  • graphitic carbon material those conventionally used for negative electrode active materials of non-aqueous secondary batteries are preferably used.
  • natural graphite such as flake graphite; pyrolytic carbon And artificial graphite obtained by graphitizing easily graphitized carbon such as mesophase carbon microbeads (MCMB) and carbon fibers at 2800 ° C. or higher.
  • MCMB mesophase carbon microbeads
  • the nonaqueous secondary battery of the present invention is used from the viewpoint of satisfactorily securing the effect of increasing the capacity by using the negative electrode active material for a nonaqueous secondary battery of the present invention.
  • the content of the negative electrode active material for batteries in the total negative electrode active material is preferably 1% by mass or more, and more preferably 3% by mass or more. Further, from the viewpoint of better avoiding the problem due to volume change of the negative electrode active material for non-aqueous secondary battery of the present invention, the content of the negative electrode active material for non-aqueous secondary battery of the present invention in all negative electrode active materials is 20% by mass or less, and more preferably 15% by mass or less.
  • binder used for the negative electrode mixture layer include, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), and the like.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • a conductive material may be further added to the negative electrode mixture layer as a conductive aid.
  • a conductive material is not particularly limited as long as it does not cause a chemical change in the non-aqueous secondary battery.
  • carbon black thermal black, furnace black, channel black, ketjen black, acetylene black
  • carbon fiber carbon fiber
  • metal powder copper, nickel, aluminum, silver, etc.
  • metal fiber polyphenylene derivative (as described in JP-A-59-20971), etc. be able to.
  • carbon black is preferably used, and ketjen black and acetylene black are more preferable.
  • the particle size of the carbon material used as the conductive assistant is, for example, 0.01 ⁇ m or more in terms of the average particle size (D 50% ) measured by the same method as the negative electrode active material for non-aqueous secondary battery of the present invention. Is preferably 0.02 ⁇ m or more, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the negative electrode contains, for example, a negative electrode active material, a binder, and, if necessary, a paste-like or slurry-like negative electrode mixture in which a conductive additive is dispersed in a solvent such as N-methyl-2-pyrrolidone (NMP) water.
  • NMP N-methyl-2-pyrrolidone
  • the composition is prepared (however, the binder may be dissolved in a solvent), applied to one or both sides of the current collector, dried, and then subjected to a pressing process as necessary.
  • the negative electrode is not limited to those manufactured by the above manufacturing method, and may be manufactured by other manufacturing methods.
  • the thickness of the negative electrode mixture layer is preferably 10 to 100 ⁇ m per side of the current collector.
  • the density of the negative electrode mixture layer is calculated from the mass and thickness of the negative electrode mixture layer per unit area laminated on the current collector, and is preferably 1.0 to 1.9 g / cm 3 .
  • the total amount of the negative electrode active material is preferably 80 to 99% by mass
  • the amount of the binder is preferably 1 to 20% by mass
  • a conductive assistant is used. In that case, the amount is preferably 1 to 10% by mass.
  • the negative electrode current collector a copper or nickel foil, a punching metal, a net, an expanded metal, or the like can be used, but a copper foil is usually used.
  • the upper limit of the thickness is preferably 30 ⁇ m, and the lower limit is 5 ⁇ m in order to ensure mechanical strength. Is desirable.
  • a positive electrode mixture layer containing a positive electrode active material, a binder, a conductive additive and the like can be used on one side or both sides of the current collector.
  • a Li-containing transition metal oxide capable of occluding and releasing Li (lithium) ions is used.
  • the Li-containing transition metal oxide include those conventionally used for non-aqueous secondary batteries, specifically, Li y CoO 2 (where 0 ⁇ y ⁇ 1.1). Li z NiO 2 (where 0 ⁇ z ⁇ 1.1), Li e MnO 2 (where 0 ⁇ e ⁇ 1.1), Li a Co b M 1 1-b O 2 (However, M 1 is at least one metal element selected from the group consisting of Mg, Mn, Fe, Ni, Cu, Zn, Al, Ti, Ge, and Cr, and 0 ⁇ a ⁇ 1.1.
  • Li c Ni 1-d M 2 d O 2 (wherein M 2 is Mg, Mn, Fe, Co, Cu, Zn, Al, Ti, Ge and At least one metal element selected from the group consisting of Cr, 0 ⁇ c ⁇ 1.1, 0 ⁇ d Is 1.0.), Li f Mn g Ni h Co 1-g-h O 2 ( where is 0 ⁇ f ⁇ 1.1,0 ⁇ g ⁇ 1.0,0 ⁇ h ⁇ 1.0 Li) -containing transition metal oxides having a layered structure such as.), And only one of these may be used, or two or more may be used in combination.
  • the same binders as those exemplified above as the binder for the negative electrode mixture layer can be used.
  • the conductive auxiliary agent related to the positive electrode mixture layer for example, graphite (graphite carbon material) such as natural graphite (flaky graphite), artificial graphite; acetylene black, ketjen black, channel black, furnace black, Examples thereof include carbon blacks such as carbon blacks such as lamp black and thermal black; carbon fibers.
  • the positive electrode for example, a paste-like or slurry-like positive electrode mixture-containing composition in which a positive electrode active material, a binder, and a conductive additive are dispersed in a solvent such as NMP is prepared (however, the binder is dissolved in the solvent). It may be manufactured through a step of applying a press treatment as necessary after applying this to one or both sides of the current collector and drying it.
  • the positive electrode is not limited to those manufactured by the above manufacturing method, and may be manufactured by other manufacturing methods.
  • the thickness of the positive electrode mixture layer is preferably, for example, 10 to 100 ⁇ m per side of the current collector, and the density of the positive electrode mixture layer is the mass of the positive electrode mixture layer per unit area laminated on the current collector. Calculated from the thickness, it is preferably 3.0 to 4.5 g / cm 3 .
  • the amount of the positive electrode active material is preferably 60 to 95% by mass
  • the amount of the binder is preferably 1 to 15% by mass
  • the positive electrode current collector As the positive electrode current collector, the same ones used for positive electrodes of conventionally known non-aqueous secondary batteries can be used, and for example, an aluminum foil having a thickness of 10 to 30 ⁇ m is preferable.
  • the separator As the separator according to the nonaqueous secondary battery of the present invention, it is preferable that the separator has sufficient strength and can hold a large amount of nonaqueous electrolyte, and has a thickness of 5 to 50 ⁇ m and an open area ratio of 30 to 70%. Or a microporous membrane made of polyolefin such as polypropylene (PP).
  • the microporous membrane constituting the separator may be, for example, one using only PE or one using PP only, may contain an ethylene-propylene copolymer, and may be made of PE.
  • a laminate of a membrane and a PP microporous membrane may be used.
  • the separator according to the non-aqueous secondary battery includes a porous layer (A) mainly composed of a resin having a melting point of 140 ° C. or lower and a resin having a melting point of 150 ° C. or higher or an inorganic filler having a heat resistance temperature of 150 ° C. or higher.
  • a laminated separator composed of a porous layer (B) included as a main body can be used.
  • melting point means a melting temperature measured using a differential scanning calorimeter (DSC) in accordance with the provisions of JIS K 7121.
  • Heat resistant temperature is 150 ° C. or higher” means at least 150 ° C. This means that no deformation such as softening is observed.
  • the porous layer (A) according to the laminated separator is mainly for ensuring a shutdown function, and the melting point of the resin, which is a component in which the nonaqueous secondary battery is the main component of the porous layer (A).
  • the resin related to the porous layer (A) melts and closes the pores of the separator, thereby causing a shutdown that suppresses the progress of the electrochemical reaction.
  • Examples of the resin having a melting point of 140 ° C. or lower as the main component of the porous layer (A) include PE, and the form thereof is a substrate such as a microporous film used in a non-aqueous secondary battery or a nonwoven fabric. And PE particles coated thereon.
  • the volume of the resin having a main melting point of 140 ° C. or less is 50% by volume or more, and more preferably 70% by volume or more.
  • the volume is 100% by volume.
  • the porous layer (B) according to the laminated separator has a function of preventing a short circuit due to direct contact between the positive electrode and the negative electrode even when the internal temperature of the non-aqueous secondary battery is increased, Its function is ensured by a resin having a melting point of 150 ° C. or higher or an inorganic filler having a heat resistant temperature of 150 ° C. or higher. That is, when the battery becomes high temperature, even if the porous layer (A) shrinks, the porous layer (B) which does not easily shrink can directly generate positive and negative electrodes that can be generated when the separator is thermally contracted. It is possible to prevent a short circuit due to the contact of. Moreover, since this heat-resistant porous layer (B) acts as a skeleton of the separator, thermal contraction of the porous layer (A), that is, thermal contraction of the entire separator itself can be suppressed.
  • the porous layer (B) is formed mainly of a resin having a melting point of 150 ° C. or higher
  • the form thereof is, for example, a microporous film formed of a resin having a melting point of 150 ° C. or higher (for example, a battery made of PP as described above)
  • the composition for forming a porous layer (B) containing fine particles of a resin having a melting point of 150 ° C. or higher is applied to the porous layer (A).
  • a coating layer type in which a porous layer (B) containing fine particles of a resin having a melting point of 150 ° C. or higher is laminated.
  • Examples of the resin constituting the fine particles of the resin having a melting point of 150 ° C. or higher include crosslinked polymethyl methacrylate, crosslinked polystyrene, crosslinked polydivinylbenzene, crosslinked styrene-divinylbenzene copolymer, polyimide, melamine resin, phenol resin, benzoguanamine And various cross-linked polymers such as formaldehyde condensates; heat-resistant polymers such as PP, polysulfone, polyether sulfone, polyphenylene sulfide, PTFE, polyacrylonitrile, aramid, and polyacetal.
  • crosslinked polymethyl methacrylate crosslinked polystyrene, crosslinked polydivinylbenzene, crosslinked styrene-divinylbenzene copolymer, polyimide, melamine resin, phenol resin, benzoguanamine
  • various cross-linked polymers such as formaldehyde condensates
  • the particle diameter of the fine particles of the resin having a melting point of 150 ° C. or higher is an average particle diameter D 50% measured by the same method as that of the negative electrode active material for a non-aqueous secondary battery of the present invention, for example, 0.01 ⁇ m or more. Is preferably 0.1 ⁇ m or more, more preferably 10 ⁇ m or less, and even more preferably 2 ⁇ m or less.
  • the total volume of the constituent components of the porous layer (B) (the total volume excluding pores) ), It is preferably 50% by volume or more, preferably 70% by volume or more, more preferably 80% by volume or more, and still more preferably 90% by volume or more.
  • the porous layer (B) is mainly composed of an inorganic filler having a heat resistant temperature of 150 ° C. or higher
  • a composition for forming the porous layer (B) containing an inorganic filler having a heat resistant temperature of 150 ° C. or higher (coating liquid) ) Is applied to the porous layer (A), and a porous layer (B) containing an inorganic filler having a heat resistant temperature of 150 ° C. or higher is laminated.
  • the inorganic filler according to the porous layer (B) has a heat-resistant temperature of 150 ° C. or higher, is stable with respect to the non-aqueous electrolyte of the non-aqueous secondary battery, and is oxidized and reduced within the operating voltage range of the non-aqueous secondary battery.
  • Any electrochemically stable material that is difficult to be treated may be used, but fine particles are preferable from the viewpoint of dispersion and the like, and alumina, silica, and boehmite are preferable.
  • Alumina, silica, and boehmite have high oxidation resistance, and the particle size and shape can be adjusted to desired values, etc., making it easy to accurately control the porosity of the porous layer (B). It becomes.
  • the thing of the said illustration may be used individually by 1 type, and may use 2 or more types together, for example.
  • an inorganic filler having a heat resistant temperature of 150 ° C. or higher and a resin fine particle having a melting point of 150 ° C. or higher may be used in combination.
  • a substantially spherical shape (a true spherical shape is included), a substantially ellipsoid shape (an ellipsoid shape is included), plate shape, etc.
  • Various shapes can be used.
  • the average particle diameter of the inorganic filler having a heat resistant temperature of 150 ° C. or higher (the average particle diameter of the plate-like filler and the other shape filler. The same applies hereinafter) of the porous layer (B) is too small, the ion permeability is high. Since it falls, it is preferable that it is 0.3 micrometer or more, and it is more preferable that it is 0.5 micrometer or more.
  • the average particle diameter is preferably 5 ⁇ m or less, and more preferably 2 ⁇ m or less.
  • the average particle diameter of the inorganic filler having a heat resistant temperature of 150 ° C. or higher as used herein is an average particle diameter (D 50% ) determined by the same method as the average particle diameter of the negative electrode active material.
  • the amount in the porous layer (B) is the amount of the porous layer (B). Is 50% by volume or more, preferably 70% by volume or more, more preferably 80% by volume or more, and 90% by volume or more. More preferably it is.
  • the inorganic filler having a heat resistant temperature of 150 ° C. or higher and the fine particles of the resin having a melting point of 150 ° C. or higher are used in combination, it is sufficient that both of them form the main body of the porous layer (B).
  • the total amount of these components may be 50% by volume or more in the total volume of the constituent components of the porous layer (B) (total volume excluding the pores), and 70% by volume or more. It is preferable to make it 80% by volume or more, more preferably 90% by volume or more. Thereby, the effect similar to the case where the inorganic filler in a porous layer (B) is made into high content as mentioned above is securable.
  • porous layer (B) fine particles of a resin having a melting point of 150 ° C. or higher or inorganic fillers having a heat resistant temperature of 150 ° C. or higher are bound, or the porous layer (B) and the porous layer (A)
  • an organic binder is preferably contained in order to integrate them.
  • Organic binders include ethylene-vinyl acetate copolymers (EVA, structural units derived from vinyl acetate of 20 to 35 mol%), ethylene-acrylic acid copolymers such as ethylene-ethyl acrylate copolymers, fluorine-based binders Examples include rubber, SBR, CMC, hydroxyethyl cellulose (HEC), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinyl pyrrolidone (PVP), cross-linked acrylic resin, polyurethane, and epoxy resin.
  • a heat-resistant binder having a heat-resistant temperature is preferably used.
  • the organic binder those exemplified above may be used singly or in combination of two or more.
  • highly flexible binders such as EVA, ethylene-acrylic acid copolymer, fluorine rubber, and SBR are preferable.
  • highly flexible organic binders include Mitsui DuPont Polychemical's “Evaflex Series (EVA)”, Nihon Unicar's EVA, Mitsui DuPont Polychemical's “Evaflex-EAA Series (Ethylene).
  • EVA Evaflex Series
  • EVA Nihon Unicar's EVA
  • -Acrylic acid copolymer) ", EEA of Nihon Unicar”
  • Daiel Latex Series (Fluororubber) of Daikin Industries
  • TRD-2001 (SBR) of JSR
  • BM-400B Nippon Zeon "
  • the organic binder when used for the porous layer (B), it may be used in the form of an emulsion dissolved or dispersed in a solvent for a composition for forming the porous layer (B) described later.
  • the coating laminate type separator is, for example, a composition for forming a porous layer (B) containing a fine resin particle having a melting point of 150 ° C. or higher or an inorganic filler having a heat resistant temperature of 150 ° C. or higher (a liquid composition such as a slurry). Etc.) may be applied to the surface of the microporous membrane for constituting the porous layer (A) and dried at a predetermined temperature to form the porous layer (B).
  • the composition for forming the porous layer (B) contains fine particles of a resin having a melting point of 150 ° C. or higher or an inorganic filler having a heat resistant temperature of 150 ° C. or higher, and, if necessary, an organic binder and the like. (Including the medium, the same shall apply hereinafter)).
  • the organic binder can be dissolved in a solvent.
  • the solvent used in the composition for forming the porous layer (B) is not particularly limited as long as it can uniformly disperse the inorganic filler and can uniformly dissolve or disperse the organic binder.
  • Common organic solvents such as hydrocarbons, furans such as tetrahydrofuran, and ketones such as methyl ethyl ketone and methyl isobutyl ketone are preferably used.
  • alcohols ethylene glycol, propylene glycol, etc.
  • various propylene oxide glycol ethers such as monomethyl acetate may be appropriately added to these solvents.
  • water may be used as a solvent.
  • alcohols methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, etc.
  • the composition for forming the porous layer (B) has a solid content containing, for example, 10 to 80% by mass of resin fine particles having a melting point of 150 ° C. or higher, an inorganic filler having a heat resistant temperature of 150 ° C. or higher, and an organic binder. It is preferable to do.
  • the porous layer (A) and the porous layer (B) do not have to be one each, and a plurality of layers may be present in the separator.
  • the porous layer (A) may be arranged on both sides of the porous layer (B), or the porous layer (B) may be arranged on both sides of the porous layer (A).
  • increasing the number of layers may increase the thickness of the separator and increase the internal resistance of the battery or decrease the energy density. Therefore, it is not preferable to increase the number of layers.
  • the total number of layers of the porous layer (A) and the porous layer (B) is preferably 5 or less.
  • the thickness of a separator (a separator made of a polyolefin microporous film or the laminated separator) according to a non-aqueous secondary battery is more preferably 10 to 30 ⁇ m.
  • the thickness of the porous layer (B) [when the separator has a plurality of porous layers (B), the total thickness thereof] is determined by each of the functions of the porous layer (B). From the viewpoint of exhibiting more effectively, it is preferably 3 ⁇ m or more. However, if the porous layer (B) is too thick, the energy density of the battery may be lowered. Therefore, the thickness of the porous layer (B) is preferably 8 ⁇ m or less.
  • the thickness of the porous layer (A) [when the separator has a plurality of porous layers (I), the total thickness thereof. same as below. ] Is preferably 6 ⁇ m or more, more preferably 10 ⁇ m or more, from the viewpoint of more effectively exerting the above-described action (particularly the shutdown action) due to the use of the porous layer (A).
  • the porous layer (A) is too thick, there is a possibility that the energy density of the battery may be lowered.
  • the force that the porous layer (A) tends to shrink is increased, and the heat of the entire separator is increased. There is a possibility that the action of suppressing the shrinkage becomes small. Therefore, the thickness of the porous layer (A) is preferably 25 ⁇ m or less, more preferably 20 ⁇ m or less, and further preferably 14 ⁇ m or less.
  • the porosity of the separator as a whole is preferably 30% or more in a dried state in order to secure the amount of electrolyte solution retained and to improve ion permeability.
  • the separator porosity is preferably 70% or less in a dry state.
  • the porosity of the separator: P (%) can be calculated by obtaining the sum for each component i from the thickness of the separator, the mass per area, and the density of the constituent components using the following equation (1).
  • a i ratio of component i when the total mass is 1
  • ⁇ i density of component i (g / cm 3 )
  • m mass per unit area of the separator (g / cm 2 )
  • t thickness of separator (cm).
  • the porosity of the porous layer (A) obtained by this method is preferably 30 to 70%.
  • the porosity of the porous layer (B) obtained by this method is preferably 20 to 60%.
  • the separator preferably has a high mechanical strength, for example, a puncture strength of 3N or more is preferable.
  • the negative electrode active material for a non-aqueous secondary battery according to the present invention has a large volume expansion / contraction during charging / discharging, and is mechanically applied to the separator facing the negative electrode due to expansion / contraction of the entire negative electrode by repeated charging / discharging cycles. Damage will be added. If the piercing strength of the separator is 3N or more, good mechanical strength is ensured, and mechanical damage to the separator can be reduced.
  • Examples of the separator having a puncture strength of 3N or more include the above-described laminated separator, and in particular, an inorganic filler having a heat resistant temperature of 150 ° C. or higher in the porous layer (A) mainly composed of a resin having a melting point of 140 ° C. or lower.
  • a separator in which a porous layer (B) containing as a main component is laminated is preferable. This is probably because the mechanical strength of the inorganic filler is high, so that the mechanical strength of the entire separator can be increased by supplementing the mechanical strength of the porous layer (A).
  • the piercing strength can be measured by the following method.
  • a separator is fixed on a plate having a hole with a diameter of 2 inches so as not to be wrinkled or bent, and a semispherical metal pin having a tip diameter of 1.0 mm is lowered onto a measurement sample at a speed of 120 mm / min.
  • an average value is calculated
  • Non-aqueous electrolyte As the non-aqueous electrolyte solution according to the non-aqueous secondary battery of the present invention, a solution in which a lithium salt is dissolved in an organic solvent containing a phosphonoacetate compound satisfying the general formula (2) is used. It is preferable.
  • R 1 , R 2 and R 3 each independently represent an alkyl group, alkenyl group or alkynyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom, and n Represents an integer of 0-6.
  • Examples of the phosphonoacetate compound include the following compounds.
  • the content of the phosphonoacetate compound represented by the general formula (2) in the non-aqueous electrolyte used in the non-aqueous secondary battery improves battery swelling particularly when stored at high temperature in a high-voltage charge state. From the viewpoint of ensuring a good suppressing effect, the content is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. On the other hand, if the amount of the phosphonoacetate compound in the non-aqueous electrolyte is too large, the load characteristics, charge / discharge cycle characteristics, and storage characteristics of the battery may be degraded. Therefore, the content of the phosphonoacetate compound represented by the general formula (2) in the nonaqueous electrolytic solution used for the nonaqueous secondary battery is preferably 5% by mass or less, and 2.5% by mass. The following is more preferable.
  • the non-aqueous electrolyte used for the non-aqueous secondary battery contains 1,3-dioxane.
  • 1,3-dioxane is more preferably used in combination with the phosphonoacetate compound represented by the general formula (2). In that case, the charge / discharge cycle characteristics of the nonaqueous secondary battery are further improved. It becomes possible.
  • the content of 1,3-dioxane in the non-aqueous electrolyte used in the non-aqueous secondary battery increases the load characteristics of the battery when charged at a high voltage and the capacity recovery after high-temperature storage. From the viewpoint of securing the effect of enhancing the charge / discharge cycle characteristics of the battery by the combination with the phosphonoacetate compound represented by (2), it is preferably 0.1% by mass or more, and 0.5% by mass or more. More preferably. On the other hand, if the amount of 1,3-dioxane in the non-aqueous electrolyte is too large, the load characteristics, charge / discharge cycle characteristics, and storage characteristics of the battery may be degraded. Therefore, the content of 1,3-dioxane in the non-aqueous electrolyte used for the non-aqueous secondary battery is preferably 5% by mass or less, and more preferably 2.5% by mass or less.
  • a non-aqueous electrolyte containing a halogen-substituted cyclic carbonate acts on the negative electrode and has an action of suppressing the reaction between the negative electrode and the non-aqueous electrolyte component. Therefore, a nonaqueous secondary battery with better charge / discharge cycle characteristics can be obtained by using a nonaqueous electrolytic solution that also contains a halogen-substituted cyclic carbonate.
  • halogen-substituted cyclic carbonate a compound represented by the following general formula (3) can be used.
  • R 4 , R 5 , R 6 and R 7 represent hydrogen, a halogen element or an alkyl group having 1 to 10 carbon atoms, and a part or all of hydrogen of the alkyl group is halogen. may be substituted with an element, at least one of R 4, R 5, R 6 and R 7 are halogen, R 4, R 5, R 6 and R 7 have different respective Two or more may be the same.
  • R 4 , R 5 , R 6 and R 7 are alkyl groups, the smaller the number of carbon atoms, the better.
  • the halogen element fluorine is particularly preferable.
  • FEC 4-fluoro-1,3-dioxolan-2-one
  • the content of the halogen-substituted cyclic carbonate in the non-aqueous electrolyte used for the non-aqueous secondary battery is preferably 0.1% by mass or more from the viewpoint of ensuring better the effect of its use. More preferably, it is 5% by mass or more. However, if the content of the halogen-substituted cyclic carbonate in the non-aqueous electrolyte is too large, the effect of improving storage characteristics may be reduced. Therefore, the content of the halogen-substituted cyclic carbonate in the non-aqueous electrolyte used for the non-aqueous secondary battery is preferably 10% by mass or less, and more preferably 5% by mass or less.
  • VC non-aqueous electrolyte containing vinylene carbonate
  • VC acts on a negative electrode (in particular, a negative electrode using a carbon material as a negative electrode active material) and has an action of suppressing a reaction between the negative electrode and a non-aqueous electrolyte component. Therefore, a nonaqueous secondary battery having better charge / discharge cycle characteristics can be obtained by using a nonaqueous electrolytic solution that also contains VC.
  • the content of VC in the non-aqueous electrolyte used for the non-aqueous secondary battery is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, from the viewpoint of better securing the effect of the use. It is more preferable that However, if the content of VC in the non-aqueous electrolyte is too large, the effect of improving storage characteristics may be reduced. Therefore, the content of VC in the non-aqueous electrolyte used for the non-aqueous secondary battery is preferably 10% by mass or less, and more preferably 4.0% by mass or less.
  • the lithium salt used in the non-aqueous electrolyte is not particularly limited as long as it is dissociated in a solvent to form Li + ions and hardly causes a side reaction such as decomposition in a voltage range used as a battery.
  • LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 and other inorganic lithium salts LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ⁇ 2), LiN (RfOSO 2 ) 2 [where Rf is a fluoroalkyl group] and the like can be used. .
  • the concentration of this lithium salt in the non-aqueous electrolyte is preferably 0.5 to 1.5 mol / l, more preferably 0.9 to 1.25 mol / l.
  • the organic solvent used in the non-aqueous electrolyte is not particularly limited as long as it dissolves the lithium salt and does not cause side reactions such as decomposition in the voltage range used as a battery.
  • cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, chain carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; chain esters such as methyl propionate; cyclic esters such as ⁇ -butyrolactone; dimethoxyethane, Chain ethers such as diethyl ether, 1,3-dioxolane, diglyme, triglyme and tetraglyme; cyclic ethers such as 1,4-dioxane, tetrahydrofuran and 2-methyltetrahydrofuran; acetonitrile, propionitrile, methoxypropionitrile and the like Nitriles; sulfites such as ethylene glycol s
  • Non-aqueous electrolytes used for non-aqueous secondary batteries include acid anhydrides and sulfonate esters for the purpose of further improving charge / discharge cycle characteristics and improving safety such as high-temperature storage and overcharge prevention.
  • Additives such as dinitrile, 1,3-propane sultone, diphenyl disulfide, cyclohexylbenzene, biphenyl, fluorobenzene, and t-butylbenzene can also be added as appropriate.
  • a gel obtained by adding a known gelling agent such as a polymer to the non-aqueous electrolyte can be used.
  • Non-aqueous secondary battery of this invention there is no restriction
  • any of a coin shape, a button shape, a sheet shape, a laminated shape, a cylindrical shape, a flat shape, a square shape, a large size used for an electric vehicle, etc. may be used.
  • a rectangular (square tube) outer can, a flat outer can, a laminated film outer casing, etc. having a small thickness with respect to the width are used.
  • the rectangular shape having the exterior body (exterior can) as described above In the case of a battery or a flat battery, the effect is particularly remarkable.
  • a laminated electrode body in which the positive electrode and the negative electrode are laminated via the separator, or the positive electrode and the negative electrode are laminated via the separator Can be used as a spirally wound electrode body. Further, depending on the form of the battery, a plurality of positive electrodes and negative electrodes can be used in these laminated electrode bodies and wound electrode bodies.
  • the porous layer (A) mainly composed of a resin having a melting point of 140 ° C. or lower is used.
  • a separator in which a porous layer (B) mainly containing an inorganic filler having a heat resistant temperature of 150 ° C. or higher is used, it is preferable to dispose the porous layer (B) so as to face at least the positive electrode. .
  • the oxidation of the separator by the positive electrode can be suppressed better, It is also possible to improve the storage characteristics and charge / discharge cycle characteristics of the battery at high temperatures. Further, when an additive such as vinylene carbonate or cyclohexylbenzene is added to the non-aqueous electrolyte, there is a possibility that the battery characteristics may be remarkably deteriorated by forming a film on the positive electrode side and clogging the pores of the separator. Therefore, an effect of suppressing clogging of the pores can be expected by causing the relatively porous porous layer (B) to face the positive electrode.
  • an additive such as vinylene carbonate or cyclohexylbenzene
  • the porous layer (A) faces the negative electrode, and thus, for example, the porous separator is porous during shutdown.
  • the thermoplastic resin melted from the layer (A) is suppressed from being absorbed by the electrode mixture layer, and can be efficiently used to close the pores of the separator.
  • the mass of the positive electrode active material contained in the positive electrode is p
  • the mass of the negative electrode active material contained in the negative electrode is n.
  • P / n is preferably 1.0 to 3.6.
  • the expansion / contraction of the volume accompanying the charging / discharging of the battery can be suppressed, and the deterioration of the charging / discharging cycle characteristics of the battery due to the pulverization of the material particles can be suppressed more favorably.
  • a higher battery capacity can be ensured by setting the ratio of p / n to 1.0 or more.
  • the coprecipitated compound was washed with water, filtered and dried to obtain a hydroxide containing Ni, Co and Mn in a molar ratio of 6: 2: 2. 0.196 mol of this hydroxide and 0.204 mol of LiOH.H 2 O were dispersed in ethanol to form a slurry, and then mixed with a planetary ball mill for 40 minutes and dried at room temperature to obtain a mixture. . Next, the mixture is put in an alumina crucible, heated to 600 ° C. in a dry air flow of 2 dm 3 / min, kept at that temperature for 2 hours for preheating, further heated to 900 ° C. and heated to 12 ° C. Lithium-containing composite oxide A was synthesized by firing for a period of time.
  • the obtained lithium-containing composite oxide A was washed with water and then heat-treated in the atmosphere (oxygen concentration is about 20 vol%) at 850 ° C. for 12 hours, and then pulverized in a mortar to obtain a powder.
  • the lithium-containing composite oxide A after pulverization was stored in a desiccator.
  • the composition analysis was performed as follows using ICP method. First, 0.2 g of the lithium-containing composite oxide A was sampled and placed in a 100 mL container. Thereafter, 5 mL of pure water, 2 mL of aqua regia, and 10 mL of pure water were added in order and dissolved by heating. After cooling, the mixture was further diluted 25 times and analyzed by ICP (“ICP-757” manufactured by JARRELASH) (calibration). Line method). From the obtained results, the composition of the lithium-containing composite oxide A was derived and found to be a composition represented by Li 1.02 Ni 0.6 Co 0.2 Mn 0.2 O 2 .
  • the coprecipitated compound was washed with water, filtered and dried to obtain a hydroxide containing Ni, Mn and Co in a molar ratio of 90: 5: 5. 0.196 mol of this hydroxide, 0.204 mol of LiOH.H 2 O and 0.001 mol of TiO 2 were dispersed in ethanol to form a slurry, and then mixed for 40 minutes with a planetary ball mill. And dried to obtain a mixture. Next, the mixture is put in an alumina crucible, heated to 600 ° C. in a dry air flow of 2 dm 3 / min, held at that temperature for 2 hours for preheating, further heated to 800 ° C. and heated to 12 ° C. Lithium-containing composite oxide B was synthesized by firing for a period of time. The obtained lithium-containing composite oxide B was pulverized into a powder in a mortar and then stored in a desiccator.
  • the composition analysis was performed by a calibration curve method using the ICP method described above, the results obtained have been derived composition of the lithium-containing complex oxide B, Li 1.02 It was found that the composition was represented by Ni 0.895 Co 0.05 Mn 0.05 Ti 0.005 O 2 .
  • Example 1 ⁇ Preparation of positive electrode> LiCoO 2 as a positive electrode active material: 70 parts by mass, LiMn 0.2 Ni 0.6 Co 0.2 O 2 : 30 parts by mass as the lithium-containing composite oxide A, and artificial graphite as a conductive auxiliary agent: 1 Part by mass and Ketjen Black: 1 part by mass and PVDF as a binder: 10 parts by mass were mixed so as to be uniform using NMP as a solvent to prepare a positive electrode mixture-containing paste.
  • the positive electrode mixture-containing paste is intermittently applied to both surfaces of a current collector made of an aluminum foil having a thickness of 15 ⁇ m by adjusting the thickness, dried, and then subjected to a calendar treatment so that the total thickness becomes 130 ⁇ m. The thickness of the mixture layer was adjusted, and the positive electrode was produced by cutting so that the width was 54.5 mm. Further, a tab was welded to the exposed portion of the aluminum foil of the positive electrode to form a lead portion.
  • ⁇ Production of negative electrode> 5 is a material in which the surface of SiO is coated with carbon (the amount of carbon in the composite is 20% by mass; hereinafter referred to as “SiO / carbon composite”) and graphitic carbon having an average particle diameter D 50 of 16 ⁇ m.
  • SiO / carbon composite a material in which the surface of SiO is coated with carbon (the amount of carbon in the composite is 20% by mass; hereinafter referred to as “SiO / carbon composite”) and graphitic carbon having an average particle diameter D 50 of 16 ⁇ m.
  • Mixture mixed at a mass ratio of 95: 98 parts by mass, CMC aqueous solution having a concentration of 1% by mass adjusted to a viscosity of 1500 to 5000 mPa ⁇ s: 1.0 part by mass, and SBR: 1.0 part by mass Was mixed with ion-exchanged water having a specific conductivity of 2.0 ⁇ 10 5 ⁇ / cm or more as a solvent to prepare an aqueous negative
  • the SiO / carbon composite is obtained by subjecting SiO having a particle size distribution adjusted by pulverization and classification under the conditions of a treatment temperature of 1100 ° C. and a treatment time of 4 hours using toluene as a liquid source.
  • the SiO / carbon composite obtained after the CVD treatment has a D 10% of 5 ⁇ m, a D 50% of 9 ⁇ m, a D 90% of 13 ⁇ m, a half width of the Si (220) diffraction peak of 0.8 °, and I a / Ib is 3.3 and I510 / I1343 is 0.10.
  • the negative electrode mixture-containing paste is intermittently applied to both sides of a current collector made of a copper foil having a thickness of 8 ⁇ m while adjusting the thickness, dried, and then subjected to a calendar process so that the total thickness becomes 110 ⁇ m.
  • the thickness of the mixture layer was adjusted, and the negative electrode was produced by cutting so that the width was 55.5 mm. Further, a tab was welded to the exposed portion of the copper foil of the negative electrode to form a lead portion.
  • ⁇ Preparation of separator> Add 5 kg of ion-exchanged water and 0.5 kg of a dispersant (aqueous polycarboxylic acid ammonium salt, solid content concentration 40 mass%) to 5 kg of boehmite with an average particle diameter D of 50% of 1 ⁇ m. Dispersion was prepared by crushing for 10 hours with a ball mill at times / minute. The treated dispersion was vacuum-dried at 120 ° C. and observed with a scanning electron microscope (SEM). As a result, the boehmite was almost plate-shaped.
  • a dispersant aqueous polycarboxylic acid ammonium salt, solid content concentration 40 mass
  • PE microporous separator for non-aqueous secondary battery [porous layer (A): thickness 12 ⁇ m, porosity 40%, average pore diameter 0.08 ⁇ m, PE melting point 135 ° C.] on one side corona discharge treatment (discharge amount 40 W ⁇ min / m 2 ), and a slurry for forming a porous layer (B) is applied to the treated surface by a micro gravure coater and dried to form a porous layer (B) having a thickness of 4 ⁇ m, and then laminated.
  • a mold separator was obtained.
  • the mass per unit area of the porous layer (B) in this separator was 5.5 g / m 2 , the boehmite volume content was 95% by volume, and the porosity was 45%.
  • ⁇ Battery assembly> The positive electrode and the negative electrode obtained as described above were overlapped with the separator porous layer (B) facing the positive electrode and wound in a spiral shape to produce a wound electrode body.
  • the obtained wound electrode body was crushed into a flat shape, placed in an aluminum alloy outer can having a thickness of 5 mm, a width of 42 mm, and a height of 61 mm, and the non-aqueous electrolyte was injected.
  • a non-aqueous secondary battery having the structure shown in FIG. 1 and the appearance shown in FIG. 2 was produced.
  • This battery includes a cleavage vent for lowering the pressure when the internal pressure rises at the top of the can.
  • FIG. 1A is a plan view
  • FIG. 1B is a partial cross-sectional view thereof.
  • FIG. 2 is spirally wound through the separator 3 as described above, and then pressed so as to be flattened and accommodated in a rectangular tube-shaped outer can 4 together with the electrolyte as a flat wound electrode body 6 Has been.
  • a metal foil, an electrolytic solution, and the like as a current collector used for manufacturing the positive electrode 1 and the negative electrode 2 are not illustrated.
  • the separator layers are not shown separately.
  • the outer can 4 is made of an aluminum alloy and constitutes an outer casing of the battery.
  • the outer can 4 also serves as a positive electrode terminal.
  • the insulator 5 which consists of PE sheets is arrange
  • the positive electrode lead body 7 and the negative electrode lead body 8 thus drawn are drawn out.
  • a stainless steel terminal 11 is attached to a sealing lid plate 9 made of aluminum alloy for sealing the opening of the outer can 4 through a PP insulating packing 10, and an insulator 12 is attached to the terminal 11.
  • a stainless steel lead plate 13 is attached.
  • the cover plate 9 is inserted into the opening of the outer can 4 and welded to join the opening of the outer can 4 to seal the inside of the battery.
  • a non-aqueous electrolyte inlet 14 is provided in the cover plate 9, and a sealing member is inserted into the non-aqueous electrolyte inlet 14, for example, laser welding or the like. (See FIG. 1 and FIG. 2, in practice, the non-aqueous electrolyte inlet 14 is actually sealed with the non-aqueous electrolyte inlet.) Although it is a member, for ease of explanation, it is shown as a non-aqueous electrolyte inlet 14).
  • the lid plate 9 is provided with a cleavage vent 15 as a mechanism for discharging the internal gas to the outside when the temperature of the battery rises.
  • the outer can 4 and the lid plate 9 function as a positive electrode terminal by directly welding the positive electrode lead body 7 to the lid plate 9, and the negative electrode lead body 8 is welded to the lead plate 13.
  • the terminal 11 functions as a negative electrode terminal by conducting the negative electrode lead body 8 and the terminal 11 through the lead plate 13, but depending on the material of the outer can 4, the sign may be reversed. There is also.
  • FIG. 2 is a perspective view schematically showing the external appearance of the battery shown in FIG. 1.
  • FIG. 2 is shown for the purpose of showing that the battery is a square battery.
  • FIG. 1 schematically shows a battery, and only specific members among the members constituting the battery are shown. Also in FIG. 1, the inner peripheral portion of the electrode body is not cross-sectional.
  • Examples 2 to 5 and Comparative Examples 1 to 4 A negative electrode was produced in the same manner as in Example 1 except that the SiO / carbon composite was changed to the one shown in Table 1, and the nonaqueous secondary battery was made in the same manner as in Example 1 except that these negative electrodes were used.
  • the carbon content of the SiO / carbon composite was adjusted by the CVD processing time. Specifically, the CVD processing time in the SiO / carbon composite used in Example 3 is 2.4 hours, and the CVD processing time in the SiO / carbon composite used in Comparative Example 1 is 3 hours.
  • Example 6 A positive electrode was produced in the same manner as in Example 1 except that the lithium-containing composite oxide B was used in place of the lithium-containing composite oxide A, and the non-aqueous solution was used in the same manner as in Example 1 except that this positive electrode was used. A secondary battery was produced.
  • each battery after the initial discharge capacity measurement was subjected to constant current-constant voltage charging (total charging time: 1 hour) at a constant current of 0.5 C and a constant voltage of 4.35 V at 25 ° C., and then at 25 ° C. Stored in a thermostatic bath for 7 days. Then, each battery was taken out from the thermostat and constant current discharge (discharge end voltage: 2.7 V) was performed at 1C.
  • ⁇ 45 ° C 30 day storage test> Except for changing the storage time in the thermostatic bath to 30 days for each of the batteries of Examples and Comparative Examples (batteries different from those subjected to a storage test at 25 ° C. for 7 days and a storage test at 45 ° C. for 7 days), 45 The initial discharge capacity and the discharge capacity after storage at 45 ° C. for 30 days were measured by the same method as the storage test at 7 ° C., and the capacity retention rate was calculated.
  • the structure of the SiO / carbon composite used for the negative electrode is shown in Table 1, and the evaluation results are shown in Table 2.
  • the initial discharge capacity in Table 2 shows the value measured during the storage test at 25 ° C. for 7 days as a relative value when the value in the nonaqueous secondary battery of Example 1 is 100.
  • Examples 1 to 2 in which the negative electrode active material was used in combination with SiO having an average particle diameter D of 50% and a Si (220) diffraction peak having an appropriate half-value width and graphite carbon were used in combination.
  • the non-aqueous secondary battery of No. 6 has a large initial discharge capacity, and has a high capacity retention rate after storage at 25 ° C. for 7 days, 45 ° C. for 7 days, and 45 ° C. for 30 days, and has excellent storage characteristics. is doing.
  • the battery of Comparative Example 1 using SiO with an average particle diameter D of 50% too small and the battery of Comparative Example 3 using SiO with a half-width of the (220) diffraction peak of Si being too large are 45 ° C.
  • the capacity retention rate after storage for 30 days is low, and the storage characteristics are inferior.
  • the battery of Comparative Example 2 using SiO FWHM of (220) diffraction peak of Si is too small, and the average cell diameter D 50% is Comparative Example 4 using the SiO too large, the initial discharge capacity small.
  • the non-aqueous secondary battery of the present invention has various battery characteristics including storage characteristics, it has been known for a long time for use in power supplies of small and multifunctional portable devices. It can be preferably used for various applications to which the used non-aqueous secondary battery is applied.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Silicon Compounds (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention vise à fournir une batterie secondaire non aqueuse ayant une capacité élevée et de bonnes caractéristiques de stockage, et un matériau actif d'anode pour former la batterie secondaire non aqueuse. A cet effet, le problème est résolu par les éléments suivants : un matériau actif d'anode de batterie secondaire non aqueuse caractérisé en ce qu'il comprend un matériau qui comprend Si et O dans les éléments constituants, ayant une taille de particule moyenne D50% de 6 à 10 µm telle que déterminée par le procédé de diffusion de diffraction laser, et ayant une largeur à mi-hauteur de 0,6 à 1,0° pour le pic de diffraction (220) du Si déterminé par un procédé de diffraction des rayons X utilisant des rayons CuKα ; et une batterie secondaire non aqueuse caractérisée par l'utilisation du matériau actif d'anode de batterie secondaire non aqueuse et d'un matériau carboné à base de graphite en tant que matériaux actifs d'anode.
PCT/JP2013/074969 2012-10-30 2013-09-17 Matériau actif d'anode pour batterie secondaire non aqueuse et batterie secondaire non aqueuse Ceased WO2014069117A1 (fr)

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CN106537663A (zh) * 2014-07-15 2017-03-22 信越化学工业株式会社 非水电解质二次电池用负极材料以及负极活性物质颗粒的制造方法
CN109952672A (zh) * 2016-11-14 2019-06-28 日立化成株式会社 锂离子二次电池用负极材、锂离子二次电池用负极和锂离子二次电池
JP2021044250A (ja) * 2016-02-05 2021-03-18 株式会社Ｇｓユアサ 蓄電素子

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KR20210094685A (ko) * 2020-01-21 2021-07-30 대주전자재료 주식회사 규소-규소 복합산화물-탄소 복합체, 이의 제조방법 및 이를 포함하는 음극 활물질

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