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WO2015140937A1 - Électrode pour batterie à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux et bloc-batterie - Google Patents

Électrode pour batterie à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux et bloc-batterie Download PDF

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Publication number
WO2015140937A1
WO2015140937A1 PCT/JP2014/057404 JP2014057404W WO2015140937A1 WO 2015140937 A1 WO2015140937 A1 WO 2015140937A1 JP 2014057404 W JP2014057404 W JP 2014057404W WO 2015140937 A1 WO2015140937 A1 WO 2015140937A1
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Prior art keywords
negative electrode
electrode
active material
peak
battery
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PCT/JP2014/057404
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English (en)
Japanese (ja)
Inventor
堀田康之
森田朋和
久保木貴志
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株式会社 東芝
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Priority to PCT/JP2014/057404 priority Critical patent/WO2015140937A1/fr
Publication of WO2015140937A1 publication Critical patent/WO2015140937A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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

  • Embodiments relate to a nonaqueous electrolyte battery electrode, a nonaqueous electrolyte secondary battery, and a battery pack.
  • Embodiment aims at providing the electrode for nonaqueous electrolyte batteries excellent in cycling characteristics.
  • An electrode for a nonaqueous electrolyte battery includes a current collector, and a mixture layer containing a carbonaceous material and a composite containing a metal in the carbonaceous material and a binder on the current collector.
  • the peak derived from CH 2 obtained by X-ray photoelectron spectroscopic analysis of the active material is 18 mol% or more of the peak in C1s.
  • the electrode for a nonaqueous electrolyte battery according to the first embodiment includes a current collector, a negative electrode composite containing a carbonaceous material and an active material including a composite containing a metal in the carbonaceous material and a binder on the current collector. It has an agent layer.
  • the electrode of the embodiment will be described by taking the negative electrode as an example, the electrode of the embodiment may be used for the positive electrode. Further, in the following description, the embodiment will be described taking a non-aqueous electrolyte secondary battery as an example, but the electrode of the embodiment can be used for various batteries.
  • the negative electrode 100 of the first embodiment includes a negative electrode mixture layer 101 and a current collector 102.
  • the negative electrode mixture layer 101 is a layer of a mixture containing an active material disposed on the current collector 102.
  • the negative electrode mixture layer 101 includes a negative electrode active material 103, a conductive material 104, and a binder 105.
  • the binder 105 joins the negative electrode mixture layer 101 and the current collector.
  • the thickness of the negative electrode mixture layer 101 is preferably in the range of 1.0 ⁇ m to 150 ⁇ m. Therefore, when the negative electrode current collector 102 is supported on both surfaces, the total thickness of the negative electrode mixture layer 101 is in the range of 2.0 ⁇ m to 300 ⁇ m. A more preferable range of the thickness of one surface is 30 ⁇ m or more and 100 ⁇ m or less. Within this range, the large current discharge characteristics and cycle life are greatly improved.
  • the mixing ratio of the negative electrode active material 103, the conductive agent 104, and the binder 105 in the negative electrode mixture layer 101 is 57% by mass to 95% by mass of the negative electrode active material 103, and 3% by mass to 20% by mass of the conductive agent 104.
  • the binder 105 is preferably in the range of 2% by mass to 40% by mass in order to obtain good large current discharge characteristics and cycle life.
  • the current collector 102 of the embodiment is a conductive member that binds to the negative electrode mixture layer 101.
  • a conductive substrate having a porous structure or a non-porous conductive substrate can be used as the current collector 102. These conductive substrates can be formed from, for example, copper, stainless steel, or nickel.
  • the thickness of the current collector is preferably 5 ⁇ m or more and 20 ⁇ m or less. This is because within this range, the electrode strength and weight reduction can be balanced.
  • the negative electrode active material of the embodiment is preferably a carbonaceous material and a composite containing at least a metal in the carbonaceous material from the viewpoint of cycle characteristics and capacity characteristics.
  • the carbonaceous material of the negative electrode active material preferably contains at least a composite containing a metal and a metal oxide or a composite containing a metal, a metal oxide, and a metal carbide.
  • the metal may be an alloy.
  • the average primary particle size of the negative electrode active material is, for example, not less than 0.5 ⁇ m and not more than 50 ⁇ m.
  • the metal and the metal oxide are selected from the group consisting of Si, Sn, Al, In, Ga, Pb, Ti, Ni, Mg, W, Mo, and Fe, an alloy containing the selected element, Preferably, the oxide is at least one selected from oxides of the selected elements and oxides containing the selected elements.
  • the metal and metal oxide are assumed to be silicon and silicon oxide.
  • the alloy may contain a metal other than the selected element.
  • the negative electrode active material include a form including a silicon oxide phase in a carbonaceous material and a silicon phase in the silicon oxide phase, and a form including a composite in which silicon particles are coated with silicon oxide and silicon carbide in the carbonaceous material. Etc.
  • the carbonaceous material of the negative electrode active material 103 is conductive and forms an active material.
  • the carbonaceous material one or more selected from the group consisting of graphite, hard carbon, soft carbon, amorphous carbon and acetylene black can be used.
  • the carbonaceous material can be composed of one or several kinds. From the viewpoint of obtaining an electrode having excellent cycle characteristics, a high-strength carbonaceous material is preferable. As the high-strength carbonaceous material, those containing hard carbon are preferable.
  • the carbonaceous material may contain carbon fibers for the purpose of maintaining the structure and preventing aggregation of silicon and silicon oxide and improving the conductivity.
  • the average diameter of the carbon fibers is preferably 10 nm or more and 1000 nm or less. If the carbon fiber content is too large, the battery capacity is reduced, so that the negative electrode active material preferably contains 5% by mass or less.
  • the peak derived from CH 2 obtained by X-ray photoelectron spectroscopy of the negative electrode active material 103 is preferably 18 mol% or more of the peak in C1s. It is more preferable that the CH 2 -derived peak (C1s binding energy shift) obtained by X-ray photoelectron spectroscopy of the negative electrode active material 103 is 21 mol% or more of the peak occupied by C1s.
  • the peak derived from CH 2 obtained by X-ray photoelectron spectroscopy is less than 18 mol% of the peak in C1s, the brittleness of the negative electrode active material 103 increases.
  • the carbonaceous material is preferably a mixture of graphite and hard carbon. Graphite is preferable in terms of enhancing the conductivity of the active material, and has a large effect of covering the entire hard carbon active material and relaxing expansion and contraction.
  • This peak is defined as peak a.
  • the peak intensity ratio between the peak a and the peak b satisfies the relationship of b / a> 0.15.
  • the carbonaceous material is obtained by sintering a material containing a phenol resin because the above preferable active material can be obtained. Furthermore, it is preferable that at least one component of the precursor of the carbonaceous material is naphthol.
  • the carbonaceous material is obtained by sintering a material containing a phenol resin and a naphthol / formaldehyde condensate because the preferable active material can be obtained.
  • Li compound such as lithium silicate and lithium carbonate, such as Li 4 SiO 4 is, in the carbonaceous material, may be dispersed in or on the silicon oxide phase.
  • the lithium salt added to the carbonaceous material is considered to cause a solid reaction with the silicon oxide phase in the composite by heat treatment to form lithium silicate.
  • SiO 2 precursor and a lithium compound may be added to the structural carbonaceous material covering the silicon phase and the silicon oxide phase.
  • the bond between SiO 2 generated from silicon monoxide and the carbonaceous material becomes strong, and Li 4 SiO 4 having excellent lithium ion conductivity is generated in the silicon oxide phase.
  • the SiO 2 precursor include alkoxides such as silicon ethoxide.
  • the lithium compound include lithium carbonate, lithium oxide, lithium hydroxide, lithium oxalate, and lithium chloride.
  • the conductive material 104 has an effect of increasing the conductivity of the negative electrode, and is preferably present dispersed in the negative electrode mixture layer 101.
  • Examples of the conductive material 104 include acetylene black, carbon black, and graphite.
  • the binder 105 is a material that is excellent in binding property between the negative electrode active materials and excellent in binding property between the negative electrode mixture layer 101 and the current collector 102.
  • the binder 105 include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), polyvinyl alcohol, polyvinyl acetate, polyacrylic acid, polyacrylic acid metal salts, polysaccharides such as alginic acid and cellulose, and the like.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • PVdF polyvinyl alcohol
  • polyvinyl acetate polyacrylic acid
  • polyacrylic acid metal salts polysaccharides such as alginic acid and cellulose, and the like.
  • DEDM ethylene-propylene-diene copolymer
  • SBR styrene-butadiene rubber
  • polyimide polyaramid and the like
  • two or more binders may be used in combination, and the binder excellent in binding between the active materials and the binder excellent in binding between the active material and the current collector. If a combination of the above and a combination of a high hardness and a good flexibility are used, a negative electrode having excellent life characteristics can be produced.
  • the binder 105 of the embodiment joins the negative electrode mixture layer 101 and the current collector 102, but joins the negative electrode mixture layer 101 and the current collector 102 with an azole compound having an amino group as a substituent. Form may be sufficient.
  • the negative electrode active material according to the embodiment can be synthesized through mixing and firing treatment of raw materials by mechanical treatment in a solid phase or liquid phase, stirring treatment, and the like.
  • SiO X (0.8 ⁇ X ⁇ 1.5) is used as the negative electrode active material.
  • Fine particles produced by using fine particles or a mixed powder of silicon and SiO X as a raw material and rapidly heating and rapidly cooling them are preferred.
  • the average primary particle size of these fine particles is preferably 10 nm or more and 1000 nm or less, for example.
  • a negative electrode active material including a composite in which silicon particles are coated with silicon oxide and silicon carbide in a carbonaceous material, silicon particles are coated with carbon as a negative electrode active material, and an inert gas atmosphere Fine particles produced by heat treatment below are preferred.
  • the negative electrode active material is not limited to these, and a material containing the above-described metal or metal and metal oxide can be appropriately used depending on the purpose.
  • the organic material includes at least a carbon material precursor.
  • the organic material at least one of carbon materials such as graphite, coke, low-temperature calcinated charcoal, and pitch can be further used.
  • a material that melts by heating, such as pitch is melted during mechanical milling and does not proceed well into a composite state. Therefore, it is preferable to mix with a material that does not melt, such as coke and graphite.
  • the dynamic compounding process include a turbo mill, a ball mill, a mechano-fusion, and a disk mill.
  • the operating conditions of the mechanical compounding process are different for each device, but it is preferable to perform them until the pulverization / combination sufficiently proceeds.
  • silicon and carbon react to form silicon carbide that is inactive with respect to the lithium insertion reaction. For this reason, it is necessary to determine an appropriate condition for the treatment so that pulverization / combination sufficiently proceeds and silicon carbide is not generated.
  • the mixing and stirring treatment can be performed by, for example, various stirring devices, ball mills, bead mill devices, and combinations thereof.
  • the composite of the fine silicon-based particles with the carbon material precursor and the carbon material is preferably performed by liquid phase mixing in a liquid using a dispersion medium. This is because it is difficult for the dry mixing means to uniformly disperse the fine silicon-based particles and the carbon material precursor without aggregating them.
  • a dispersion medium an organic solvent, water, or the like can be used, but it is preferable to use a liquid having good affinity with both the silicon-based particles, the carbon material precursor, and the carbon material.
  • the carbon material precursor is preferably a liquid or easily polymerizable monomer or oligomer that is soluble in a liquid or a dispersion medium in the mixing stage in order to uniformly mix with the negative electrode active material having a small particle size.
  • resin-based organic materials that form furan resin, xylene resin, ketone resin, amino resin, melamine resin, urea resin, aniline resin, urethane resin, polyimide resin, polyester resin, epoxy resin, phenol resin, and the like.
  • the phenol resin is suitable as a material for obtaining the negative electrode active material of the embodiment because it has a low oxygen content, a high crosslinking density, and is easily carbonized at a relatively low temperature.
  • a naphthalene-based material may be added to these resin-based organic materials from the viewpoint of imparting further conductivity and strength to the negative electrode active material.
  • naphthol materials include 1-naphthol, 2-naphthol, 3-methyl-1-naphthol, 3-methylnaphthalen-2-ol, 3-methoxy-2-naphthol, 1-amino-4-naphthol.
  • 2-amino-1-naphthol 5-amino-1-naphthol, 6-amino-1-naphthol, 1- (dimethylaminomethyl) -2-naphthol, 5-amino-2-naphthol, 7-aminonaphthalene 2-ol, 8-methylnaphthalen-1-ol, 4-bromo-1-naphthol, 3-bromo-2-naphthol, 2,4-dibromo-1-naphthol, 1,6-dibromo-2-naphthol, 4 -Chloro-1-naphthol, 2,4-dichloro-1-naphthol, 1-chloronaphthalen-2-ol, 6-amino-1-naphthol, 2-methyl Lunaphthalen-1-ol, 4-methyl-1-naphthol, 5,6,7,8-tetrahydro-1-naphthol, 1,
  • a naphthol-based material to be mixed with a resin-based organic material can be mixed as a condensation obtained by reacting with formaldehyde or hexamine in advance.
  • the condensed naphthol-based material is more preferable from the viewpoint of imparting further conductivity and strength to the negative electrode active material.
  • the mixed material becomes a slurry.
  • the slurry-like mixture is dried or dried and cured to form a negative electrode active material / organic material composite. Examples of the drying and curing steps include evaporating the dispersion medium and performing a heat treatment for several hours in an oven at 200 ° C. or lower.
  • Carbonization firing process S02
  • the carbonization firing is performed in an inert atmosphere such as in Ar.
  • the carbon material precursor such as polymer or pitch therein is carbonized.
  • SiO X is separated into two phases of a silicon phase and a silicon oxide phase by generating silicon crystals by a disproportionation reaction.
  • X 1
  • the reaction is represented by the following formula (1). 2SiO ⁇ Si + SiO 2 (1)
  • This disproportionation reaction proceeds at a temperature higher than 800 ° C. and separates into a fine silicon phase and a silicon oxide phase.
  • the higher the reaction temperature the larger the silicon phase crystals and the smaller the half width of the Si (220) peak.
  • the firing temperature at which a half width in the preferred range is obtained is in the range of 850 ° C to 1600 ° C.
  • silicon or crystalline silicon produced by disproportionation reaction changes to silicon carbide by reacting with carbon at a temperature higher than 1400 ° C. Since silicon carbide is completely inert to lithium insertion, the capacity of the active material is reduced when silicon carbide is formed. Therefore, from the viewpoint of battery capacity, the temperature for carbonization firing is preferably 850 ° C. or higher and 1400 ° C. or lower, more preferably 900 ° C. or higher and 1100 ° C. or lower. The firing time is preferably between about 1 hour and 12 hours.
  • the particles obtained by the composite treatment may be coated with carbon.
  • a material used for coating a material that is heated in an inert atmosphere such as pitch, resin, or polymer to become a carbonaceous material can be used. Specifically, those which are often carbonized by firing at about 1200 ° C. such as petroleum pitch, mesophase pitch, furan resin, cellulose, rubbers are preferable.
  • the polymerized and solidified composite particles dispersed in a monomer are subjected to carbonization firing.
  • the solid is obtained by dissolving the polymer in a solvent, dispersing the composite particles, and then evaporating the solvent, and subjecting it to carbonization firing.
  • carbon coating by CVD can also be performed as another method used for carbon coating.
  • This method is a method in which a gaseous carbon source is passed over an inert gas as a carrier gas on a sample heated to 800 ° C. or higher and 1000 ° C. or lower and carbonized on the sample surface.
  • benzene, toluene, styrene or the like can be used as the carbon source.
  • the sample since the sample is heated at 800 ° C. or more and 1000 ° C. or less when carbon coating by CVD is performed, it may be performed simultaneously with the carbonization firing. During the carbon coating, the lithium compound and the SiO 2 source may be added simultaneously.
  • the negative electrode active material according to this embodiment is obtained by the manufacturing method as described above.
  • the obtained negative electrode active material may be pulverized to adjust the particle size so as to have a target particle size.
  • the negative electrode active material 103, the conductive agent 104, and the binder 105 are suspended in a commonly used solvent to prepare a slurry.
  • the negative electrode 100 is produced by applying the slurry to the current collector 102, drying it, and then pressing it.
  • the embedding of the negative electrode active material 103 into the current collector 102 can be adjusted by the pressure of the press.
  • a press at a pressure lower than 0.2 kN / cm is not preferable because embedding does not occur much.
  • the pressing pressure of the layer obtained by drying the slurry is preferably 0.5 kN / cm or more and 5 kN / cm or less.
  • a nonaqueous electrolyte secondary battery according to a second embodiment will be described.
  • the nonaqueous electrolyte secondary battery according to the second embodiment is housed in an exterior material, a positive electrode accommodated in the exterior material, and spatially separated from the positive electrode in the exterior material, for example, via a separator.
  • FIG. 3 is a conceptual cross-sectional view of a flat type nonaqueous electrolyte secondary battery 200 in which the bag-shaped exterior material 202 is made of a laminate film.
  • the flat wound electrode group 201 is housed in a bag-like exterior material 202 made of a laminate film in which an aluminum foil is interposed between two resin layers.
  • the flat wound electrode group 201 is laminated in the order of a negative electrode 203, a separator 204, a positive electrode 205, and a separator 204, as shown in FIG. And it is formed by winding the laminate in a spiral shape and press-molding it.
  • the electrode closest to the bag-shaped outer packaging material 202 is a negative electrode, and the negative electrode current collector on the side of the bag-shaped outer packaging material 202 is not formed with a negative electrode mixture.
  • the negative electrode mixture is formed only on one side.
  • the other negative electrode 203 is configured by forming a negative electrode mixture on both surfaces of the negative electrode current collector.
  • the positive electrode 205 is configured by forming a positive electrode mixture on both surfaces of a positive electrode current collector.
  • the negative electrode terminal is electrically connected to the negative electrode current collector of the outermost negative electrode 203
  • the positive electrode terminal is electrically connected to the positive electrode current collector of the inner positive electrode 205.
  • the negative electrode terminal 206 and the positive electrode terminal 207 extend to the outside from the opening of the bag-shaped exterior material 202.
  • the liquid non-aqueous electrolyte is injected from the opening of the bag-shaped exterior material 202.
  • the wound electrode group 201 and the liquid non-aqueous electrolyte are sealed by heat-sealing the opening of the bag-shaped exterior material 202 with the negative electrode terminal 206 and the positive electrode terminal 207 interposed therebetween.
  • Examples of the negative electrode terminal 206 include aluminum or an aluminum alloy containing elements such as Mg, Ti, Zn, Mn, Fe, Cu, and Si.
  • the negative electrode terminal 206 is preferably made of the same material as the negative electrode current collector in order to reduce the contact resistance with the negative electrode current collector.
  • the positive electrode terminal 207 can be made of a material having electrical stability and conductivity in the range of 3 to 4.25 V with respect to the lithium ion metal. Specifically, aluminum or an aluminum alloy containing an element such as Mg, Ti, Zn, Mn, Fe, Cu, or Si can be given.
  • the positive electrode terminal 207 is preferably made of the same material as the positive electrode current collector in order to reduce the contact resistance with the positive electrode current collector.
  • the bag-shaped exterior material 202, the positive electrode 205, the electrolyte, and the separator 204, which are components of the nonaqueous electrolyte secondary battery 200, will be described in detail.
  • Bag-shaped exterior material 202 is formed from a laminate film having a thickness of 0.5 mm or less. Alternatively, a metal container having a thickness of 1.0 mm or less is used as the exterior material. The metal container is more preferably 0.5 mm or less in thickness.
  • the shape of the bag-shaped exterior material 202 can be selected from a flat type (thin type), a square type, a cylindrical type, a coin type, and a button type.
  • the exterior material include, for example, an exterior material for a small battery that is loaded on a portable electronic device or the like, an exterior material for a large battery that is loaded on a two- to four-wheeled vehicle, etc., depending on the battery size.
  • the laminate film a multilayer film in which a metal layer is interposed between resin layers is used.
  • the metal layer is preferably an aluminum foil or an aluminum alloy foil for weight reduction.
  • a polymer material such as polypropylene (PP), polyethylene (PE), nylon, polyethylene terephthalate (PET) can be used.
  • PP polypropylene
  • PE polyethylene
  • PET polyethylene terephthalate
  • the laminate film can be molded into the shape of an exterior material by sealing by heat sealing.
  • Metal containers are made from aluminum or aluminum alloy.
  • the aluminum alloy is preferably an alloy containing elements such as magnesium, zinc, and silicon.
  • transition metals such as iron, copper, nickel, and chromium are included in the alloy, the amount is preferably 100 ppm by mass or less.
  • the positive electrode 205 has a structure in which a positive electrode mixture containing an active material is supported on one surface or both surfaces of a positive electrode current collector.
  • the thickness of one surface of the positive electrode mixture is preferably in the range of 1.0 ⁇ m or more and 150 ⁇ m or less from the viewpoint of maintaining the large current discharge characteristics and cycle life of the battery. Therefore, when the positive electrode current collector is supported on both surfaces, the total thickness of the positive electrode mixture is desirably in the range of 20 ⁇ m to 300 ⁇ m. A more preferable range on one side is 30 ⁇ m or more and 120 ⁇ m or less. Within this range, large current discharge characteristics and cycle life are improved.
  • the positive electrode mixture may contain a conductive agent in addition to the positive electrode active material and the binder that binds the positive electrode active materials.
  • the positive electrode active material examples include various oxides such as manganese dioxide, lithium manganese composite oxide, lithium-containing nickel cobalt oxide (for example, LiCOO 2 ), lithium-containing nickel cobalt oxide (for example, LiNi 0.8 CO 0.2 O). 2 ) and a lithium manganese composite oxide (for example, LiMn 2 O 4 , LiMnO 2 ) are preferable because a high voltage can be obtained.
  • various oxides such as manganese dioxide, lithium manganese composite oxide, lithium-containing nickel cobalt oxide (for example, LiCOO 2 ), lithium-containing nickel cobalt oxide (for example, LiNi 0.8 CO 0.2 O). 2 ) and a lithium manganese composite oxide (for example, LiMn 2 O 4 , LiMnO 2 ) are preferable because a high voltage can be obtained.
  • Examples of the conductive agent include acetylene black, carbon black, and graphite.
  • binder examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-diene copolymer (EPDM), styrene-butadiene rubber (SBR), and the like. .
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • EPDM ethylene-propylene-diene copolymer
  • SBR styrene-butadiene rubber
  • the blending ratio of the positive electrode active material, the conductive agent and the binder is 80% by mass to 95% by mass of the positive electrode active material, 3% by mass to 20% by mass of the conductive agent, and 2% by mass to 7% by mass of the binder.
  • the range is preferable because good large current discharge characteristics and cycle life can be obtained.
  • a conductive substrate having a porous structure or a non-porous conductive substrate can be used as the current collector.
  • the thickness of the current collector is preferably 5 ⁇ m or more and 20 ⁇ m or less. This is because within this range, the electrode strength and weight reduction can be balanced.
  • the positive electrode 205 is prepared by, for example, preparing a slurry by suspending an active material, a conductive agent, and a binder in a commonly used solvent, applying the slurry to a current collector, drying, and then pressing the slurry. Is done.
  • the positive electrode 205 may also be manufactured by forming an active material, a conductive agent, and a binder in the form of a pellet to form a positive electrode layer, which is formed on a current collector.
  • Negative electrode 203 As the negative electrode 203, the negative electrode 100 described in the first embodiment is used.
  • Electrolyte As the electrolyte, a non-aqueous electrolyte, an electrolyte-impregnated polymer electrolyte, a polymer electrolyte, or an inorganic solid electrolyte can be used.
  • the non-aqueous electrolyte is a liquid electrolyte prepared by dissolving an electrolyte in a non-aqueous solvent, and is held in the voids in the electrode group.
  • non-aqueous solvent a non-aqueous solvent mainly composed of a mixed solvent of propylene carbonate (PC) or ethylene carbonate (EC) and a non-aqueous solvent having a viscosity lower than that of PC or EC (hereinafter referred to as a second solvent) is used. It is preferable.
  • PC propylene carbonate
  • EC ethylene carbonate
  • second solvent a non-aqueous solvent having a viscosity lower than that of PC or EC
  • the second solvent for example, chain carbon is preferable.
  • DMC dimethyl carbonate
  • MEC methyl ethyl carbonate
  • DEC diethyl carbonate
  • ethyl propionate methyl propionate
  • BL ⁇ -butyrolactone
  • AN acetonitrile
  • EA ethyl acetate
  • MA methyl acetate
  • the viscosity of the second solvent is preferably 2.8 cmp or less at 25 ° C.
  • the blending amount of ethylene carbonate or propylene carbonate in the mixed solvent is preferably 1.0% to 80% by volume ratio. A more preferable blending amount of ethylene carbonate or propylene carbonate is 20% to 75% by volume.
  • Examples of the electrolyte contained in the non-aqueous electrolyte include lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), and lithium arsenic hexafluoride (LiAsF 6 ). And lithium salts (electrolytes) such as lithium trifluorometasulfonate (LiCF 3 SO 3 ) and lithium bistrifluoromethylsulfonylimide [LiN (CF 3 SO 2 ) 2 ]. Of these, LiPF 6 and LiBF 4 are preferably used.
  • the amount of electrolyte dissolved in the non-aqueous solvent is desirably 0.5 mol / L or more and 2.0 mol / L or less.
  • the separator 204 can be used.
  • the separator 204 is a porous separator.
  • a porous film containing polyethylene, polypropylene, or polyvinylidene fluoride (PVdF), a synthetic resin nonwoven fabric, or the like can be used.
  • PVdF polyvinylidene fluoride
  • a porous film made of polyethylene, polypropylene, or both is preferable because it can improve the safety of the secondary battery.
  • the thickness of the separator 204 is preferably 30 ⁇ m or less. If the thickness exceeds 30 ⁇ m, the distance between the positive and negative electrodes may be increased and the internal resistance may be increased. Further, the lower limit value of the thickness is preferably 5 ⁇ m. If the thickness is less than 5 ⁇ m, the strength of the separator 204 may be significantly reduced and an internal short circuit is likely to occur.
  • the upper limit value of the thickness is more preferably 25 ⁇ m, and the lower limit value is more preferably 1.0 ⁇ m.
  • the separator 204 preferably has a thermal shrinkage rate of 20% or less when kept at 120 ° C. for 1 hour. If the heat shrinkage rate exceeds 20%, the possibility of a short circuit due to heating increases. The thermal shrinkage rate is more preferably 15% or less.
  • the separator 204 preferably has a porosity in the range of 30 to 70%. This is due to the following reason. If the porosity is less than 30%, it may be difficult to obtain high electrolyte retention in the separator 204. On the other hand, if the porosity exceeds 60%, sufficient strength of the separator 204 may not be obtained. A more preferable range of the porosity is 35 to 70%.
  • the separator 204 preferably has an air permeability of 500 seconds / 100 cm 3 or less. If the air permeability exceeds 500 seconds / 100 cm 3 , it may be difficult to obtain high lithium ion mobility in the separator 204.
  • the lower limit value of the air permeability is 30 seconds / 100 cm 3 . This is because if the air permeability is less than 30 seconds / 100 cm 3 , sufficient separator strength may not be obtained.
  • the upper limit value of the air permeability is more preferably 300 seconds / 100 cm 3 , and the lower limit value is more preferably 50 seconds / 100 cm 3 .
  • the battery pack according to the third embodiment includes one or more non-aqueous electrolyte secondary batteries (that is, single cells) according to the second embodiment.
  • the battery pack includes a plurality of single cells, the single cells are electrically connected in series, parallel, or connected in series and parallel.
  • the battery pack 300 will be specifically described with reference to the conceptual diagram of FIG. 5 and the block diagram of FIG. In the battery pack 300 shown in FIG. 5, the flat type nonaqueous electrolyte battery 200 shown in FIG. 5 is used as the unit cell 301.
  • the plurality of single cells 301 are stacked such that the negative electrode terminal 302 and the positive electrode terminal 303 extending to the outside are aligned in the same direction, and are fastened with an adhesive tape 304 to constitute an assembled battery 305. These unit cells 301 are electrically connected to each other in series as shown in FIG.
  • the printed wiring board 306 is disposed to face the side surface of the unit cell 301 from which the negative electrode terminal 302 and the positive electrode terminal 303 extend.
  • a thermistor 307, a protection circuit 308, and a terminal 309 for energizing external devices are mounted on the printed wiring board 306, as shown in FIG. 6, as shown in FIG. 6, a thermistor 307, a protection circuit 308, and a terminal 309 for energizing external devices are mounted.
  • An insulating plate (not shown) is attached to the surface of the printed wiring board 306 facing the assembled battery 305 in order to avoid unnecessary connection with the wiring of the assembled battery 305.
  • the positive electrode side lead 310 is connected to the positive electrode terminal 303 located at the lowermost layer of the assembled battery 305, and the tip thereof is inserted into the positive electrode side connector 311 of the printed wiring board 306 and electrically connected thereto.
  • the negative electrode side lead 312 is connected to the negative electrode terminal 302 located on the uppermost layer of the assembled battery 305, and the tip thereof is inserted into and electrically connected to the negative electrode side connector 313 of the printed wiring board 306.
  • These connectors 311 and 313 are connected to the protection circuit 308 through wirings 314 and 315 formed on the printed wiring board 306.
  • the thermistor 307 is used to detect the temperature of the unit cell 305, and the detection signal is transmitted to the protection circuit 308.
  • the protection circuit 308 can cut off the plus-side wiring 316a and the minus-side wiring 316b between the protection circuit 308 and the terminal 309 for energizing external devices under a predetermined condition.
  • the predetermined condition is, for example, when the temperature detected by the thermistor 307 is equal to or higher than a predetermined temperature.
  • the predetermined condition is when an overcharge, overdischarge, overcurrent, or the like of the unit cell 301 is detected. This detection of overcharge or the like is performed for each single cell 301 or the entire single cell 301.
  • the battery voltage When detecting each single cell 301, the battery voltage may be detected, or the positive electrode potential or the negative electrode potential may be detected. In the latter case, a lithium electrode used as a reference electrode is inserted into each unit cell 301. 5 and 6, a voltage detection wiring 317 is connected to each single cell 301, and a detection signal is transmitted to the protection circuit 308 through the wiring 317.
  • Protective sheets 318 made of rubber or resin are disposed on the three side surfaces of the assembled battery 305 excluding the side surfaces from which the positive electrode terminal 303 and the negative electrode terminal 302 protrude.
  • the assembled battery 305 is stored in the storage container 319 together with each protective sheet 318 and the printed wiring board 306. That is, the protective sheet 318 is disposed on each of the inner side surface in the long side direction and the inner side surface in the short side direction of the storage container 319, and the printed wiring board 306 is disposed on the inner side surface on the opposite side in the short side direction.
  • the assembled battery 305 is located in a space surrounded by the protective sheet 318 and the printed wiring board 306.
  • the lid 320 is attached to the upper surface of the storage container 319.
  • a heat shrink tape may be used for fixing the assembled battery 305.
  • protective sheets are arranged on both side surfaces of the assembled battery, the heat shrinkable tape is circulated, and then the heat shrinkable tape is heat shrunk to bind the assembled battery.
  • 5 and 6 show the configuration in which the single cells 301 are connected in series, but in order to increase the battery capacity, they may be connected in parallel, or a combination of series connection and parallel connection may be used.
  • the assembled battery packs can be further connected in series and in parallel. According to this embodiment described above, it is possible to provide a battery pack having excellent charge / discharge cycle performance by including the nonaqueous electrolyte secondary battery having excellent charge / discharge cycle performance in the third embodiment. it can.
  • the battery pack is preferably one that exhibits excellent cycle characteristics when a large current is taken out.
  • Specific examples include a power source for a digital camera, a vehicle for a two- to four-wheel hybrid electric vehicle, a two- to four-wheel electric vehicle, an assist bicycle, and the like.
  • a battery pack using a nonaqueous electrolyte secondary battery having excellent high temperature characteristics is suitably used for in-vehicle use. Specific examples will be given below and their effects will be described.
  • Example 1 Under the following conditions, SiO was pulverized, kneaded and formed into a composite, and fired in Ar gas to obtain a negative electrode active material.
  • the grinding of SiO was performed as follows.
  • the raw material SiO powder was pulverized by a continuous bead mill apparatus using beads having a bead diameter of 0.5 ⁇ m for a predetermined time using ethanol as a dispersion medium. Further, this SiO powder was pulverized by using a 0.1 ⁇ m ball with a planetary ball mill using ethanol as a dispersion medium to produce a fine SiO powder.
  • the silicon monoxide powder obtained by pulverization treatment and the graphite powder of 3 ⁇ m were combined with the carbonaceous material by the following method.
  • 2.8 g of SiO powder, 0.1 g of graphite powder, and 0.01 g of carbon fiber having an average diameter of 180 nm were added to a mixed solution of 3.0 g of resole resin and 5 g of ethanol, and kneaded with a kneader to form a slurry.
  • ethanol was evaporated at 80 ° C., and the mixture was placed in an oven at 150 ° C. and cured for 2 hours to obtain a carbon composite.
  • the obtained carbon composite was fired at 1100 ° C. for 3 hours in Ar gas, cooled to room temperature, pulverized and passed through a 20 ⁇ m-diameter sieve to obtain a negative electrode active material under the sieve.
  • Example 1 The active material obtained in Example 1 was subjected to a charge / discharge test described below, a charge / discharge test using a cylindrical cell, an X-ray diffraction measurement, and an X-ray photoelectron spectroscopy measurement to evaluate charge / discharge characteristics and physical properties.
  • the obtained negative electrode active material was kneaded using water as a dispersion medium with 15% by mass of graphite having an average diameter of 3 ⁇ m, 3.5% by mass of SBR resin, and 5% by mass of carboxymethyl cellulose, and on a 12 ⁇ m thick copper foil with a gap of 80 ⁇ m. After coating and drying at 100 ° C. for 2 hours and rolling at 2.0 kN / cm, a sample cut to a predetermined size was vacuum-dried at 100 ° C. for 12 hours to obtain a test electrode.
  • the charge / discharge test was performed by charging at a current density of 1 mA / cm 2 up to a potential difference of 0.01 V between the reference electrode and the test electrode, followed by constant voltage charging at 0.01 V for 16 hours, and discharging at 1 mA / cm 2 .
  • the current density was up to 1.5V.
  • 50 cycles were performed by performing 50 cycles of charging at a current density of 1 mA / cm 2 to a potential difference of 0.01 V between the reference electrode and the test electrode and discharging to 1.5 V at a current density of 1 mA / cm 2.
  • the retention rate of the eye discharge capacity was measured.
  • X-ray photoelectron spectroscopy measurement The battery was completely discharged to 0 V and then disassembled, and the taken-out negative electrode was sectioned by milling. X-ray photoelectron spectroscopy measurement was performed on the negative electrode active material region in the cross section, and the C1s peak appearing in the vicinity of 284 eV was subjected to wave number separation to obtain a CH 2 -derived peak in C1s. The measurement was performed using Quantum-2000 manufactured by PHI under the following conditions. X-ray source: Monochromate-Al-K ⁇ ray (1486.6 eV) 43 W Photoelectron extraction angle: 45 ° (measurement depth: 4 nm) Measurement area: 15 ⁇ m ⁇
  • Example 2 The same evaluation as in Example 1 was performed using the same materials as in Example 1 except that 2.2 g of resole resin and 0.8 g of ⁇ -naphthol were used as carbonaceous materials instead of 3.0 g of resole resin. It was.
  • Example 3 The obtained negative electrode active material sample was kneaded using N-methylpyrrolidone as a dispersion medium with 15% by mass of graphite having an average diameter of 3 ⁇ m and 8% by mass of polyimide, and applied to a copper foil having a thickness of 12 ⁇ m with a gap of 80 ⁇ m. Except for rolling at 0.0 kN / cm, heat treatment at 250 ° C. for 2 hours in Ar gas, cutting to a predetermined size, and vacuum drying at 100 ° C. for 12 hours to obtain test electrodes. Evaluation similar to 1 was performed.
  • Example 4 The same evaluation was performed using the same materials as in Example 1 except that 1.5 g of resole resin and 1.5 g of ⁇ -naphthol / formaldehyde condensate were used instead of 3.0 g of resole resin as a carbonaceous material. It was.
  • the ⁇ -naphthol / formaldehyde condensate was added to a separable flask equipped with a stirrer, a reflux condenser and a thermometer with 30 g of ⁇ -naphthol and 25 g of 37% formaldehyde aqueous solution, and 50 wt% sodium hydroxide aqueous solution added to the uniformly stirred solution. 0.9 g was added, and after stirring, the temperature was raised to 80 ° C. and maintained for 2 hours.
  • Example 5 The same evaluation as in Example 1 was performed using the same material as in Example 1 except that the carbon composite for obtaining the negative electrode active material in Example 1 was baked at 900 ° C. for 1 h in Ar gas. It was.
  • Silicon fine particles having an average particle size of about 80 nm and 3 ⁇ m graphite powder were combined with a carbonaceous material by the following method.
  • 2.8 g of Si powder, 0.1 g of graphite powder, and 0.01 g of carbon fiber having an average diameter of 180 nm were added to a mixed solution of 3.0 g of resole resin and 5 g of ethanol, and kneaded with a kneader to form a slurry. After kneading, ethanol was evaporated at 80 ° C., and the mixture was placed in an oven at 150 ° C. and cured for 2 hours to obtain a carbon composite. The obtained carbon composite was fired at 1100 ° C. for 3 hours in Ar gas, cooled to room temperature, pulverized and passed through a 20 ⁇ m-diameter sieve to obtain a negative electrode active material under the sieve.
  • the obtained negative electrode active material sample was kneaded using N-methylpyrrolidone as a dispersion medium with 15% by mass of graphite having an average diameter of 3 ⁇ m and 8% by mass of polyimide, and applied to a copper foil having a thickness of 12 ⁇ m with a gap of 80 ⁇ m. Except for rolling at 0.0 kN / cm, heat treatment at 250 ° C. for 2 hours in Ar gas, cutting to a predetermined size, and vacuum drying at 100 ° C. for 12 hours to obtain test electrodes. Evaluation similar to 1 was performed.
  • Example 7 The same evaluation as in Example 1 was performed using the same materials as in Example 5 except that 2.2 g of resole resin and 0.8 g of ⁇ -naphthol were used instead of 3.0 g of resole resin as the carbonaceous material. It was.
  • Example 8 The same materials as in Example 5 were used except that 1.5 g of resole resin and 1.5 g of ⁇ -naphthol / formaldehyde condensate were used instead of 3.0 g of resole resin as the carbonaceous material. Was evaluated.
  • Example 9 The same evaluation as in Example 1 was performed using the same materials as in Example 5 except that the carbon composite for obtaining the negative electrode active material in Example 5 was baked at 900 ° C. for 1 h in Ar gas. It was.
  • the obtained negative electrode active material was kneaded using water as a dispersion medium with 15% by mass of graphite having an average diameter of 6 ⁇ m, 3.5% by mass of SBR resin, and 5% by mass of carboxymethyl cellulose on a copper foil having a thickness of 12 ⁇ m with a gap of 80 ⁇ m. After coating, drying at 100 ° C. for 2 hours, rolling at 2.0 kN / cm, the sample cut to a predetermined size was vacuum dried at 100 ° C. for 12 hours, and used as a test electrode in the same manner as in Example 1. Was evaluated.
  • Silicon fine particles having an average particle diameter of about 80 nm and graphite powder of 6 ⁇ m were combined with a carbonaceous material by the following method. 2.8 g of SiO powder, 0.5 g of graphite powder, and 0.01 g of carbon fibers with an average diameter of 180 nm were added to a mixed liquid of 3.0 g of furfuryl alcohol, 10 g of ethanol and 0.125 g of water, and kneaded with a kneader. A slurry was formed.
  • the obtained negative electrode active material sample was kneaded using N-methylpyrrolidone as a dispersion medium with 15% by mass of graphite having an average diameter of 3 ⁇ m and 8% by mass of polyimide, and applied to a copper foil having a thickness of 12 ⁇ m with a gap of 80 ⁇ m. Except for rolling at 0.0 kN / cm, heat treatment at 250 ° C. for 2 hours in Ar gas, cutting to a predetermined size, and vacuum drying at 100 ° C. for 12 hours to obtain test electrodes. Evaluation similar to 1 was performed.
  • Comparative Example 3 The carbon composite obtained in Comparative Example 1 was fired at 2000 ° C. for 3 hours in Ar gas, cooled to room temperature, pulverized, and passed through a 20 ⁇ m diameter sieve to obtain a negative electrode active material under the sieve. Evaluation similar to Example 1 was performed.
  • the following examples and comparative examples are summarized in Table 1.
  • the negative electrode of the example has good cycle characteristics. That is, in Comparative Examples 1 to 3, as the charging / discharging progressed, the conductive path was interrupted due to defects such as cracking of the composite particles, and thus the cycle characteristics deteriorated.
  • Electrode for nonaqueous electrolyte batteries 101 ... Negative electrode mixture layer, 102 ... Current collector, 103 ... Negative electrode active material, 104 ... Conductive material, 105 ... Binder, 200 ... Nonaqueous electrolyte secondary battery, 200 ... Winding electrode group, 200: bag-shaped exterior material, 202: negative electrode, 203 ... separator, 204 ... positive electrode, 300 ... battery pack, 301 ... single cell, 302 ... negative electrode terminal, 303 ... positive electrode terminal, 304 ... adhesive tape, 305 ... assembled battery, 306 ... printed wiring board, 307 ... thermistor, 308 ... protection circuit, 309 ...
  • terminal for energization 310 ... positive electrode side lead, 311 ... positive electrode side connector, 312 ... negative electrode side lead, 313 ... negative electrode side connector, 314 ... wiring, 315 ... wiring, 316a ... plus-side wiring, 316b ... minus-side wiring, 317 ... wiring, 318 ... protective sheet, 319 ... storage container, 320 ... lid

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Abstract

Le but de l'invention est de fournir une électrode pour batteries à électrolyte non aqueux ayant une longue durée de vie. L'électrode pour batteries selon un mode de réalisation est une électrode qui comporte un collecteur de courant et, disposée sur le collecteur de courant, une couche de mélange comprenant : une substance carbonée ; un matériau actif comprenant un composite qui comprend une substance carbonée et un métal contenu dans celle-ci ; et un liant. L'électrode est caractérisée par le fait que le matériau actif, lorsqu'il est analysé par une spectroscopie photoélectronique à rayons X, donne des pics dans lesquels 18 % en moles ou plus des pics C1s sont pris en compte par le pic affecté à CH2.
PCT/JP2014/057404 2014-03-18 2014-03-18 Électrode pour batterie à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux et bloc-batterie WO2015140937A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018062051A1 (fr) * 2016-09-30 2018-04-05 帝人株式会社 Corps fritté en composite de carbure de silicium et procédé pour sa fabrication

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010038609A1 (fr) * 2008-09-30 2010-04-08 住友ベークライト株式会社 Matériau carboné pour électrode négative de batterie secondaire au lithium, électrode négative de batterie secondaire au lithium, batterie secondaire au lithium et procédé de fabrication d’un matériau carboné pour électrode négative de batterie secondaire au lithium
JP2011076743A (ja) * 2009-09-29 2011-04-14 Sumitomo Bakelite Co Ltd リチウム二次電池負極合剤、リチウム二次電池負極およびリチウム二次電池
JP2011076742A (ja) * 2009-09-29 2011-04-14 Sumitomo Bakelite Co Ltd リチウム二次電池負極合剤、リチウム二次電池負極およびリチウム二次電池
JP2012124121A (ja) * 2010-12-10 2012-06-28 Hitachi Chem Co Ltd リチウム二次電池用負極材の製造方法
JP2013051216A (ja) * 2012-12-10 2013-03-14 Nec Energy Devices Ltd 非水電解質二次電池
JP2013193886A (ja) * 2012-03-15 2013-09-30 Mitsubishi Chemicals Corp 複合炭素材及びその製造方法、その複合炭素材を用いた負極並びに蓄電デバイス
JP2014029833A (ja) * 2012-07-03 2014-02-13 Jfe Chemical Corp リチウムイオン二次電池用負極材料およびその製造方法ならびにこれを用いたリチウムイオン二次電池用負極ならびにリチウムイオン二次電池
JP2014029848A (ja) * 2012-06-29 2014-02-13 Jfe Chemical Corp リチウムイオン二次電池負極用複合粒子及びその製造方法、リチウムイオン二次電池用負極並びにリチウムイオン二次電池

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010038609A1 (fr) * 2008-09-30 2010-04-08 住友ベークライト株式会社 Matériau carboné pour électrode négative de batterie secondaire au lithium, électrode négative de batterie secondaire au lithium, batterie secondaire au lithium et procédé de fabrication d’un matériau carboné pour électrode négative de batterie secondaire au lithium
JP2011076743A (ja) * 2009-09-29 2011-04-14 Sumitomo Bakelite Co Ltd リチウム二次電池負極合剤、リチウム二次電池負極およびリチウム二次電池
JP2011076742A (ja) * 2009-09-29 2011-04-14 Sumitomo Bakelite Co Ltd リチウム二次電池負極合剤、リチウム二次電池負極およびリチウム二次電池
JP2012124121A (ja) * 2010-12-10 2012-06-28 Hitachi Chem Co Ltd リチウム二次電池用負極材の製造方法
JP2013193886A (ja) * 2012-03-15 2013-09-30 Mitsubishi Chemicals Corp 複合炭素材及びその製造方法、その複合炭素材を用いた負極並びに蓄電デバイス
JP2014029848A (ja) * 2012-06-29 2014-02-13 Jfe Chemical Corp リチウムイオン二次電池負極用複合粒子及びその製造方法、リチウムイオン二次電池用負極並びにリチウムイオン二次電池
JP2014029833A (ja) * 2012-07-03 2014-02-13 Jfe Chemical Corp リチウムイオン二次電池用負極材料およびその製造方法ならびにこれを用いたリチウムイオン二次電池用負極ならびにリチウムイオン二次電池
JP2013051216A (ja) * 2012-12-10 2013-03-14 Nec Energy Devices Ltd 非水電解質二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018062051A1 (fr) * 2016-09-30 2018-04-05 帝人株式会社 Corps fritté en composite de carbure de silicium et procédé pour sa fabrication
JPWO2018062051A1 (ja) * 2016-09-30 2019-02-14 帝人株式会社 炭化ケイ素複合焼結体及びその製造方法

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