WO2016104024A1 - Batterie au lithium-ion - Google Patents

Batterie au lithium-ion Download PDF

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Publication number
WO2016104024A1
WO2016104024A1 PCT/JP2015/083054 JP2015083054W WO2016104024A1 WO 2016104024 A1 WO2016104024 A1 WO 2016104024A1 JP 2015083054 W JP2015083054 W JP 2015083054W WO 2016104024 A1 WO2016104024 A1 WO 2016104024A1
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positive electrode
negative electrode
battery
active material
lithium
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PCT/JP2015/083054
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English (en)
Japanese (ja)
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陽 安田
剛史 西山
原　賢二
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日立化成株式会社
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Priority to JP2016566049A priority Critical patent/JPWO2016104024A1/ja
Publication of WO2016104024A1 publication Critical patent/WO2016104024A1/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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lithium ion battery.
  • Lithium ion batteries are high energy density secondary batteries, and are used as power sources for portable devices such as notebook computers and mobile phones, taking advantage of their characteristics.
  • lithium-ion batteries are expected to be used not only for consumer applications such as portable devices, but also for large-scale power storage systems for natural energy such as solar power and wind power generation.
  • the amount of power per system is required on the order of several MWh.
  • Patent Document 1 uses a positive electrode in which a predetermined amount of an active material mixture containing a lithium / manganese composite oxide is applied to both sides of a current collector.
  • Patent Document 2 has a battery capacity of 3 Ah or more, a positive electrode active material mixture containing lithium-manganese composite oxide is used for the positive electrode, and a negative electrode active material containing amorphous carbon is used for the negative electrode.
  • a battery using a material mixture is disclosed.
  • an object of the present invention is to provide a high-capacity lithium ion battery with high input / output while ensuring safety.
  • a further object is to provide a lithium ion battery having good input / output characteristics and excellent life characteristics.
  • a negative electrode of a lithium ion battery provided with an electrode group in which a positive electrode and a negative electrode are arranged via a separator, and an electrolytic solution in a battery container is configured as follows.
  • the negative electrode contains amorphous carbon, and the amorphous carbon has a weight of 550 ° C. in an air flow of 70% or more with respect to a weight of 25 ° C., and a weight of 650 ° C. is measured by thermogravimetry. 20% or less based on the weight at 25 ° C.
  • the amorphous carbon has a specific surface area determined from nitrogen adsorption measurements it is at 1.0m 2 /g ⁇ 4.0m 2 / g, and the carbon dioxide adsorption amount until the relative pressure 0.03 (273K) is , which is 0.01cm 3 /g ⁇ 4.0cm 3 / g.
  • the positive electrode contains layered lithium / nickel / manganese / cobalt composite oxide (NMC) and spinel type lithium / manganese oxide (sp-Mn).
  • NMC nickel / manganese / cobalt composite oxide
  • sp-Mn spinel type lithium / manganese oxide
  • the positive electrode contains olivine type lithium iron phosphate (LFP).
  • the positive electrode contains layered lithium-nickel-manganese-cobalt composite oxide (NMC) and olivine-type lithium iron phosphate (LFP).
  • NMC lithium-nickel-manganese-cobalt composite oxide
  • LFP olivine-type lithium iron phosphate
  • the present invention it is possible to provide a high-capacity lithium ion battery with high input / output while ensuring safety. Furthermore, it is possible to provide a lithium ion battery having good input / output characteristics and excellent life characteristics.
  • the lithium ion battery has a positive electrode, a negative electrode, a separator, and an electrolytic solution in a battery container.
  • a separator is disposed between the positive electrode and the negative electrode.
  • lithium ions inserted into the positive electrode active material are desorbed and released into the electrolytic solution.
  • the lithium ions released into the electrolytic solution move in the electrolytic solution, pass through a separator made of a microporous film, and reach the negative electrode.
  • the lithium ions that have reached the negative electrode are inserted into the negative electrode active material constituting the negative electrode.
  • charging and discharging can be performed by inserting and desorbing lithium ions between the positive electrode active material and the negative electrode active material.
  • a configuration example of an actual lithium ion battery will be described later (see, for example, FIG. 1).
  • the positive electrode, the negative electrode, the electrolytic solution, the separator, and other components that are components of the lithium ion battery according to the present embodiment will be described in order.
  • the positive electrode (positive electrode plate) of the present embodiment is composed of a current collector (positive electrode current collector) and a positive electrode mixture formed thereon.
  • the positive electrode mixture is a layer including at least a positive electrode active material provided on the current collector.
  • the layered lithium / nickel / manganese / cobalt composite oxide (NMC) and the spinel type lithium are used.
  • -It contains a mixed active material with manganese oxide (spinel-type lithium-manganese composite oxide, sp-Mn).
  • the positive electrode mixture is formed (applied) on both surfaces of the current collector, for example.
  • a cylindrical lithium ion battery has an internal pressure reduction mechanism such as a safety valve or a cleavage valve that discharges gas to the outside of the container when a predetermined internal pressure is reached in order to prevent an increase in the internal pressure in the battery container. Yes.
  • the battery container may be damaged (including cracks, expansion, and ignition) even when the internal pressure reduction mechanism is provided.
  • a positive electrode mixture containing layered lithium / nickel / manganese / cobalt composite oxide (NMC) and spinel type lithium / manganese oxide (sp-Mn) is used.
  • the positive electrode mixture density is 2.4 g / cm 3 or more and 2.7 g / cm 3 or less
  • the positive electrode mixture application amount is 175 g / m 2 or more and 250 g / m 2 or less
  • layered lithium / nickel / manganese / NMC / sp-Mn which is a weight ratio (mixing ratio) between the cobalt composite oxide (NMC) and the spinel type lithium manganese oxide (sp-Mn)
  • the battery can be increased in capacity and input / output while ensuring safety even in an abnormal state.
  • the weight ratio may be simply referred to as “weight ratio of active material”.
  • the resistance of the positive electrode is increased and the input / output characteristics may be deteriorated.
  • the density of the positive electrode mixture exceeds 2.7 g / cm 3 , there is a concern that the safety may be lowered, and other safety measures may need to be strengthened.
  • the coating amount of the positive electrode mixture is less than 175 g / m 2 , the amount of the active material that contributes to charging / discharging decreases, and the energy density of the battery may decrease.
  • the coating amount of the positive electrode mixture exceeds 250 g / m 2 , the resistance of the positive electrode mixture increases, and the input / output characteristics may be deteriorated.
  • the weight ratio of active material (NMC / sp-Mn) is less than 10/90, the energy density of the battery may be reduced.
  • the weight ratio (NMC / sp-Mn) of the active material exceeds 60/40, there is a concern that the safety may be lowered, and other safety measures may need to be strengthened.
  • the positive electrode mixture by setting the positive electrode mixture density, the positive electrode mixture application amount, and the weight ratio of the active material (NMC / sp-Mn) to the above ranges, high capacity lithium ions having a discharge capacity of 30 Ah or more Also in the battery, it is possible to realize a battery with high input / output and high energy density while ensuring safety.
  • the discharge capacity X is 30 Ah or more and less than 100 Ah. Even in a high-capacity lithium ion battery, a battery with high input / output and high energy density can be realized while ensuring safety.
  • the element M includes Ti (titanium), Zr (zirconium), Nb (niobium), Mo (molybdenum), W (tungsten), Al (aluminum), Si (silicon), Ga (gallium), Ge (germanium), and Sn. It is at least one element selected from the group consisting of (tin).
  • sp-Mn spinel type lithium manganese oxide represented by the following composition formula (Formula 2).
  • the element M ′ is at least one element selected from the group consisting of Mg (magnesium), Ca (calcium), Sr (strontium), Al, Ga, Zn (zinc), and Cu (copper).
  • the positive electrode active material As described above, a mixture of layered lithium / nickel / manganese / cobalt composite oxide (NMC) and spinel type lithium / manganese oxide (sp-Mn) is used as the positive electrode active material (positive electrode active material).
  • NMC nickel / manganese / cobalt composite oxide
  • sp-Mn spinel type lithium / manganese oxide
  • Mg or Al As the element M ′ in the composition formula (Formula 2).
  • Mg or Al the battery life can be extended.
  • the safety of the battery can be improved.
  • Mn in the compound is stable in the charged state, and thus heat generation due to the charging reaction can be suppressed. Thereby, the safety
  • spinel type lithium manganese oxide (sp-Mn) has useful characteristics, but spinel type lithium manganese oxide (sp-Mn) itself has a small theoretical capacity and a low density. Therefore, when only a spinel type lithium manganese oxide (sp-Mn) is used as a positive electrode active material to constitute a battery, it is difficult to increase the battery capacity (discharge capacity).
  • the layered lithium-nickel-manganese-cobalt composite oxide (NMC) has a large theoretical capacity, and has a theoretical capacity equivalent to that of LiCoO 2 which is widely used as a positive electrode active material for lithium ion batteries.
  • layered lithium / nickel / manganese / cobalt composite oxide (NMC) and spinel type lithium / manganese oxide (sp-Mn) are used in combination, and the density of the positive electrode mixture is further increased.
  • NMC nickel / manganese / cobalt composite oxide
  • sp-Mn spinel type lithium / manganese oxide
  • the positive electrode mixture contains a positive electrode active material, a binder, and the like, and is formed on the current collector.
  • a positive electrode active material, a binder, and other materials such as a conductive material and a thickener used as needed are mixed in a dry form to form a sheet, which is pressure-bonded to a current collector (dry method).
  • a positive electrode active material, a binder, and other materials such as a conductive material and a thickener used as necessary are dissolved or dispersed in a dispersion solvent to form a slurry, which is applied to a current collector and dried. (Wet method).
  • layered lithium / nickel / manganese / cobalt composite oxide (NMC) and spinel type lithium / manganese oxide (sp-Mn) are used as described above. These are used in powder form (granular) and mixed.
  • a substance having a composition different from that of the substance constituting the main cathode active material may be adhered to the surface of the cathode active material.
  • Surface adhesion substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, sulfuric acid Examples thereof include sulfates such as calcium and aluminum sulfate, carbonates such as lithium carbonate, calcium carbonate and magnesium carbonate, and carbon.
  • the surface active substance is impregnated and added to the positive electrode active material by adding the positive electrode active material to a liquid in which the surface adhesive substance is dissolved or suspended in a solvent. Thereafter, the positive electrode active material impregnated with the surface adhering substance is dried.
  • the positive electrode active material is added to a liquid obtained by dissolving or suspending the precursor of the surface adhesion material in a solvent, so that the precursor of the surface adhesion material is impregnated and added to the positive electrode active material. Thereafter, the positive electrode active material impregnated with the precursor of the surface adhering material is heated. Further, a liquid obtained by dissolving or suspending the precursor of the surface adhesion substance and the precursor of the positive electrode active material in a solvent is baked.
  • the surface adhering substance can be attached to the surface of the positive electrode active material.
  • the amount of the surface adhering substance is preferably in the following range with respect to the weight of the positive electrode active material.
  • the lower limit of the range is preferably 0.1 ppm or more, more preferably 1 ppm or more, and even more preferably 10 ppm or more.
  • the upper limit is preferably 20% or less, more preferably 10% or less, and still more preferably 5% or less.
  • the surface adhering substance can suppress the oxidation reaction of the non-aqueous electrolyte solution on the surface of the positive electrode active material, and can improve the battery life.
  • the adhesion amount is too small, the above effect is not sufficiently exhibited.
  • the adhesion amount is too large, the resistance may increase in order to inhibit the entry and exit of lithium ions. Therefore, the above range is preferable.
  • the positive electrode active material particles of layered lithium / nickel / manganese / cobalt composite oxide (NMC) and spinel type lithium / manganese oxide (sp-Mn), bulk, polyhedral, spherical, elliptical, plate, Needles, columns, etc. are used.
  • the primary particles are aggregated to form secondary particles, and the shape of the secondary particles is spherical or elliptical.
  • the active material in the electrode expands and contracts as it is charged / discharged, so that the active material is easily damaged or the conductive path is broken due to the stress.
  • particles in which primary particles are aggregated to form secondary particles rather than using single particles of only primary particles, because the stress of expansion and contraction can be relieved and the above deterioration can be prevented.
  • spherical or oval spherical particles rather than plate-like particles having axial orientation, since the orientation in the electrode is reduced, so that the expansion and contraction of the electrode during charge / discharge is reduced.
  • other materials such as a conductive material are easily mixed uniformly when forming the electrode.
  • the range of the median diameter D50) of the secondary particles is as follows.
  • the lower limit of the range is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, further preferably 3 ⁇ m or more, and the upper limit is 20 ⁇ m or less, preferably 18 ⁇ m or less, more preferably 16 ⁇ m or less, and even more preferably. Is 15 ⁇ m or less.
  • the tap density (fillability) may be lowered, and a desired tap density may not be obtained.
  • the upper limit it takes time to diffuse lithium ions in the particles, so that the battery performance is lowered. There is a risk of inviting.
  • the said upper limit there exists a possibility that a mixing property with other materials, such as a binder and a electrically conductive material, may fall at the time of formation of an electrode. Therefore, when this mixture is slurried and applied, it may not be applied uniformly and may cause problems such as streaking.
  • the tap density (fillability) may be improved by mixing two or more kinds of positive electrode active materials having different median diameters D50.
  • the median diameter D50 means the particle diameter at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method.
  • the range of the average particle diameter of the primary particles when the primary particles are aggregated to form secondary particles is as follows.
  • the lower limit of the range is 0.01 ⁇ m or more, preferably 0.05 ⁇ m or more, more preferably 0.08 ⁇ m or more, particularly preferably 0.1 ⁇ m or more
  • the upper limit is 3 ⁇ m or less, preferably 2 ⁇ m or less, more preferably 1 ⁇ m.
  • it is particularly preferably 0.6 ⁇ m or less.
  • the range of the BET specific surface area of the positive electrode active material particles of layered type lithium / nickel / manganese / cobalt composite oxide (NMC) or spinel type lithium / manganese oxide (sp-Mn) is as follows.
  • the lower limit of the range is 0.2 m 2 / g or more, preferably 0.3 m 2 / g or more, more preferably 0.4 m 2 / g or more, and the upper limit is 4.0 m 2 / g or less, preferably 2 .5m 2 / g, more preferably not more than 1.5 m 2 / g. If it is less than the said minimum, there exists a possibility that battery performance may fall.
  • the BET specific surface area is a specific surface area (area per unit g) determined by the BET method.
  • Examples of the conductive material for the positive electrode include metal materials such as copper and nickel; graphite such as natural graphite and artificial graphite (graphite); carbon black such as acetylene black; and carbonaceous materials such as amorphous carbon such as needle coke. Is mentioned. Of these, one type may be used alone, or two or more types may be used in combination.
  • the range of the content of the conductive material relative to the weight of the positive electrode mixture is as follows.
  • the lower limit of the range is 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, and the upper limit is 50% by mass or less, preferably 30% by mass or less, more preferably 15%. It is below mass%. If it is less than the above lower limit, the conductivity may be insufficient. Moreover, when the said upper limit is exceeded, there exists a possibility that battery capacity may fall.
  • the binder for the positive electrode active material is not particularly limited, and when the positive electrode mixture is formed by a coating method, a material having good solubility and dispersibility in the dispersion solvent is selected.
  • resin polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, and nitrocellulose; SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), fluorine Rubbery polymers such as rubber, isoprene rubber, butadiene rubber, ethylene-propylene rubber; fluorinated polymers such as styrene / butadiene / styrene block copolymers or hydrogenated products thereof, polytetrafluoroethylene / vinylidene fluoride copolymers, etc.
  • Molecule a polymer composition having ion conductivity of alkali metal ions (particularly lithium ions), and the like. Of these, one type may be used alone, or two or more types may be used in combination. From the viewpoint of the stability of the positive electrode, it is preferable to use a fluorine-based polymer such as polyvinylidene fluoride (PVDF) or a polytetrafluoroethylene / vinylidene fluoride copolymer.
  • PVDF polyvinylidene fluoride
  • PVDF polytetrafluoroethylene / vinylidene fluoride copolymer
  • the range of the binder content relative to the weight of the positive electrode mixture is as follows.
  • the lower limit of the range is 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and the upper limit is 80% by mass or less, preferably 60% by mass or less, more preferably 40% by mass.
  • it is particularly preferably 10% by mass or less. If the content of the binder is too low, the positive electrode active material cannot be sufficiently bound, the positive electrode has insufficient mechanical strength, and battery performance such as cycle characteristics may be deteriorated. On the other hand, if it is too high, battery capacity and conductivity may be reduced.
  • the layer formed on the current collector using the above wet method or dry method is preferably consolidated by a hand press or a roller press in order to improve the packing density of the positive electrode active material.
  • the material of the current collector for the positive electrode is not particularly limited, and specific examples include metal materials such as aluminum, stainless steel, nickel plating, and titanium; and carbonaceous materials such as carbon cloth and carbon paper. Of these, metal materials, particularly aluminum, are preferred.
  • the shape of the current collector is not particularly limited, and materials processed into various shapes can be used.
  • the metal material include a metal foil, a metal plate, and a metal thin film.
  • the carbonaceous material include a carbon plate and a carbon thin film. Among these, it is preferable to use a metal thin film. In addition, you may form a thin film suitably in mesh shape.
  • the thickness of the thin film is arbitrary, but the range is as follows. The lower limit of the range is 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and the upper limit is 1 mm or less, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less. If it is less than the said minimum, intensity
  • Negative electrode In this embodiment, the negative electrode shown below is applicable to a high-capacity, high-input / output lithium-ion battery.
  • the negative electrode (negative electrode plate) of the present embodiment includes a current collector (negative electrode current collector) and a negative electrode mixture formed on both surfaces thereof.
  • a negative electrode compound material is not restrict
  • the negative electrode mixture contains a negative electrode active material capable of electrochemically occluding and releasing lithium ions.
  • At least amorphous carbon is used, other carbonaceous materials, metal oxides such as tin oxide and silicon oxide, metal composite oxides, lithium alloys such as lithium alone and lithium aluminum alloys, Sn and You may use 1 type, or 2 or more types of metals etc. which can form an alloy with lithium, such as Si.
  • the carbonaceous material is a lithium ion that has high conductivity, excellent low-temperature characteristics, cycle stability, negative electrode active material with the following physical properties, good input / output characteristics, and excellent life characteristics
  • a battery can be provided.
  • a negative electrode containing amorphous carbon is used as the negative electrode active material.
  • the amorphous carbon has a weight of 550 ° C. in an air stream determined by thermogravimetry (TG) of 70% or more with respect to a weight of 25 ° C., and a weight of 650 ° C. with respect to a weight of 25 ° C. 20% or less.
  • the weight at 550 ° C. in the air stream is preferably 85% or more with respect to the weight at 25 ° C.
  • the weight at 650 ° C. is preferably 10% or less with respect to the weight at 25 ° C.
  • it is more preferable that the weight at 550 ° C. in the air stream is 95% or more with respect to the weight at 25 ° C.
  • the weight at 650 ° C. is less than 5% with respect to the weight at 25 ° C.
  • thermogravimetric measurement device can be measured by, for example, a TG analysis (Thermo Gravimetry Analysis) device (for example, TG / DTA6200, manufactured by SII Nanotechnology Co., Ltd.). The measurement conditions are that a sample of 10 mg can be collected and measured at a heating rate of 1 ° C./min using alumina as a reference under a flow of dry air of 300 ml / min.
  • TG analysis Thermo Gravimetry Analysis
  • the amorphous carbon has a weight of 550 ° C. in an air stream determined by thermogravimetry at 70% or more with respect to a weight of 25 ° C., and a weight of 650 ° C. with respect to a weight of 25 ° C.
  • the carbonaceous material is not particularly limited as long as it is 20% or less, but is preferably a carbonaceous material obtained by firing and pulverizing a material exhibiting graphitizability from the viewpoint of enhancing irreversible capacity, input / output characteristics, and life characteristics. Specifically, a material exhibiting graphitizability is fired, for example, in an inert atmosphere at 800 ° C.
  • the amorphous carbon can be obtained by adjusting the median particle diameter to 5 to 30 ⁇ m.
  • the material exhibiting graphitizability is not particularly limited, and examples thereof include thermoplastic resins, naphthalene, anthracene, phenanthrolen, coal tar, tar pitch, etc., preferably coal-based coal tar or petroleum It is a system tar.
  • the amorphous carbon here is generally classified into non-graphitizable carbon and graphitizable carbon.
  • Graphitizable carbon has graphitization properties that graphitize by heat treatment at 800 ° C. or higher.
  • non-graphitizable carbon has non-graphitization property that hardly graphitizes even by heat treatment at 2800 ° C. or higher.
  • graphitizable carbon has an atomic arrangement structure that easily forms a layered structure, and has a property of easily changing to a graphite structure by heat treatment at a relatively low temperature as compared with non-graphitizable carbon. That is, graphitizable carbon is more preferable as the amorphous carbon.
  • the amorphous carbon can be used as it is as a negative electrode active material for a lithium ion battery.
  • a large specific surface area is expected, and desired characteristics may not be exhibited. Therefore, it is preferable to adjust the physical properties shown in the following (1) to (5) by forming a carbon layer or the like on the surface of the amorphous carbon.
  • the range of the median particle diameter (D50) is as follows.
  • the thickness is preferably 5 ⁇ m to 30 ⁇ m, more preferably 10 ⁇ m to 25 ⁇ m, and even more preferably 12 ⁇ m to 23 ⁇ m. If it is less than the lower limit, the specific surface area increases and the irreversible capacity increases, which may lead to loss of the initial battery capacity, and the contact between the particles may be deteriorated, resulting in deterioration of input / output characteristics. In addition, if the above upper limit is exceeded, the diffusion distance of Li from the particle surface to the inside becomes long, so that the input / output characteristics may be deteriorated, and the application surface of the negative electrode mixture becomes non-uniform at the time of electrode formation, and electrode formation May cause trouble.
  • the range is as follows.
  • the amount is less than the above lower limit, the occlusion of lithium ions in the negative electrode tends to be reduced during charging, and lithium may be deposited on the negative electrode surface, and input / output characteristics may be deteriorated.
  • the above upper limit is exceeded, the reactivity with the non-aqueous electrolyte increases, and the generated gas in the vicinity of the negative electrode may increase, the initial battery capacity may be lost, and the life characteristics may be deteriorated.
  • the specific surface area by nitrogen adsorption can be calculated
  • the ranges are as follows.
  • 0.01cm 3 /g ⁇ 4.0cm 3 / g more preferably 0.05cm 3 /g ⁇ 1.5cm 3 / g, more preferably 0.1cm 3 /g ⁇ 1.2cm 3 / g.
  • the amount is less than the above lower limit, the occlusion of lithium ions in the negative electrode tends to be reduced during charging, and lithium may be deposited on the negative electrode surface, and input / output characteristics may be deteriorated.
  • the above upper limit is exceeded, the reactivity with the non-aqueous electrolyte increases, and the generated gas in the vicinity of the negative electrode may increase, the initial battery capacity may be lost, and the life characteristics may be deteriorated.
  • the specific surface area for carbon dioxide adsorption can be determined from the adsorption isotherm obtained by carbon dioxide adsorption measurement at 273 K using the BET method.
  • the range of tap density is as follows. Preferably, it is 0.1 g / cm 3 to 2.0 g / cm 3 , more preferably 0.3 g / cm 3 to 1.5 g / cm 3 , and still more preferably 0.4 g / cm 3 to 1.2 g. / cm 3 . If it is less than the said minimum, the filling density of the negative electrode active material in a negative electrode compound material may fall, and there exists a possibility that a predetermined battery capacity cannot be ensured. On the other hand, when the above upper limit is exceeded, there are less voids between the negative electrode active materials in the negative electrode mixture, and it may be difficult to ensure conductivity between particles.
  • the range of the R value (IG / ID) is as follows. It is preferably 0.8 to 2.0, more preferably 0.9 to 1.5, and still more preferably 1.0 to 1.2. If it is less than the lower limit, the irreversible capacity increases, which may cause a loss of initial battery capacity. If the upper limit is exceeded, the input / output characteristics may deteriorate.
  • the Raman spectrum can be measured using a Raman spectrometer (for example, DXR manufactured by Thermo Fisher Scientific).
  • the amorphous carbon in the present invention has 70% or more of the weight of 550 ° C. with respect to the weight of 25 ° C. in the air stream determined by thermogravimetry (TG), and the weight of 650 ° C. is 25 ° C. It can also be obtained by forming a carbon layer on the surface of amorphous carbon particles serving as nuclei of 20% or less by weight.
  • the carbon layer can be formed, for example, by attaching an organic compound (carbon precursor) that remains carbonaceous by heat treatment to the surface of the amorphous carbon, and then firing.
  • the method for attaching the organic compound to the surface of the amorphous carbon is not particularly limited. For example, after the amorphous carbon as a nucleus is dispersed and mixed in a mixed solution in which the organic compound is dissolved or dispersed in a solvent. Examples include a wet method for removing a solvent, a dry method in which amorphous carbon and an organic compound are mixed with each other, and mechanical energy is applied to the mixture, and a vapor phase method such as a CVD method. Among these, the wet method is preferable from the viewpoint of being uniform and easy to control the reaction system and maintaining the shape of the amorphous carbon.
  • the organic compound may be a polymer compound such as a thermoplastic resin or a thermosetting resin, and is not particularly limited.
  • the thermoplastic polymer compound is carbonized via a liquid phase and has a small specific surface area. In order to generate carbon, it is preferable to coat the amorphous carbon surface because the specific surface area of the negative electrode active material itself is reduced, and as a result, the initial irreversible capacity of the lithium ion battery can be reduced.
  • the thermoplastic polymer compound is not particularly limited. For example, ethylene heavy end pitch, crude oil pitch, coal tar pitch, asphalt cracking pitch, pitch generated by thermally decomposing polyvinyl chloride, naphthalene, etc. A synthetic pitch produced by polymerization in the presence of superacidity can be used.
  • thermoplastic synthetic resins such as polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, and polyvinyl butyral, and natural products such as starch and cellulose can also be used. These organic compounds may be used alone or in combination of two or more.
  • the solvent for dissolving and dispersing the organic compound is not particularly limited.
  • the organic compound when the organic compound is pitches, it is generated during tetrahydrofuran, toluene, xylene, benzene, quinoline, pyridine, or coal dry distillation.
  • a liquid mixture having a relatively low boiling point (creosote oil) or the like can be used.
  • the organic compound is polyvinyl chloride, for example, tetrahydrofuran, cyclohexanone, nitrobenzene, etc.
  • the organic compound when the organic compound is polyvinyl acetate, polyvinyl butyral, etc., for example, alcohols, esters, ketones, etc.
  • the organic compound is polyvinyl alcohol
  • water can be used.
  • a surfactant may be added to promote the mixing and dispersion of amorphous carbon in the solution and improve the adhesion between the organic compound and amorphous carbon. preferable.
  • the removal of the solvent can be performed by heating in a normal pressure or reduced pressure atmosphere.
  • the temperature at the time of solvent removal is preferably 200 ° C. or lower when the atmosphere is air.
  • oxygen in the atmosphere reacts with the organic compound and the solvent (especially when creosote oil is used), the amount of carbon produced by the calcination fluctuates, and the porosity increases, so There are cases where the physical properties of the present invention as a substance deviate and the desired properties cannot be expressed.
  • Firing conditions for carbon coating may be appropriately determined in consideration of the carbonization rate of the organic compound, and are not particularly limited, but are preferably 700 to 1400 ° C., more preferably 800 in a non-oxidizing atmosphere. It is preferably in the range of ⁇ 1300 ° C.
  • the non-oxidizing atmosphere include an inert gas atmosphere such as nitrogen, argon, and helium, a vacuum atmosphere, and a circulated combustion exhaust gas atmosphere.
  • the firing time is appropriately selected depending on the type of organic compound used and the amount of the organic compound used, and is not particularly limited.
  • the baking apparatus to be used is not particularly limited as long as it is a reaction apparatus having a heating mechanism, and examples thereof include a baking apparatus capable of processing by a continuous method, a batch method, or the like.
  • a fluidized bed reaction furnace for example, there are a fluidized bed reaction furnace, a rotary furnace, a tunnel furnace, a batch furnace, and the like, which can be appropriately selected according to the purpose.
  • the amorphous carbon obtained by the firing treatment may be agglomerated of individual particles, it is preferable to disintegrate, and further when adjustment to the desired median particle diameter is necessary.
  • a pulverization process may be performed.
  • thermogravimetric measurement result (TG) of the amorphous carbon (after coating) formed with the carbon layer by the above method is a non-crystalline amorphous material due to the influence of the formed carbon layer (crystallinity, coating amount, etc.) It may be different from the result of thermogravimetric measurement of carbonaceous material (before coating).
  • the weight at 550 ° C. in the air stream has 70% or more with respect to the weight at 25 ° C., and the weight at 650 ° C. Is preferably 20% or less based on the weight of 25 ° C.
  • the crystallinity of the carbon layer on the surface of the amorphous carbon particles is preferably lower than that of amorphous carbon serving as a nucleus.
  • the crystallinity of the carbon layer lower than that of amorphous carbon as a nucleus, the familiarity between the negative electrode active material for a lithium ion battery and the electrolytic solution is improved, and as a result, the lifetime characteristics tend to be improved.
  • amorphous carbon is used as a negative electrode active material, it is excellent in safety, input / output characteristics, and life characteristics.
  • the amorphous carbon in the present invention includes those comprising an amorphous carbon as a nucleus and a carbon layer formed on the surface of the amorphous carbon.
  • the method for forming the carbon layer here is not particularly limited, but desired physical properties can be controlled by appropriately selecting various firing conditions (type of organic compound, coating amount, firing temperature, etc.). As a result, desired characteristics can be expressed.
  • a carbonaceous material having high conductivity such as graphite or activated carbon may be mixed and used as the negative electrode active material.
  • a carbonaceous material having high conductivity such as graphite or activated carbon
  • graphite material materials having the characteristics shown in (1) to (3) below may be used.
  • Intensity ratio X value (I (110) / I (004)) between the peak intensity (I (110)) on the (110) plane and the peak intensity (I (004)) on the (004) plane in X-ray diffraction ) Is 0.1 or more and 0.45 or less. Battery performance can be improved by using the graphite under such conditions as the negative electrode active material.
  • a carbonaceous material having a different property from the carbonaceous material used as the negative electrode active material may be added as a conductive material.
  • the above properties indicate one or more characteristics of X-ray diffraction parameters, median diameter, aspect ratio, BET specific surface area, orientation ratio, Raman R value, tap density, true density, pore distribution, circularity, and ash content. .
  • a carbonaceous material that is not symmetric when the volume-based particle size distribution is centered on the median diameter is used as the conductive material.
  • a carbonaceous material having a different Raman R value from a carbonaceous material used as a negative electrode active material as a conductive material, or a carbonaceous material having a different X-ray parameter from a carbonaceous material used as a negative electrode active material as a conductive material is used as the conductive material.
  • a carbonaceous material having a different Raman R value from a carbonaceous material used as a negative electrode active material as a conductive material or a carbonaceous material having a different X-ray parameter from a carbonaceous material used as a negative electrode active material as a conductive material.
  • a carbonaceous material having high conductivity such as graphite, amorphous, activated carbon or the like can be used.
  • graphite graphite
  • carbon black such as acetylene black
  • amorphous carbon such as needle coke
  • the range of the content of the conductive material relative to the weight of the negative electrode mixture is as follows.
  • the lower limit of the range is 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and the upper limit is 45% by mass or less, preferably 40% by mass or less. If it is less than the above lower limit, it is difficult to obtain the effect of improving conductivity, and if it exceeds the above upper limit, the initial irreversible capacity may be increased.
  • the material of the current collector for the negative electrode is not particularly limited, and specific examples include metal materials such as copper, nickel, stainless steel, and nickel-plated steel. Among these, copper is preferable from the viewpoint of ease of processing and cost.
  • the shape of the current collector is not particularly limited, and materials processed into various shapes can be used. Specific examples include metal foil, metal cylinder, metal coil, metal plate, metal thin film, expanded metal, punch metal, and foam metal. Among these, a metal thin film is preferable, and a copper foil is more preferable.
  • the copper foil includes a rolled copper foil formed by a rolling method and an electrolytic copper foil formed by an electrolytic method, both of which are suitable for use as a current collector.
  • the thickness of the current collector is not limited, but if the thickness is less than 25 ⁇ m, its strength can be increased by using a strong copper alloy (phosphor bronze, titanium copper, Corson alloy, Cu—Cr—Zr alloy, etc.) rather than pure copper. Can be improved.
  • a strong copper alloy phosphor bronze, titanium copper, Corson alloy, Cu—Cr—Zr alloy, etc.
  • the range of the negative electrode compound material density is as follows.
  • the lower limit of the negative electrode composite density is preferably 0.7 g / cm 3 or more, more preferably 0.8 g / cm 3 , still more preferably 0.9 g / cm 3 or more, and the upper limit is 2 g / cm 3 or less.
  • Preferably it is 1.9 g / cm 3 or less, more preferably 1.8 g / cm 3 or less, and even more preferably 1.7 g / cm 3 or less.
  • the binder for the negative electrode active material is not particularly limited as long as it is a material that is stable with respect to the non-aqueous electrolyte and the dispersion solvent used when forming the electrode.
  • resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, cellulose, nitrocellulose; SBR (styrene-butadiene rubber), isoprene rubber, butadiene rubber, fluorine rubber, NBR ( Acrylonitrile- (butadiene rubber)), rubber-like polymers such as ethylene-propylene rubber, styrene / ethylene / butadiene / styrene copolymers, polymer compositions having ion conductivity of alkali metal ions (particularly lithium ions), and the like. . These may be used alone or in combination of two or more.
  • any type of solvent can be used as long as it can dissolve or disperse the negative electrode active material, the binder, and the conductive material and the thickener used as necessary.
  • an aqueous solvent or an organic solvent may be used.
  • the aqueous solvent include water, a mixed solvent of alcohol and water
  • the organic solvent include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, and the like.
  • NMP N-methylpyrrolidone
  • dimethylformamide dimethylacetamide
  • methyl ethyl ketone cyclohexanone
  • a thickener it is preferable to use a thickener.
  • a dispersing agent or the like is added to the thickener, and a slurry is formed using a latex such as SBR.
  • the said dispersion solvent may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the range of the binder content relative to the weight of the negative electrode mixture is as follows.
  • the lower limit of the range is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 0.6% by mass or more.
  • the upper limit is 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 8% by mass or less.
  • the proportion of the binder that does not contribute to the battery capacity increases, which may lead to a decrease in battery capacity. Moreover, if it is less than the said minimum, there exists a possibility of causing the fall of the intensity
  • the range of the binder content relative to the weight of the negative electrode mixture when a rubbery polymer typified by SBR is used as the main component as the binder is as follows.
  • the lower limit of the range is 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more, and the upper limit is 5% by mass or less, preferably 3% by mass or less, more preferably. Is 2% by mass or less.
  • the range of the binder content relative to the weight of the negative electrode mixture in the case where a fluorine-based polymer typified by polyvinylidene fluoride is used as the main component as the binder is as follows.
  • the lower limit of the range is 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and the upper limit is 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less. is there.
  • Thickener is used to adjust the viscosity of the slurry.
  • the thickener is not particularly limited, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used alone or in combination of two or more.
  • the range of the content of the thickener relative to the weight of the negative electrode mixture when the thickener is used is as follows.
  • the lower limit of the range is 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more, and the upper limit is 5% by mass or less, preferably 3% by mass or less, more preferably. Is 2% by mass or less.
  • the density of the negative electrode mixture is set to 0.8 g / cm 3 or more and 1.05 g / cm 3 or less in addition to the conditions of the positive electrode mixture described in the section of “1. Further, by setting the coating amount of the negative electrode mixture to 50 g / m 2 or more and 100 g / m 2 or less, it is possible to improve battery characteristics such as improvement of output characteristics.
  • the porosity of the negative electrode mixture is set to 32% or more and 46% or less, so that the output characteristics are improved. It is possible to improve battery characteristics such as improvement.
  • the positive electrode mixture having the conditions described in the section “1. Positive electrode” is used, and the negative electrode mixture has the conditions described in the section “1. Positive electrode”.
  • battery characteristics such as input / output characteristics and life characteristics can be improved.
  • Electrolytic Solution The electrolytic solution of the present embodiment is composed of a lithium salt (electrolyte) and a non-aqueous solvent that dissolves the lithium salt. You may add an additive as needed.
  • the lithium salt is not particularly limited as long as it is a lithium salt that can be used as an electrolyte of a non-aqueous electrolyte for a lithium ion battery.
  • a lithium salt that can be used as an electrolyte of a non-aqueous electrolyte for a lithium ion battery.
  • inorganic lithium salt LiPF 6, LiBF 4, LiAsF 6, LiSbF inorganic fluoride salts and the like 6, LiClO 4, Libro 4, LiIO and perhalogenate such as 4, an inorganic chloride salts such as LiAlCl 4, etc. Is mentioned.
  • lithium salts may be used alone or in combination of two or more.
  • lithium hexafluorophosphate LiPF 6
  • LiPF 6 lithium hexafluorophosphate
  • a preferable example in the case of using two or more lithium salts is a combination of LiPF 6 and LiBF 4 .
  • the proportion of LiBF 4 in the total of both is preferably 0.01% by mass or more and 20% by mass or less, and more preferably 0.1% by mass or more and 5% by mass or less.
  • Another preferred example is the combined use of an inorganic fluoride salt and a perfluoroalkanesulfonylimide salt.
  • the proportion of the inorganic fluoride salt in the total of both is 70% by mass or more and 99% by mass. % Or less, more preferably 80% by mass or more and 98% by mass or less. According to the above two preferred examples, characteristic deterioration due to high temperature storage can be suppressed.
  • the concentration of the electrolyte in the non-aqueous electrolyte solution is as follows.
  • the lower limit of the concentration is 0.5 mol / L or more, preferably 0.6 mol / L or more, more preferably 0.7 mol / L or more.
  • the upper limit of the concentration is 2 mol / L or less, preferably 1.8 mol / L or less, more preferably 1.7 mol / L or less. If the concentration is too low, the electric conductivity of the electrolytic solution may be insufficient. On the other hand, if the concentration is too high, the viscosity increases and the electrical conductivity may decrease. Such a decrease in electrical conductivity may reduce the performance of the lithium ion battery.
  • the non-aqueous solvent is not particularly limited as long as it is a non-aqueous solvent that can be used as an electrolyte solvent for a lithium ion battery.
  • a non-aqueous solvent that can be used as an electrolyte solvent for a lithium ion battery.
  • the following cyclic carbonate, chain carbonate, chain ester, cyclic ether, and chain ether are used. Etc.
  • an alkylene group constituting the cyclic carbonate preferably has 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms.
  • Specific examples include ethylene carbonate, propylene carbonate, butylene carbonate, and the like. Of these, ethylene carbonate and propylene carbonate are preferable.
  • the chain carbonate is preferably a dialkyl carbonate, and the two alkyl groups each preferably have 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms.
  • symmetrical chain carbonates such as dimethyl carbonate, diethyl carbonate and di-n-propyl carbonate; asymmetric chain carbonates such as ethyl methyl carbonate, methyl-n-propyl carbonate and ethyl-n-propyl carbonate Is mentioned.
  • dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are preferable.
  • a mixed solvent in which two or more compounds are used in combination.
  • a high dielectric constant solvent of cyclic carbonates in combination with a low viscosity solvent such as chain carbonates or chain esters.
  • a high dielectric constant solvent of cyclic carbonates in combination with a low viscosity solvent such as chain carbonates or chain esters.
  • One of the preferable combinations is a combination mainly composed of cyclic carbonates and chain carbonates.
  • the total of the cyclic carbonates and the chain carbonates in the non-aqueous solvent is 80% by volume or more, preferably 85% by volume or more, more preferably 90% by volume or more, and the cyclic carbonates and the chain carbonates.
  • the cyclic carbonates have a capacity in the following range with respect to the total of the above.
  • the lower limit of the capacity of the cyclic carbonates is 5% or more, preferably 10% or more, more preferably 15% or more, and the upper limit is 50% or less, preferably 35% or less, more preferably 30% or less.
  • cyclic carbonates and chain carbonates include ethylene carbonate and dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and ethyl methyl carbonate, and the like.
  • a combination in which propylene carbonate is further added to the combination of these ethylene carbonate and chain carbonate is also mentioned as a preferable combination.
  • the volume ratio of ethylene carbonate to propylene carbonate is preferably 99: 1 to 40:60, more preferably 95: 5 to 50:50.
  • the range of the amount of propylene carbonate in the non-aqueous solvent is as follows.
  • the lower limit of the amount of propylene carbonate is 0.1% by volume or more, preferably 1% by volume or more, more preferably 2% by volume or more, and the upper limit is 10% by volume or less, preferably 8% by volume or less, more preferably 5% by volume or less. According to such a combination, the low temperature characteristics can be further improved while maintaining the characteristics of the combination of ethylene carbonate and chain carbonates.
  • the additive is not particularly limited as long as it is an additive for a non-aqueous electrolyte solution of a lithium ion battery.
  • nitrogen, sulfur or a heterocyclic compound containing nitrogen and sulfur, a cyclic carboxylic acid ester, a fluorine-containing cyclic examples thereof include carbonates and other compounds having an unsaturated bond in the molecule.
  • additives such as an overcharge prevention material, a negative electrode film forming material, a positive electrode protection material, and a high input / output material may be used depending on the required function.
  • negative electrode film-forming material examples include succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, and the like. Of these, succinic anhydride and maleic anhydride are preferable. Two or more of these negative electrode film forming materials may be used in combination.
  • Examples of the positive electrode protective material include methyl methanesulfonate, busulfan, methyl toluenesulfonate, dimethyl sulfate, diethyl sulfate, dimethyl sulfone, and diethyl sulfone. Of these, methyl methanesulfonate, busulfan, and dimethylsulfone are preferable. Two or more of these positive electrode protective materials may be used in combination.
  • perfluoroalkyl polyoxyethylene ether and fluorinated alkyl ester are preferable.
  • the ratio of the additive in the non-aqueous electrolyte solution is not particularly limited, but the range is as follows. In addition, when using a some additive, the ratio of each additive is meant.
  • the lower limit of the ratio of the additive to the non-aqueous electrolyte is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and the upper limit is preferably 5%. It is at most 3% by mass, more preferably at most 3% by mass, even more preferably at most 2% by mass.
  • the other additives described above can suppress rapid electrode reactions during abnormalities due to overcharging, improve capacity maintenance characteristics and cycle characteristics after high-temperature storage, and improve input / output characteristics.
  • Separator is not particularly limited as long as it has ion permeability while electronically insulating the positive electrode and the negative electrode, and has resistance to oxidation on the positive electrode side and reducibility on the negative electrode side.
  • a material (material) of the separator satisfying such characteristics a resin, an inorganic material, glass fiber, or the like is used.
  • olefin polymer fluorine polymer, cellulose polymer, polyimide, nylon or the like is used.
  • resin olefin polymer, fluorine polymer, cellulose polymer, polyimide, nylon or the like is used.
  • materials that are stable with respect to non-aqueous electrolytes and have excellent liquid retention properties For example, porous sheets or nonwoven fabrics made from polyolefins such as polyethylene and polypropylene may be used. preferable.
  • oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate are used.
  • thin film-shaped base materials such as a nonwoven fabric, a woven fabric, and a microporous film, can be used as a separator.
  • the thin film-shaped substrate those having a pore diameter of 0.01 to 1 ⁇ m and a thickness of 5 to 50 ⁇ m are preferably used.
  • a separator in which a composite porous layer is formed using the above-described inorganic material in a fiber shape or a particle shape by using a binder such as a resin can be used as a separator.
  • this composite porous layer may be formed on the surface of the positive electrode or the negative electrode to form a separator.
  • a composite porous layer in which alumina particles having a 90% particle size of less than 1 ⁇ m are bound using a fluororesin as a binder may be formed on the surface of the positive electrode.
  • a cleavage valve may be provided. By opening the cleavage valve, it is possible to suppress an increase in pressure inside the battery and to improve safety.
  • a component that emits an inert gas (for example, carbon dioxide) as the temperature rises may be provided.
  • an inert gas for example, carbon dioxide
  • the cleavage valve can be opened quickly due to the generation of inert gas, and safety can be improved.
  • the material used for the component include lithium carbonate and polyalkylene carbonate resin, and lithium carbonate, polyethylene carbonate, and polypropylene carbonate are particularly preferable.
  • the positive electrode plate was produced as follows.
  • the positive electrode active material layered type lithium / nickel / manganese / cobalt composite oxide (NMC) and spinel type lithium / manganese oxide (sp-Mn) are mixed in a predetermined active material weight ratio (NMC / sp-Mn).
  • NMC nickel / manganese / cobalt composite oxide
  • sp-Mn spinel type lithium / manganese oxide
  • NMC / sp-Mn active material weight ratio
  • scaly graphite average particle size: 20 ⁇ m
  • polyvinylidene fluoride as a binder were sequentially added and mixed to obtain a mixture of positive electrode materials.
  • NMP N-methyl-2-pyrrolidone
  • a predetermined amount of this slurry was applied to both surfaces of a 20 ⁇ m thick aluminum foil as a positive electrode current collector substantially uniformly and uniformly.
  • the aluminum foil had a rectangular shape with a short side (width) of 350 mm, and an uncoated portion with a width of 50 mm was left along the long side on one side.
  • the drying process was performed and it consolidated by the press to the predetermined density.
  • a positive electrode plate having a width of 350 mm was obtained by cutting. At this time, a notch was made in the uncoated portion, and the remaining notch was used as a lead piece.
  • the width of the lead piece was 10 mm, and the interval between adjacent lead pieces was 20 mm.
  • the negative electrode plate was produced as follows. Amorphous carbon was used as the negative electrode active material. Specifically, amorphous carbon having a particle size of 10 ⁇ m and a specific surface area of 5.1 m 2 / g was used.
  • Polyvinylidene fluoride was added as a binder to the amorphous carbon.
  • a slurry was formed by adding N-methyl-2-pyrrolidone (NMP) as a dispersion solvent and kneading. A predetermined amount of this slurry was applied to both surfaces of a rolled copper foil having a thickness of 10 ⁇ m, which is a negative electrode current collector, substantially uniformly and uniformly.
  • the rolled copper foil had a rectangular shape with a short side (width) of 355 mm, and left an uncoated part with a width of 50 mm along the long side on one side.
  • the drying process was performed and it consolidated by the press to the predetermined density.
  • the negative electrode mixture density was 1.0 g / cm 3 .
  • a negative electrode plate having a width of 355 mm was obtained by cutting. At this time, a notch was made in the uncoated portion, and the remaining notch was used as a lead piece.
  • the width of the lead piece was 10 mm, and the interval between adjacent lead pieces was 20 mm.
  • the negative electrode composite porosity was measured.
  • the negative electrode composite material porosity is the ratio [volume%] of the volume of the pores to the volume of the negative electrode composite material.
  • the volume of the negative electrode mixture can be calculated, for example, from the product of the application area (formation area) of the negative electrode mixture and its thickness (film thickness). Further, the volume of the pores can be calculated from the pore volume measured by mercury porosimetry (mercury intrusion method).
  • the positive electrode mixture and the negative electrode mixture may be formed on at least one side or both sides of the positive electrode or negative electrode current collector.
  • Fig. 1 shows a cross-sectional view of a lithium ion battery.
  • the positive electrode plate and the negative electrode plate are wound with a polyethylene separator having a thickness of 30 ⁇ m interposed therebetween so that they are not in direct contact with each other.
  • the lead piece of the positive electrode plate and the lead piece of the negative electrode plate are respectively positioned on the opposite end surfaces of the wound electrode group. Further, the lengths of the positive electrode plate, the negative electrode plate, and the separator were adjusted, and the diameter of the wound electrode group was set to 65 ⁇ 0.1 mm or 40 ⁇ 0.1 mm.
  • the lead pieces 9 led out from the positive electrode plate are deformed, and all of them are gathered near the bottom of the flange 7 on the positive electrode side and brought into contact with each other.
  • the flange portion 7 on the positive electrode side is integrally formed so as to protrude from the periphery of the pole column (positive electrode external terminal 1) substantially on the extension line of the axis of the wound electrode group 6, and has a bottom portion and a side portion. .
  • the lead piece 9 is connected and fixed to the bottom of the flange 7 by ultrasonic welding.
  • the lead piece 9 led out from the negative electrode plate and the bottom of the flange 7 on the negative electrode side are similarly connected and fixed.
  • the negative electrode side flange portion 7 is integrally formed so as to protrude from the periphery of the pole column (negative electrode external terminal 1 ′) substantially on the extension line of the axis of the wound electrode group 6, and the bottom portion and the side portion are formed. Have.
  • an insulating coating 8 was formed by covering the side of the flange 7 on the positive electrode external terminal 1 side and the side of the flange 7 of the negative electrode external terminal 1 ′. Similarly, an insulating coating 8 was formed on the outer periphery of the wound electrode group 6. For example, this adhesive tape is applied from the side of the flange 7 on the positive electrode external terminal 1 side to the outer peripheral surface of the wound electrode group 6 and further from the outer peripheral surface of the wound electrode group 6 to the negative electrode external terminal 1 ′. Insulating coating 8 is formed by winding several times over the side of side flange 7.
  • the insulating coating (adhesive tape) 8 an adhesive tape in which the base material was polyimide and an adhesive material made of hexamethacrylate was applied on one surface thereof was used.
  • the thickness of the insulating coating 8 (the number of windings of the adhesive tape) is adjusted so that the maximum diameter portion of the wound electrode group 6 is slightly smaller than the inner diameter of the battery case 5 made of stainless steel.
  • the battery was inserted into the battery container 5.
  • the battery container 5 had an outer diameter of 67 mm or 42 mm and an inner diameter of 66 mm or 41 mm.
  • the ceramic washer 3 ′ is fitted into the pole column whose tip constitutes the positive electrode external terminal 1 and the pole column whose tip constitutes the negative electrode external terminal 1 ′.
  • the ceramic washer 3 ′ is made of alumina, and the thickness of the portion in contact with the back surface of the battery lid 4 is 2 mm, the inner diameter is 16 mm, and the outer diameter is 25 mm.
  • the positive external terminal 1 is passed through the ceramic washer 3, and with the other ceramic washer 3 placed on the other battery lid 4, the negative external terminal Pass 1 'through another ceramic washer 3.
  • the ceramic washer 3 is made of alumina and has a flat plate shape with a thickness of 2 mm, an inner diameter of 16 mm, and an outer diameter of 28 mm.
  • the peripheral end surface of the battery lid 4 is fitted into the opening of the battery container 5, and the entire area of both contact portions is laser-welded.
  • the positive electrode external terminal 1 and the negative electrode external terminal 1 ′ pass through a hole (hole) in the center of the battery cover 4 and project outside the battery cover 4.
  • the battery lid 4 is provided with a cleavage valve 10 that cleaves in response to an increase in the internal pressure of the battery.
  • the cleavage pressure of the cleavage valve 10 was 13 to 18 kgf / cm 2 .
  • the metal washer 11 is fitted into the positive external terminal 1 and the negative external terminal 1 ′. Thereby, the metal washer 11 is disposed on the ceramic washer 3.
  • the metal washer 11 is made of a material smoother than the bottom surface of the nut 2.
  • the metal nut 2 is screwed to the positive electrode external terminal 1 and the negative electrode external terminal 1 ′, and the battery lid 4 is connected to the flange portion 7 and the nut 2 through the ceramic washer 3, the metal washer 11, and the ceramic washer 3 ′. Secure by tightening between.
  • the tightening torque value at this time was 70 kgf ⁇ cm.
  • the metal washer 11 did not rotate until the tightening operation was completed.
  • the power generation element inside the battery container 5 is shielded from the outside air by the compression of the rubber (EPDM) O-ring 12 interposed between the back surface of the battery lid 4 and the flange 7.
  • LiPF 6 lithium hexafluorophosphate
  • ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate were mixed at a volume ratio of 2: 3: 2. What was done was used. Note that the cylindrical lithium ion battery 20 manufactured in this example is not provided with a current interrupting mechanism that operates to interrupt the current in accordance with the increase in the internal pressure of the battery container 5.
  • the positive electrode mixture density about the prepared lithium ion battery, the positive electrode mixture density, the positive electrode mixture coating amount, and the weight ratio of the layered lithium / nickel / manganese / cobalt composite oxide (NMC) to the spinel type lithium / manganese oxide (sp-Mn)
  • NMC nickel / manganese / cobalt composite oxide
  • sp-Mn spinel type lithium / manganese oxide
  • a charge / discharge cycle with a current value of 0.5 C was repeated twice in a voltage range of 4.2 to 2.7 V in an environment of 25 ° C. Further, after charging the battery to 4.2 V, a nail having a diameter of 5 mm was inserted into the center of the battery (cell) at a speed of 1.6 mm / second, and the positive electrode and the negative electrode were short-circuited inside the battery container. At this time, changes in the appearance of the battery were confirmed.
  • Example A (Examples A1 to A80)
  • positive electrode composites were prepared by changing the weight ratio of active material (NMC / sp-Mn), positive electrode mixture density, and positive electrode mixture application amount, and the diameter of the wound electrode group A battery having a diameter of 40 mm, an outer diameter of 42 mm, and an inner diameter of 41 mm was produced.
  • Discharge capacity at each current value (0.5C and 3C), volumetric energy density at current value 0.5C, output characteristics (discharge capacity at current value 3C / discharge capacity at current value 0.5C) and safety (nail penetration test) And external short circuit test).
  • the presence or absence of damage to the battery container was confirmed. Damage to the battery container includes cracks, expansion and ignition.
  • Examples A81 to A144 As shown in Table 4 and Table 5, the positive electrode mixture was prepared by changing the weight ratio of active material (NMC / sp-Mn), the positive electrode mixture density, and the positive electrode mixture application amount, and the diameter of the wound electrode group A battery with 65 mm, outer diameter 67 mm, and inner diameter 66 mm was produced. Discharge capacity at each current value (0.5C and 3C), volumetric energy density at current value 0.5C, output characteristics (discharge capacity at current value 3C / discharge capacity at current value 0.5C) and safety (nail penetration test) And external short circuit test). The results are shown in Table 4 and Table 5.
  • Examples A145 and A146 The lithium ion battery life shown below was evaluated.
  • the battery was charged to 4.2 V in an environment of 25 ° C., then left for one month in an environment of 40 ° C., and the capacity after being left in an environment of 25 ° C. was measured.
  • Table 6 shows the capacity ratio before and after being left.
  • the capacity before standing was the capacity obtained by constant current discharge at a current value of 0.5 C and a final voltage of 2.7 V after charging the battery to 4.2 V in an environment of 25 ° C.
  • Evaluation targets are the lithium ion battery of Example A144 and the lithium ion batteries of Examples A145 and A146 shown below. The results are shown in Table 6.
  • Example A145 A lithium ion battery was prepared in the same manner as in Example A144, except that an Al-substituted spinel type lithium / manganese oxide was used as the spinel type lithium / manganese oxide (sp-Mn), and the lifetime was evaluated.
  • sp-Mn spinel type lithium / manganese oxide
  • Example A146 A lithium ion battery was prepared and evaluated for life in the same manner as in Example A144 except that Mg-substituted spinel type lithium / manganese oxide was used as the spinel type lithium / manganese oxide (sp-Mn).
  • the positive electrode mixture was prepared by changing the weight ratio of the active material (NMC / sp-Mn), the positive electrode mixture density, and the positive electrode mixture coating amount.
  • a battery having a diameter of 67 mm and an inner diameter of 66 mm was produced.
  • Discharge capacity at each current value 0.5C and 3C
  • volumetric energy density at current value 0.5C 0.5C
  • output characteristics discharge capacity at current value 3C / discharge capacity at current value 0.5C
  • safety node penetration test
  • External short circuit test The results are shown in Table 8.
  • Example A145 and A146 shown in Table 6 it has confirmed that it was longer life than Example A144. This will be described in detail below.
  • Example A144 in Table 5 and Comparative Example A2 in Table 8 were compared, the weight ratio of active material (NMC / sp-Mn) was 50/50, respectively, and the positive electrode mixture application amount was respectively be the same at 250 g / m 2, it is seen that safety can be secured by lowering the positive electrode density from 2.8 g / cm 3 to 2.7 g / cm 3.
  • Example A144 in Table 5 and Comparative Example A3 in Table 8 are compared, the weight ratio of active materials (NMC / sp-Mn) is 50/50, respectively, and the positive electrode mixture density is 2 respectively. Even if it is the same at 0.7 g / cm 3 , it can be seen that safety can be ensured by reducing the coating amount of the positive electrode mixture from 275 g / m 2 to 250 g / m 2 .
  • Example A144 in Table 5 and Comparative Examples A4 to A6 in Table 8 are compared, even if the same positive electrode mixture density is 2.7 g / cm 3 and the same positive electrode mixture application amount is 250 g / m 2 , It can be seen that the safety can be ensured by setting the ratio of the layered lithium / nickel / manganese / cobalt composite oxide (NMC) in the active material to 50% by mass or less which is less than 70% by mass.
  • NMC cobalt composite oxide
  • FIG. 2 is a graph summarizing the discharge capacity, the weight ratio of the active material, and the rising temperature of the battery surface by the external short circuit test. Specifically, for Examples A1 to A144, the relationship between the discharge capacity X on the horizontal axis and the weight ratio Y (NMC / sp-Mn) of the active material on the vertical axis was plotted. At this time, the plots are indicated by ⁇ (black circles) for the examples where the rising temperature of the battery surface is less than 3 ° C., and the plots are indicated by ⁇ (white circles) for the examples where the rising temperature is 3 ° C. or more.
  • the straight line in the figure is a straight line that satisfies the following relational expression 2. From the graph of FIG. 2, it was found that a safer battery having a temperature increase of less than 3 ° C. in the region below relational expression 2 was obtained.
  • the preferable ratio of the positive electrode active material with respect to positive electrode compound material is 85 to 95 mass%.
  • the ratio of the positive electrode active material to the positive electrode mixture is low, the volume energy density of the battery that can ensure the safety of the battery decreases.
  • the ratio of the positive electrode active material to the positive electrode mixture is high, although the safety of the battery can be ensured, the output characteristics are deteriorated.
  • by ensuring the proportion of the positive electrode active material in the above range it is possible to increase the capacity while ensuring safety, and to improve input / output characteristics.
  • the range of the conductive material and the binder that can be mixed with the positive electrode mixture is 5% by mass or more and 15% by mass or less with respect to the positive electrode mixture. It becomes. Even when the conductive material and the binder are adjusted so as to be in such a range, the respective functions can be sufficiently exhibited.
  • the effect of the conductive material increases at 3% by mass or more and saturates at about 7% by mass. Therefore, the content of the conductive material in this embodiment is sufficient to be 3% by mass or more and 7% by mass or less.
  • 3 to 10 mass% is enough. That is, it is possible to adjust the conductive material and the binder within an effective range while ensuring a predetermined amount of the positive electrode active material.
  • the battery characteristics can be improved in the same manner as in the above example. This has been confirmed by other studies by the present inventors in which the ratio of the active material: conductive material: binder to the positive electrode mixture is changed.
  • Example B (Examples B1 to B9) [Production of positive electrode plate]
  • the positive electrode plate was produced as follows. A layered lithium-nickel-manganese-cobalt composite oxide (NMC) and a spinel-type lithium-manganese oxide (sp-Mn), which are positive electrode active materials, and an active material weight ratio (NMC / sp-Mn) of 30 / 70 and mixed. To this mixture of positive electrode active materials, scaly graphite (average particle size: 20 ⁇ m) as a conductive material and polyvinylidene fluoride as a binder were sequentially added and mixed to obtain a mixture of positive electrode materials.
  • NMC lithium-nickel-manganese-cobalt composite oxide
  • sp-Mn spinel-type lithium-manganese oxide
  • NMC / sp-Mn active material weight ratio
  • the aluminum foil had a rectangular shape with a short side (width) of 350 mm, and an uncoated portion with a width of 50 mm was left along the long side on one side. Then, the drying process was performed and it consolidated by the press to the predetermined density. Next, a positive electrode plate having a width of 350 mm was obtained by cutting.
  • a notch was made in the uncoated portion, and the remaining notch was used as a lead piece.
  • the width of the lead piece was 10 mm, and the interval between adjacent lead pieces was 20 mm.
  • the positive electrode mixture application amount was 180 g / m 2
  • the positive electrode mixture density was 2.55 g / cm 3 (Table 9).
  • the negative electrode plate was produced as follows.
  • non-graphitizable carbon or graphitizable carbon which is amorphous carbon was used as the negative electrode active material.
  • the non-graphitizable carbon has a particle diameter (median particle diameter) of 10 ⁇ m, a specific surface area of 5.1 m 2 / g, a carbon dioxide adsorption amount of 4.1 cm 3 / g, and an R value (IG / ID) of 0.96.
  • the non-graphitizable carbon having the following physical properties was used (Comparative Example B1).
  • graphitizable carbon As graphitizable carbon, graphitizable carbon having the physical properties shown in Table 10 and Table 11 was used (Examples B1 to B9, Comparative Examples B2 to B4). Specifically, in Examples B1 to B9 and Comparative Examples B2 to B4, the particle diameter (median particle diameter) is 14 ⁇ m, the specific surface area is 6.5 g / m 2 , and the R value (IG / ID) is 1.16.
  • the graphitizable carbon coated with carbon under various firing conditions was used for the graphitizable carbon serving as a nucleus (Tables 10 and 11). In the graphitizable carbon before carbon coating, the weight at 550 ° C. in the air stream determined by thermogravimetry (TG) is 94% with respect to the weight at 25 ° C., and the weight at 650 ° C. is the weight at 25 ° C. 1%.
  • Polyvinylidene fluoride was added as a binder to these negative electrode active materials.
  • a slurry was formed by adding N-methyl-2-pyrrolidone (NMP) as a dispersion solvent and kneading. A predetermined amount of this slurry was applied to both surfaces of a rolled copper foil having a thickness of 10 ⁇ m, which is a negative electrode current collector, substantially uniformly and uniformly.
  • the rolled copper foil had a rectangular shape with a short side (width) of 355 mm, and left an uncoated part with a width of 50 mm along the long side on one side. Then, the drying process was performed and it consolidated by the press to the predetermined density.
  • a negative electrode plate having a width of 355 mm was obtained by cutting. At this time, a notch was made in the uncoated part, and the remaining part of the notch was used as a lead piece.
  • the width of the lead piece was 10 mm, and the interval between adjacent lead pieces was 20 mm.
  • the discharge capacity per area of both negative electrode plates is The amount of slurry applied and the density of the mixture were adjusted so as to be equivalent.
  • the negative electrode mixture application amount is 60 g / m 2
  • the negative electrode mixture density is 1.0 g / cm 3
  • the negative electrode mixture using graphitizable carbon is The negative electrode mixture application amount was 80 g / m 2
  • the negative electrode mixture density was 1.2 g / cm 3 (Table 9).
  • the amount of slurry applied to the positive electrode plate was adjusted so that the ratio of the discharge capacity per unit area of the positive electrode plate to the discharge capacity per unit area of the negative electrode plate was approximately the same (Table 9). For this reason, a battery using non-graphitizable carbon as the negative electrode active material has a larger amount of slurry applied to the positive electrode plate than a battery using graphitizable carbon as the negative electrode active material.
  • particle diameter is the median particle diameter D50.
  • the specific surface area is a specific surface area (area per unit g) determined by the BET method.
  • the amount of carbon dioxide adsorbed was 273 K after 0.5 g of the negative electrode active material was collected in a quartz sample tube and degassed by drying under reduced pressure at 150 ° C. for 8 hours. The carbon dioxide adsorption up to a relative pressure of 0.03 was measured and calculated by the multipoint method.
  • the weight ratio at 550 ° C. and 650 ° C. with respect to 25 ° C. was determined by collecting 10 mg of the negative electrode active material using a thermogravimetric analyzer (TG) and using alumina as a reference under a flow of dry air of 300 ml / min. The speed was calculated from the result measured at 1 ° C./min.
  • the R value (IG / ID) was measured using a microscopic Raman imaging apparatus manufactured by Thermo Scientific, with a laser output of 4 mW, a step size of 2.5 ⁇ m, an exposure count of 5 times, and an exposure time of 2 seconds.
  • the tap density was gradually increased to 5 cm with a filling density measuring device (KRS-406 manufactured by Kuramotsu Kagaku Kikai Seisakusho) after gradually pouring 50 g of the negative electrode active material into a measuring cylinder with a capacity of 150 cm 3 and plugging the measuring cylinder. Then, the mass of the negative electrode active material after dropping 250 times was calculated by dividing by the capacity.
  • KRS-406 manufactured by Kuramotsu Kagaku Kikai Seisakusho
  • the positive electrode plate and the negative electrode plate are wound with a polyethylene separator having a thickness of 30 ⁇ m interposed therebetween so that they are not in direct contact with each other.
  • the lead piece of the positive electrode plate and the lead piece of the negative electrode plate are respectively positioned on the opposite end surfaces of the wound electrode group. Further, the lengths of the positive electrode plate, the negative electrode plate, and the separator were adjusted, and the diameter of the wound electrode group was set to 65 ⁇ 0.1 mm or 40 ⁇ 0.1 mm.
  • the lead pieces 9 led out from the positive electrode plate are deformed, and all of them are gathered near the bottom of the flange 7 on the positive electrode side and brought into contact with each other.
  • the flange portion 7 on the positive electrode side is integrally formed so as to protrude from the periphery of the pole column (positive electrode external terminal 1) substantially on the extension line of the axis of the wound electrode group 6, and has a bottom portion and a side portion. .
  • the lead piece 9 is connected and fixed to the bottom of the flange 7 by ultrasonic welding.
  • the lead piece 9 led out from the negative electrode plate and the bottom of the flange 7 on the negative electrode side are similarly connected and fixed.
  • the negative electrode side flange portion 7 is integrally formed so as to protrude from the periphery of the pole column (negative electrode external terminal 1 ′) substantially on the extension line of the axis of the wound electrode group 6, and the bottom portion and the side portion are formed. Have.
  • an insulating coating 8 was formed by covering the side of the flange 7 on the positive electrode external terminal 1 side and the side of the flange 7 of the negative electrode external terminal 1 ′. Similarly, an insulating coating 8 was formed on the outer periphery of the wound electrode group 6. For example, this adhesive tape is applied from the side of the flange 7 on the positive electrode external terminal 1 side to the outer peripheral surface of the wound electrode group 6 and further from the outer peripheral surface of the wound electrode group 6 to the negative electrode external terminal 1 ′. Insulating coating 8 is formed by winding several times over the side of side flange 7.
  • the insulating coating (adhesive tape) 8 an adhesive tape in which the base material was polyimide and an adhesive material made of hexamethacrylate was applied on one surface thereof was used.
  • the thickness of the insulating coating 8 (the number of windings of the adhesive tape) is adjusted so that the maximum diameter portion of the wound electrode group 6 is slightly smaller than the inner diameter of the battery case 5 made of stainless steel.
  • the battery was inserted into the battery container 5.
  • the battery container 5 had an outer diameter of 67 mm or 42 mm and an inner diameter of 66 mm or 41 mm.
  • the ceramic washer 3 ′ is fitted into the pole column whose tip constitutes the positive electrode external terminal 1 and the pole column whose tip constitutes the negative electrode external terminal 1 ′.
  • the ceramic washer 3 ′ is made of alumina, and the thickness of the portion in contact with the back surface of the battery lid 4 is 2 mm, the inner diameter is 16 mm, and the outer diameter is 25 mm.
  • the positive external terminal 1 is passed through the ceramic washer 3, and with the other ceramic washer 3 placed on the other battery lid 4, the negative external terminal Pass 1 'through another ceramic washer 3.
  • the ceramic washer 3 is made of alumina and has a flat plate shape with a thickness of 2 mm, an inner diameter of 16 mm, and an outer diameter of 28 mm.
  • the peripheral end surface of the battery lid 4 is fitted into the opening of the battery container 5, and the entire area of both contact portions is laser-welded.
  • the positive electrode external terminal 1 and the negative electrode external terminal 1 ′ pass through a hole (hole) in the center of the battery cover 4 and project outside the battery cover 4.
  • the battery lid 4 is provided with a cleavage valve 10 that cleaves in response to an increase in the internal pressure of the battery.
  • the cleavage pressure of the cleavage valve 10 was 13 to 18 kgf / cm 2 .
  • the metal washer 11 is fitted into the positive external terminal 1 and the negative external terminal 1 ′. Thereby, the metal washer 11 is disposed on the ceramic washer 3.
  • the metal washer 11 is made of a material smoother than the bottom surface of the nut 2.
  • the metal nut 2 is screwed to the positive electrode external terminal 1 and the negative electrode external terminal 1 ′, and the battery lid 4 is connected to the flange portion 7 and the nut 2 through the ceramic washer 3, the metal washer 11, and the ceramic washer 3 ′. Secure by tightening between.
  • the tightening torque value at this time was 70 kgf ⁇ cm.
  • the metal washer 11 did not rotate until the tightening operation was completed.
  • the power generation element inside the battery container 5 is shielded from the outside air by the compression of the rubber (EPDM) O-ring 12 interposed between the back surface of the battery lid 4 and the flange 7.
  • LiPF 6 lithium hexafluorophosphate
  • Examples B1 to B9 and Comparative Examples B2 to B4 in Tables 9 to 11 batteries using graphitizable carbon as a negative electrode active material were prepared, and as shown in the column of Comparative Example B1.
  • a battery using non-graphitizable carbon as a negative electrode active material was prepared.
  • input / output characteristics, storage life and cycle life were examined.
  • Examples B1 to B9 have improved input / output characteristics and improved life characteristics (storage life and cycle life) than Comparative Examples B1 to B4. This will be described below.
  • the volume energy densities at the current value of 0.5 C in Examples B1 to B9 and Comparative Examples B1 to B4 were comparable.
  • the discharge load characteristics were measured by charging and discharging 1 to 4 cycles shown in Table 12 and measuring the discharge capacity ratio. Specifically, CCCV charging method, current value 0.5C, voltage 4.2V, termination condition is 5 hours (hr) or 0.01C charging, CC discharging method, current value 0.5-3C, voltage A 2.7 V discharge was performed. Then, the ratio of the discharge capacity with a current value of 3C to the discharge capacity of 0.5C was obtained. This ratio indicates how much capacity can be secured with respect to the rated capacity in the case of rapid discharge (discharge with a large current). The evaluation results are shown in Table 10 and Table 11.
  • the charge load characteristics were measured by charging and discharging 6 to 9 cycles shown in Table 12 and measuring the charge capacity ratio.
  • the CC discharge method described in 5 cycles a current value of 0.5 C, and a voltage of 2.7 V were discharged, and 6 to 9 cycles of discharge were performed.
  • Charging / discharging was performed. Specifically, a CC charging method, charging with a current value of 0.5 to 3 C, and a voltage of 4.2 V, and a CC discharging method, discharging with a current value of 0.5 C, and a voltage of 2.7 V were performed.
  • the ratio of the charging capacity with a current value of 3C to the charging capacity with a current value of 0.5C was determined. This ratio indicates the degree of rapid charging and how much can be charged with a large current.
  • the evaluation results are shown in Table 10 and Table 11. It was confirmed that the 3C charging load characteristics in Examples B1 to B9 were improved as compared with Comparative Examples B1 to B4, and all of them had a large charge capacity ratio. Specifically, the charge capacity ratio at 3C is 51% in Comparative Example B1, while 65% in Example B1, 63% in Example B2, and 60% in Example B3. became. This tends to show high characteristics when graphitized carbon having a large weight ratio at 550 ° C. in thermogravimetry and a large specific surface area is used, and the same tendency was shown in Examples B4 to B9. . Thus, it was found that Examples B1 to B9 have input characteristics that can withstand charging with a large current, that is, rapid charging.
  • the battery cycle test As the battery cycle test, the following test was performed. In a constant temperature bath of 25 ° C., the charging conditions are CCCV charging method, current value is 0.5 C, voltage is 4.2 V, and the termination condition is 5 hours (hr) or 0.01 C. The battery was discharged at a CC discharge method, a current value of 0.5 C, and a voltage of 2.7 V. Such a charge-discharge cycle is defined as one cycle, and the discharge capacity retention rate from the first cycle when 300 cycles are repeated was calculated. A 15-minute pause is provided between charging and discharging. The evaluation results are shown in Table 10 and Table 11. The cycle life characteristics in Examples B1 to B9 were confirmed to be improved as compared with Comparative Examples B1 to B4, and the capacity retention ratios were all increased.
  • the input / output characteristics, the storage life, and the cycle life characteristics can be improved. This is probably because graphitizable carbon has higher crystallinity than non-graphitizable carbon and can suppress the decomposition of the electrolytic solution and the formation of a film, thereby improving the life.
  • the small specific surface area and the amount of carbon dioxide adsorbed are considered to contribute to the improvement of the life by suppressing the decomposition of the electrolyte and the film formation.
  • Example B graphitizable carbon is used as the negative electrode active material (amorphous carbon), and its particle size, specific surface area, weight ratio at 550 ° C. and 650 ° C. relative to 25 ° C., R value, Although the tap density was adjusted within the ranges shown in Table 10 and Table 11, these are not limited to the above ranges.
  • graphitizable carbon was used as the negative electrode active material, and the negative electrode mixture density was 1.2 g / cm 3.
  • the negative electrode mixture density is limited to this value. is not.
  • the density of the negative electrode mixture can be adjusted within the range of 0.8 to 1.40 g / cm 3 , for example.
  • the adjustment is preferably in the range of 0.9 to 1.35 g / cm 3 , preferably in the range of 0.95 to 1.30 g / cm 3 , more preferably in the range of 1.0 to 1.25 g / cm 3. It is.
  • the porosity of the negative electrode mixture when using graphitizable carbon as the negative electrode active material is preferably 25 to 55%, more preferably 28 to 52%.
  • a negative electrode plate using graphitizable carbon as the negative electrode active material and layered lithium / nickel / manganese / cobalt composite oxide (NMC) and spinel type lithium / manganese oxide (sp-Mn) as the positive electrode active material.
  • the battery characteristics can be improved by constituting a battery by combining a positive electrode plate containing). That is, even in the case of a lithium ion battery having a discharge capacity of 30 Ah or more, while ensuring the safety described in Example A, the battery has a higher capacity and higher input / output.
  • the improved input / output characteristics, storage life and cycle life can be improved.
  • Conditions relating to the positive electrode mixture include (1) a mixed active material of layered lithium / nickel / manganese / cobalt composite oxide (NMC) and spinel type lithium / manganese oxide (sp-Mn). Further, (2) the density of the positive electrode mixture is 2.4 g / cm 3 or more and 2.7 g / cm 3 or less, and (3) the coating amount of the positive electrode mixture is 175 g / m 2 or more and 250 g / m 2 or less. .
  • NMC layered lithium / nickel / manganese / cobalt composite oxide
  • sp-Mn spinel type lithium / manganese oxide
  • the weight ratio (NMC / sp-Mn) of the layered type lithium / nickel / manganese / cobalt composite oxide (NMC) to the spinel type lithium / manganese oxide (sp-Mn) is 10/90 or more and 60 / 40 or less.
  • Conditions relating to the positive electrode mixture include (1) a mixed active material of layered lithium / nickel / manganese / cobalt composite oxide (NMC) and spinel type lithium / manganese oxide (sp-Mn). Further, (2) the density of the positive electrode mixture is 2.4 g / cm 3 or more and 2.7 g / cm 3 or less, and (3) the coating amount of the positive electrode mixture is 175 g / m 2 or more and 250 g / m 2 or less. .
  • NMC layered lithium / nickel / manganese / cobalt composite oxide
  • sp-Mn spinel type lithium / manganese oxide
  • Example B1 to B9 for comparison with Comparative Example B1, the ratio between the discharge capacity per unit area of the positive electrode plate and the discharge capacity per unit area of the negative electrode plate is approximately the same.
  • the amount of slurry applied to the positive electrode plate was adjusted, which is an adjustment for adjusting the charge / discharge capacity. Therefore, in the condition ranges (2) and (3) (the density of the positive electrode mixture and the coating amount of the positive electrode mixture), even when graphitizable carbon is used as the negative electrode active material, this example B explains. It is clear that the effect is achieved.
  • Example C (Examples C1 and C2)
  • a negative electrode plate using graphitizable carbon of the present invention as a negative electrode active material and a layered lithium / nickel / manganese / cobalt composite oxide (NMC) and spinel as a positive electrode active material.
  • the positive electrode plate containing lithium lithium manganese oxide (sp-Mn) is combined, but if the graphitizable carbon of the present invention is used as the negative electrode active material, the type of the positive electrode active material is not affected. It was also confirmed that the lithium ion battery had good input / output characteristics and excellent life characteristics.
  • Examples of the positive electrode active material here include lithium-containing composite metal oxides containing the above NMC and sp-Mn, olivine type lithium salts, chalcogen compounds, manganese dioxide, and the like.
  • the lithium-containing composite metal oxide is a metal oxide containing lithium and a transition metal or a metal oxide in which a part of the transition metal in the metal oxide is substituted with a different element.
  • Examples of the different elements include Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B. Mn, Al, Co, Ni, Mg or the like is preferable. One kind or two or more kinds of different elements may be used.
  • x value which shows the molar ratio of lithium increases / decreases by charging / discharging.
  • olivine type lithium salts for example, LiFePO 4 (LFP) and the like.
  • the chalcogen compound include titanium disulfide and molybdenum disulfide.
  • a positive electrode active material can be used individually by 1 type, or can use 2 or more types together. The positive electrode active material can be appropriately changed according to desired battery characteristics and safety. Hereinafter, it demonstrates in detail based on an Example.
  • NMP N-methyl-2-pyrrolidone
  • the aluminum foil had a rectangular shape with a short side (width) of 350 mm, and an uncoated portion with a width of 50 mm was left along the long side on one side. Then, the drying process was performed and it consolidated by the press (compound density: 2.30 g / cm ⁇ 3 >). Next, a positive electrode plate having a width of 350 mm was obtained by cutting. At this time, a notch was made in the uncoated portion, and the remaining notch was used as a lead piece. The width of the lead piece was 10 mm, and the interval between adjacent lead pieces was 20 mm. Except for the change of the positive electrode plate, a lithium ion battery was produced in the same manner as in Example B8, and input / output characteristics and life evaluation were performed.
  • the average particle diameter (d50) is a value measured as d50 (median diameter) using, for example, a particle size distribution measuring apparatus using a laser light scattering method (for example, SALD-3000, manufactured by Shimadzu Corporation). It is.
  • NMP N-methyl-2-pyrrolidone
  • This slurry was applied substantially uniformly and uniformly on both surfaces of a 20 ⁇ m thick aluminum foil as a positive electrode current collector (amount of positive electrode mixture: 145 g / m 2 ).
  • the aluminum foil had a rectangular shape with a short side (width) of 350 mm, and an uncoated portion with a width of 50 mm was left along the long side on one side.
  • the drying process was performed and it consolidated by the press (compound density: 2.52 g / cm ⁇ 3 >).
  • a positive electrode plate having a width of 350 mm was obtained by cutting.
  • a notch was made in the uncoated portion, and the remaining notch was used as a lead piece.
  • the width of the lead piece was 10 mm, and the interval between adjacent lead pieces was 20 mm.
  • a lithium ion battery was produced in the same manner as in Example B8, and input / output characteristics and life evaluation were performed.
  • Comparative Example C1 A lithium ion battery was produced in the same manner as in Comparative Example B1, except that the positive electrode plate was produced using the same olivine type lithium iron phosphate (LFP) as in Example C1 as the positive electrode active material. went.
  • LFP lithium iron phosphate
  • Comparative Example C2 Comparative Example, except that a positive electrode plate was prepared using the same layered lithium-nickel-manganese-cobalt composite oxide (NMC) and olivine-type lithium iron phosphate (LFP) as the positive electrode active material.
  • NMC lithium-nickel-manganese-cobalt composite oxide
  • LFP olivine-type lithium iron phosphate
  • a lithium ion battery was prepared in the same manner as B1, and input / output characteristics and life evaluation were performed.
  • Example C1 and C2 As shown in the columns of Examples C1 and C2 in Table 13, a battery using graphitizable carbon as a negative electrode active material was prepared, and as shown in the columns of Comparative Examples C1 and C2, it was difficult as a negative electrode active material. A battery using graphitized carbon was produced. For these batteries, input / output characteristics, storage life and cycle life were examined. As a result, it was found that the input / output characteristics of Example C1 improved compared to Comparative Example C1, and that of Example C2 improved compared to Comparative Example C2, and the life characteristics (storage life and cycle life) were also improved. did. In addition, the volume energy density in current value 0.5C of Example C1, C2 and comparative example C1, C2 was comparable.
  • a charge / discharge cycle with a current value of 0.5 CA was repeated twice in a voltage range of 4.2 V to 2.0 V in an environment of 25 ° C. Furthermore, after charging the battery with constant current-constant voltage (CCCV charge) up to 4.2V, charge / discharge is performed by constant current discharge with a final voltage of 2.0V at each current value of 0.5-3CA. It was. Then, the ratio of the discharge capacity at a current value of 3 CA to the discharge capacity of 0.5 CA was determined. This ratio indicates how much capacity can be secured with respect to the rated capacity in the case of rapid discharge (discharge with a large current). The evaluation results are shown in Table 13.
  • Example C1 the 3C discharge load characteristics in Example C1 were improved as compared with Comparative Example C1, and the discharge load characteristics were also improved in Example C2 and Comparative Example C2 using the same positive electrode active material. confirmed. Specifically, the discharge capacity ratio at 3C was 95% in Comparative Example C1, whereas it was 98% in Example C1. In Comparative Example C2, it was 89%, whereas in Example C2, it was 95%. Thus, it has been found that if the graphitizable carbon of the present invention is used for the negative electrode active material, it has output characteristics that can withstand discharge with a large current without affecting the type of the positive electrode active material.
  • the charging load characteristics are as follows. After measuring the above-described discharge capacity ratio, a CC discharge method, a current value of 0.5 CA, and a voltage of 2.0 V were discharged. Furthermore, the battery was charged with a voltage of 4.2 V at each current value of a CC charging method and a current value of 0.5 to 3 CA, and then discharged with a CC discharging method, a current value of 0.5 CA, and a voltage of 2.0 V. And the ratio with respect to the charge capacity of the current value 0.5CA of the charge capacity of the current value 3CA was calculated
  • Example C1 the 3C charging load characteristic in Example C1 was improved as compared with Comparative Example C1, and the charging load characteristic was also improved in Example C2 and Comparative Example C2 using the same positive electrode active material. confirmed. Specifically, the charge capacity ratio at 3C was 95% in Comparative Example C1, whereas it was 97% in Example C1. In Comparative Example C2, it was 80%, whereas in Example C2, it was 91%. Thus, if the graphitizable carbon of the present invention is used for the negative electrode active material, it has an input characteristic that can withstand charging with a large current, that is, rapid charging without affecting the type of the positive electrode active material. found.
  • the charging conditions are CCCV charging method, current value is 0.5 C, voltage is 4.2 V, and the termination condition is 5 hours (hr) or 0.01 C.
  • the battery was discharged at a CC discharge method, a current value of 0.5 C, and a voltage of 2.0 V.
  • Such a charge-discharge cycle is defined as one cycle, and the discharge capacity retention rate from the first cycle when 300 cycles are repeated was calculated.
  • a 15-minute pause is provided between charging and discharging.
  • Example C1 The cycle life characteristics in Example C1 were confirmed to be improved as compared with Comparative Example C1, and it was confirmed that the cycle life characteristics were also improved in Example C2 and Comparative Example C2 using the same positive electrode active material. It was done. Therefore, when the graphitizable carbon of the present invention is used for the negative electrode active material, the input / output characteristics, the storage life, and the cycle life characteristics can be improved without affecting the type of the positive electrode active material.
  • the evaluation was performed without using other safety devices such as a cell controller having a current interruption mechanism in the safety evaluation, but the actual product includes the cell controller. It goes without saying that further safety measures are taken and safety is enhanced in a double and triple manner.
  • the present invention is effective when applied to a lithium ion battery.

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Abstract

L'objet de la présente invention est d'améliorer les caractéristiques d'entrée/sortie et les caractéristiques de durée de vie d'une batterie au lithium-ion qui possède une entrée/sortie élevée et une capacité élevée, tout en garantissant la sécurité. Une électrode négative de cette batterie au lithium-ion, qui comprend, dans un contenant de batterie, une solution d'électrolyte et un groupe d'électrodes dans lequel une électrode positive et l'électrode négative sont agencées avec un séparateur interposé entre elles, est configurée comme décrit ci-dessous. L'électrode négative contient un carbone amorphe ; et le poids du carbone amorphe à 550 °C dans le flux d'air est supérieur ou égal à 70 % du poids de celui-ci à 25 °C, pendant que le poids de celui-ci à 650 °C est inférieur ou égal à 20 % du poids de celui-ci à 25 °C tel que déterminé par une mesure thermogravimétrique.
PCT/JP2015/083054 2014-12-26 2015-11-25 Batterie au lithium-ion WO2016104024A1 (fr)

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JP2018003010A (ja) * 2016-06-22 2018-01-11 ユニチカ株式会社 多孔質ポリイミドフィルム形成用ポリイミド溶液、多孔質ポリイミドフィルムの製造方法および多孔質ポリイミドフィルム
JP2019215972A (ja) * 2018-06-11 2019-12-19 トヨタ自動車株式会社 非水系リチウム二次電池
JP2020009626A (ja) * 2018-07-06 2020-01-16 トヨタ自動車株式会社 非水電解質リチウムイオン二次電池
CN111656583A (zh) * 2018-01-31 2020-09-11 日立化成株式会社 锂离子二次电池用负极活性物质、锂离子二次电池用负极和锂离子二次电池
EP3680965A4 (fr) * 2018-09-28 2020-11-25 Contemporary Amperex Technology Co., Limited Élément d'électrode positive et batterie secondaire au lithium-ion
JP7510912B2 (ja) 2021-12-13 2024-07-04 プライムアースＥｖエナジー株式会社 極板の製造方法、及び、電池の製造方法

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JP2018003010A (ja) * 2016-06-22 2018-01-11 ユニチカ株式会社 多孔質ポリイミドフィルム形成用ポリイミド溶液、多孔質ポリイミドフィルムの製造方法および多孔質ポリイミドフィルム
CN111656583A (zh) * 2018-01-31 2020-09-11 日立化成株式会社 锂离子二次电池用负极活性物质、锂离子二次电池用负极和锂离子二次电池
JP2019215972A (ja) * 2018-06-11 2019-12-19 トヨタ自動車株式会社 非水系リチウム二次電池
JP2020009626A (ja) * 2018-07-06 2020-01-16 トヨタ自動車株式会社 非水電解質リチウムイオン二次電池
JP7071698B2 (ja) 2018-07-06 2022-05-19 トヨタ自動車株式会社 非水電解質リチウムイオン二次電池
EP3680965A4 (fr) * 2018-09-28 2020-11-25 Contemporary Amperex Technology Co., Limited Élément d'électrode positive et batterie secondaire au lithium-ion
US11196041B2 (en) 2018-09-28 2021-12-07 Contemporary Amperex Technology Co., Limited Positive electrode plate and lithium-ion secondary battery
JP7510912B2 (ja) 2021-12-13 2024-07-04 プライムアースＥｖエナジー株式会社 極板の製造方法、及び、電池の製造方法

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