WO2016163282A1 - Batterie secondaire au lithium-ion - Google Patents

Batterie secondaire au lithium-ion Download PDF

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Publication number
WO2016163282A1
WO2016163282A1 PCT/JP2016/060354 JP2016060354W WO2016163282A1 WO 2016163282 A1 WO2016163282 A1 WO 2016163282A1 JP 2016060354 W JP2016060354 W JP 2016060354W WO 2016163282 A1 WO2016163282 A1 WO 2016163282A1
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positive electrode
lithium
negative electrode
active material
mass
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PCT/JP2016/060354
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Japanese (ja)
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貴紀 梶本
学 落田
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日立化成株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lithium ion secondary battery.
  • Lithium ion secondary 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.
  • Cylindrical lithium ion secondary batteries employ a wound structure of a positive electrode, a negative electrode, and a separator.
  • a positive electrode material and a negative electrode material are respectively applied to two strip-shaped metal foils, a separator is sandwiched therebetween, and these laminated bodies are wound in a spiral shape to form a wound group.
  • the wound group is housed in a cylindrical battery can serving as a battery container, and after injecting an electrolytic solution, the cylindrical lithium ion secondary battery is formed.
  • a 18650 type lithium ion battery is widely used as a consumer lithium ion secondary battery.
  • the outer diameter of the 18650 type lithium ion battery is 18 mm in diameter and is small with a height of about 65 mm.
  • As the positive electrode active material of the 18650 type lithium ion battery lithium cobaltate, which is characterized by high capacity and long life, is mainly used, and the battery capacity is approximately 1.0 Ah to 2.0 Ah (3.7 Wh to 7.W. 4 Wh).
  • lithium-ion secondary 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 discloses a cylindrical lithium ion secondary battery having an electrode winding group in which a positive electrode, a negative electrode, and a separator are wound around a cylindrical battery container.
  • This battery has a discharge capacity of 30 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 mixture containing amorphous carbon is used for the negative electrode. Yes.
  • lithium ion secondary batteries have recently attracted attention as power sources used in electric vehicles, hybrid electric vehicles, and the like. In such an application to the automobile field, there is an increasing demand for excellent cycle characteristics and further safety improvement.
  • Patent Document 2 discloses a lithium ion secondary battery using a positive electrode containing a lithium phosphate compound having an olivine structure and polyvinylidene fluoride as a binder.
  • the present invention has been made in view of the above problems, and is to provide a lithium ion secondary battery that is excellent in safety and cycle characteristics and can suppress the rate of increase in resistance.
  • the present invention is a lithium ion secondary battery provided with a positive electrode, a negative electrode, and an electrolytic solution.
  • the positive electrode has a current collector and a positive electrode mixture applied to both sides of the current collector, and the positive electrode mixture is composed of a lithium / nickel / manganese / cobalt composite oxide and a lithium composite having an olivine structure.
  • An oxide and a lithium-manganese composite oxide are included as a positive electrode active material.
  • the negative electrode has a current collector and a negative electrode mixture applied to both surfaces of the current collector, and the negative electrode mixture contains amorphous carbon as a negative electrode active material.
  • a layered lithium / nickel / manganese / cobalt composite oxide can be used as the lithium / nickel / manganese / cobalt composite oxide.
  • the content of the layered lithium / nickel / manganese / cobalt composite oxide (NMC) contained in the positive electrode mixture is preferably 70% by mass or more based on the total amount of the active material in the positive electrode mixture.
  • the initial resistance can be reduced when the content of the lithium composite oxide having an olivine structure is 5% by mass or more and 15% by mass or less with respect to the total amount of the active material in the positive electrode mixture.
  • the discharge capacity can be increased.
  • Amorphous carbon is, for example, graphitizable carbon.
  • the capacity ratio of the positive electrode and the negative electrode (negative electrode capacity / positive electrode capacity) is preferably 1 or more and less than 1.3.
  • the positive electrode active material contained in the positive electrode composite material is S in the content of the lithium / nickel / manganese / cobalt composite oxide with respect to the total amount of the positive electrode active material in the positive electrode composite material, and the lithium composite oxide positive electrode having the olivine structure.
  • T the content with respect to the total amount of the positive electrode active material in the mixture
  • U the content with respect to the total amount of the positive electrode active material in the positive electrode mixture of the lithium manganese composite oxide
  • the present invention it is possible to provide a high-capacity lithium ion secondary battery that is excellent in safety, input characteristics, and cycle characteristics and that can suppress the rate of increase in resistance.
  • FIG. 1 is a perspective view in which a cylindrical (columnar) lithium ion secondary battery according to an embodiment of the present invention is partially cut away so that the inside can be seen. It is sectional drawing of the cylindrical (columnar) lithium ion secondary battery which is embodiment of this invention.
  • the lithium ion secondary 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.
  • the lithium ion secondary battery of this Embodiment is a high capacity
  • a charger When charging a lithium ion secondary battery, a charger is connected between the positive electrode and the negative electrode. At the time of charging, 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 secondary 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 the components of the lithium ion secondary battery of the present embodiment will be described sequentially.
  • the positive electrode shown below is applicable to a lithium ion secondary battery having high capacity and excellent input characteristics and cycle life.
  • the positive electrode (positive electrode plate) of the present embodiment is made of a current collector and a positive electrode mixture formed thereon.
  • the positive electrode mixture constitutes a layer including at least a positive electrode active material provided on the current collector.
  • the positive electrode active material includes a lithium / nickel / manganese / cobalt composite oxide, a lithium composite oxide having an olivine structure, and a lithium / manganese composite oxide.
  • the lithium / nickel / manganese / cobalt composite oxide is preferably a layered lithium / nickel / manganese / cobalt composite oxide (hereinafter sometimes referred to as NMC).
  • NMC layered lithium / nickel / manganese / cobalt composite oxide
  • the layered lithium / nickel / manganese / cobalt composite oxide (NMC) has a high capacity and excellent input characteristics.
  • the lithium composite oxide having the olivine structure is Li 1 + x MPO 4 (0 ⁇ x ⁇ 1, M is selected from Li, Fe, Ni, Co, Mn, Ti, Cu, Zn, Mg, and Zr) Lithium composite oxide (hereinafter sometimes referred to as LMPO) having an olivine type structure represented by one or more kinds of elements) is preferred.
  • LMPO Lithium composite oxide
  • olivine type lithium iron phosphate (LiFePO 4 ) is more preferable.
  • the lithium composite oxide having an olivine type structure is excellent in cycle characteristics and safety.
  • the lithium / manganese composite oxide is preferably a spinel type lithium / manganese composite oxide (hereinafter sometimes referred to as LMO).
  • the spinel type lithium / manganese composite oxide is Li 1+ ⁇ Mn 2 ⁇ M′ ⁇ O 4 (0 ⁇ ⁇ ⁇ 0.5, 0 ⁇ ⁇ ⁇ 2, M ′ is Al, Fe, Ni, Co, Mn, One or more elements selected from Ti, Cu, Zn, Mg, and Zr) are preferable.
  • Spinel-type lithium-manganese composite oxide (LMO) is excellent in output characteristics and safety.
  • the content of the layered lithium / nickel / manganese / cobalt composite oxide (NMC) with respect to the total amount of the active material in the positive electrode mixture is preferably 70% by mass or more and 75% by mass from the viewpoint of increasing the battery capacity. % Or more is more preferable, and it is still more preferable that it is 80 mass% or more.
  • the content of the lithium composite oxide (LMPO) with respect to the total amount of the active material in the positive electrode mixture is less than 5% by mass, a safety effect cannot be obtained. Therefore, the content is preferably 5% by mass or more and 20% by mass or less. From the viewpoint of safety and resistance, it is more preferably 8% by mass or more and 17% by mass or less, and further preferably 10% by mass or more and 15% by mass or less.
  • LMO lithium-manganese composite oxide
  • the input characteristics are deteriorated, so that it is preferably 5% by mass or more and 20% by mass or less. From the viewpoint of output characteristics and safety, it is more preferably 8% by mass or more and 17% by mass or less, and further preferably 10% by mass or more and 15% by mass or less.
  • the positive electrode active material materials other than the above NMC, LMPO, and LMO may be used.
  • the positive electrode active material other than NMC and LMPO those commonly used in this field can be used, and examples thereof include lithium-containing composite metal oxides other than NMC, LMPO, and LMO, chalcogen compounds, and manganese dioxide.
  • 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 element include Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B. Mn, Al, Co, Ni, Mg and the like are preferable.
  • One kind or two or more kinds of different elements may be used.
  • lithium-containing composite metal oxides are preferable.
  • the lithium-containing composite metal oxide include Li x CoO 2 , Li x NiO 2 , Li x MnO 2 , Li x Co y Ni 1 -y O 2 , Li x Co y M 1 -y O z , and Li x.
  • Ni 1-y M y O z , Li 2 MPO 4 F in the respective formulas, M is Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, And at least one element selected from the group consisting of V and B.
  • x 0 to 1.2
  • y 0 to 0.9
  • z 2.0 to 2.3. .
  • x value which shows the molar ratio of lithium increases / decreases by charging / discharging.
  • 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 single-side coating amount of the positive electrode mixture to the positive electrode current collector is preferably 100 g / m 2 or more and 160 g / m 2 or less, and 110 g / m 2 or more and 150 g / m 2 or less. It is more preferable.
  • the thickness of the single-sided coating film of the positive electrode mixture on the positive electrode current collector ([positive electrode thickness ⁇ positive electrode current collector] The thickness] / 2) is preferably 36 to 73 ⁇ m, more preferably 43 to 55 ⁇ m.
  • the discharge capacity is 30 Ah or more and less than 99 Ah. Even in the lithium ion secondary battery, a battery with high input / output and high energy density can be realized while ensuring safety.
  • NMC layered lithium / nickel / manganese / cobalt composite oxide
  • (1 + ⁇ ) is a composition ratio of Li (lithium)
  • x is a composition ratio of Mn (manganese)
  • y is a composition ratio of Ni (nickel)
  • (1-xyz) Indicates the composition ratio of Co (cobalt).
  • z represents the composition ratio of the element M.
  • the composition ratio of O (oxygen) is 2.
  • 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).
  • ⁇ , x, y, and z in the composition formula are ⁇ 0.15 ⁇ ⁇ 0.15, 0.1 ⁇ x ⁇ 0.5, 0.6 ⁇ x + y + z ⁇ 1.0. , 0 ⁇ z ⁇ 0.1.
  • LMPO lithium composite oxide
  • Formula 2 olivine structure represented by the following composition formula (Formula 2).
  • Li 1 + x MPO 4 (Formula 2) (0 ⁇ x ⁇ 1, M is one or more elements selected from Li, Fe, Ni, Co, Mn, Ti, Cu, Zn, Mg, and Zr)
  • (1 + x) is a composition ratio of Li
  • M is one or more elements selected from Li, Fe, Ni, Co, Mn, Ti, Cu, Zn, Mg, and Zr.
  • the composition ratio of O (oxygen) is 4.
  • x in the composition formula is determined within a range of 0 ⁇ x ⁇ 0.5.
  • Li-manganese composite oxide represented by the following composition formula (Formula 3).
  • the element M is at least one element selected from the group consisting of Al, Fe, Ni, Co, Mn, Ti, Cu, Zn, Mg, and Zr.
  • ⁇ and ⁇ in the composition formula are determined within the ranges of 0 ⁇ ⁇ ⁇ 0.2 and 0 ⁇ ⁇ 2.
  • an active material for the positive electrode positive electrode active material
  • NMC lithium-nickel-manganese-cobalt composite oxide
  • LMPO lithium composite oxide
  • Li-manganese composite oxide By using a mixture with a product (LMO), the stability of the positive electrode during charging can be increased and heat generation can be suppressed even when the capacity is increased. As a result, a lithium ion secondary battery excellent in safety can be provided. In addition, charge / discharge cycle characteristics and storage characteristics can be improved.
  • Fe or Mn as the element M in the composition formula (Formula 2).
  • the battery life can be extended.
  • the safety of the battery can be improved.
  • LMPO lithium composite oxide
  • the lithium composite oxide (LMPO) having an olivine structure has useful characteristics
  • the lithium composite oxide (LMPO) itself having an olivine structure has a small theoretical capacity and a low density. Therefore, when only a lithium composite oxide (LMPO) having an olivine type structure is used as a positive electrode active material to constitute a battery, it is difficult to increase the battery capacity (discharge capacity).
  • Mg or Al as the element M ′ in the composition formula (Chemical Formula 3).
  • Mg or Al the battery life can be extended.
  • the safety of the battery can be improved.
  • lithium-manganese composite oxide (LMO) is used as the positive electrode active material
  • Mn in the compound is stable in the charged state
  • heat generation due to the charging reaction can be suppressed.
  • security of a battery can be improved. That is, heat generation at the positive electrode can be suppressed, and the safety of the battery can be improved.
  • lithium-manganese composite oxide (LMO) has useful characteristics
  • lithium-manganese composite oxide (LMO) itself has a small theoretical capacity and a low density. Therefore, when only a lithium-manganese composite oxide (LMO) is used as the 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 the same theoretical capacity as LiCoO 2 which is widely used as a positive electrode active material for lithium ion secondary batteries.
  • 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).
  • 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 (mass) 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.
  • NMC nickel / manganese / cobalt composite oxide particles
  • particles having a lump shape, polyhedron shape, spherical shape, elliptical spherical shape, plate shape, needle shape, columnar shape, or the like can be 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.
  • NMC nickel / manganese / cobalt composite oxide
  • LMPO lithium composite oxide
  • LMO lithium / manganese composite oxide
  • the lower limit of the range is 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more
  • the upper limit is 30 ⁇ m or less, preferably 25 ⁇ m or less, more preferably 15 ⁇ m or less.
  • the tap density fillability
  • the upper limit it takes time to diffuse lithium ions in the particles, so that the battery performance is lowered. May be incurred.
  • the mixing property with other materials such as a binder and a conductive material, may fall at the time of formation of an electrode. For this reason, when the mixture is slurried and applied, it may not be applied uniformly, and problems such as streaking may occur.
  • the median diameter d50 can be obtained from the particle size distribution obtained by the laser diffraction / scattering method.
  • the range of the average particle diameter of primary particles when 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, and the upper limit is 3 ⁇ m or less, preferably 2 ⁇ m or less, more preferably 1 ⁇ m. Hereinafter, it is particularly preferably 0.6 ⁇ m or less.
  • the above upper limit is exceeded, it is difficult to form spherical secondary particles, and battery performance such as output characteristics may be reduced due to a decrease in tap density (fillability) and a decrease in specific surface area.
  • problems such as deterioration of the reversibility of charging / discharging, may arise by crystallinity fall.
  • BET specific surface area of particles of positive electrode active material containing layered lithium / nickel / manganese / cobalt composite oxide (NMC), lithium composite oxide (LMPO) having olivine structure, and lithium / manganese composite oxide (LMO) The range is as follows. Lower limit of the range is, 0.2 m 2 / g or more, preferably 0.3 m 2 / g or more, still more preferably 0.4 m 2 / g or more, and the upper limit is, 35m 2 / g or less, preferably 30 m 2 / g or less, more preferably 25 m 2 / g or less. If it is less than the said minimum, 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 (mass) 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 said minimum, electroconductivity may become inadequate. Moreover, when the said upper limit is exceeded, 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; styrene / butadiene / styrene block copolymer or its hydrogenated product, EPDM (ethylene / propylene / diene terpolymer), styrene / Thermoplastic elastomeric polymers such as ethylene / butadiene / ethylene copolymers, styrene /
  • a fluorine-based polymer such as polyvinylidene fluoride (PVdF) or a polytetrafluoroethylene / vinylidene fluoride copolymer.
  • the range of the content of the binder relative to the mass 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
  • 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. Conversely, if it is too high, the 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, titanium, and tantalum; 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 cylinder, a metal coil, a metal plate, a metal thin film, an expanded metal, a punching metal, and a foam metal, and a carbonaceous material includes a carbon plate, a carbon thin film, A carbon cylinder etc. are mentioned.
  • a metal thin film it is preferable to use a metal thin film.
  • 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-output and high-capacity lithium ion secondary battery.
  • the negative electrode (negative electrode plate) of the present embodiment is composed of a current collector and a negative electrode mixture formed on both sides (or one side) thereof.
  • the negative electrode mixture contains a negative electrode active material that can electrochemically occlude and release lithium ions.
  • the negative electrode active material preferably contains a carbon material.
  • the carbon material is roughly classified into a graphite material having a uniform crystal structure and a non-graphite material having a disordered crystal structure.
  • the graphite system includes natural graphite and artificial graphite, and the non-graphite system includes amorphous carbon.
  • Amorphous carbon includes easily graphitizable carbon that tends to become graphite by heating at 2000 to 3000 ° C. and hardly graphitized carbon that hardly becomes graphite, although the crystal structure is disordered.
  • the amorphous carbon can be produced, for example, by heat-treating petroleum pitch, polyacene, polyparaphenylene, polyfurfuryl alcohol, or polysiloxane. Or graphitizable carbon.
  • a firing temperature of about 500 to 800 ° C. is suitable for producing non-graphitizable carbon
  • a firing temperature of about 800 to 1000 ° C. is suitable for producing graphitizable carbon.
  • the non-graphitizable carbon is defined as having a surface spacing d002 value in the C-axis direction obtained by an X-ray wide angle diffraction method of 0.36 nm or more and 0.40 nm or less.
  • the graphitizable carbon preferably has a surface spacing d002 value in the C-axis direction obtained by an X-ray wide-angle diffraction method of 0.34 nm or more and less than 0.36 nm, and is 0.341 nm or more and 0.355 nm or less. More preferably, it is 0.342 nm or more and 0.350 nm or less.
  • the graphite preferably has an interplanar spacing d002 value in the C-axis direction obtained by an X-ray wide-angle diffraction method of 0.33 nm or more and less than 0.34 nm, preferably 0.335 nm or more and 0.337 nm or less. More preferred.
  • the content ratio of the carbon material is preferably 20% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more based on the total amount of the negative electrode active material.
  • the average particle diameter (50% D) of the negative electrode active material is preferably 2.0 to 50.0 ⁇ m.
  • the specific surface area can be in an appropriate range, the initial charge / discharge efficiency of the lithium ion secondary battery is excellent, and the particles are in good contact with each other and have excellent input / output characteristics.
  • the average particle diameter is 30 ⁇ m or less, unevenness on the electrode surface hardly occurs, and the short circuit of the battery can be suppressed, and the diffusion distance of Li from the particle surface to the inside becomes relatively short, so that the insertion of the lithium ion secondary battery The output characteristics tend to improve.
  • the average particle size is more preferably 5 to 30 ⁇ m, and further preferably 10 to 20 ⁇ m.
  • a sample is dispersed in purified water containing a surfactant, and a laser diffraction particle size distribution measuring apparatus (for example, product name: SALD-3000J (“SALD” is a registered trademark) manufactured by Shimadzu Corporation). )), And the average particle size is calculated as 50% D.
  • a negative electrode active material other than the carbonaceous material can be used as the negative electrode active material.
  • negative electrode active materials other than carbonaceous materials include metal oxides such as tin oxide and silicon oxide, metal composite oxides, lithium alloys such as lithium alone and lithium aluminum alloys, and alloys with lithium such as Sn and Si.
  • Various materials may be used in combination. These may be used alone or in combination of two or more.
  • the metal composite oxide is not particularly limited as long as it can occlude and release lithium.
  • a material containing both Ti (titanium), Li (lithium), and Ti and Li has a high current density. This is preferable from the viewpoint of discharge characteristics.
  • lithium metal that can occlude and release lithium by forming a compound with lithium, or a group 14 element such as silicon, germanium, and tin that can occlude and release lithium by forming a compound with lithium and inserting into a crystal gap
  • oxides or nitrides may be used in combination with the above graphite or graphitizable carbon.
  • the second carbonaceous material a form using a carbonaceous material that is not symmetric when the volume-based particle size distribution is centered on the median diameter as the second carbonaceous material (conductive material).
  • the second carbonaceous material a form using a carbonaceous material having a different Raman R value from the carbonaceous material used as the negative electrode active material, or as the second carbonaceous material (conductive material), as the negative electrode active material
  • a carbonaceous material having a different X-ray parameter from the first carbonaceous material used There is a form using a carbonaceous material having a different X-ray parameter from the first carbonaceous material used.
  • the second carbonaceous 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 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, punching metal, and foam metal. Among these, a metal thin film is preferable, and a copper foil is more preferable. 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.
  • 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 / butadiene / styrene block copolymers or hydrogenated products thereof; EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene / Thermoplastic elastomeric polymer such as butadiene / styrene copolymer, sty
  • 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.
  • aqueous solvent examples include water, a mixed solvent of alcohol and water
  • organic solvent examples include N-methylpyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, Methyl acrylate, diethyltriamine, N, N-dimethylaminopropylamine, tetrahydrofuran (THF), toluene, acetone, diethyl ether, dimethylacetamide, hexamethylphosphalamide, dimethyl sulfoxide, benzene, xylene, quinoline, pyridine, methylnaphthalene And hexane.
  • NMP N-methylpyrrolidone
  • dimethylformamide dimethylacetamide
  • methyl ethyl ketone examples of the organic solvent
  • cyclohexanone examples include methyl acetate, Methyl acrylate, diethy
  • a thickener when an aqueous solvent is used, it is preferable to use a thickener.
  • a dispersing agent or the like is added to the thickener, and a slurry such as SBR is made into a slurry.
  • 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 content of the binder with respect to the mass 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, the fall of the intensity
  • the range of the binder content relative to the mass 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 mass 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 mass of the negative electrode mixture 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 amount is less than the above lower limit, the applicability of the slurry may decrease. Moreover, when the said upper limit is exceeded, the ratio of the negative electrode active material to a negative electrode compound material will fall, and there exists a possibility of the fall of battery capacity and the raise between resistances of a negative electrode active material.
  • 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 solution for a lithium ion secondary battery.
  • the following inorganic lithium salt, fluorine-containing organic lithium salt, or oxalate borate Examples include salts.
  • 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.
  • fluorine-containing organic lithium salt examples include perfluoroalkane sulfonates such as LiCF 3 SO 3 ; LiN (CF 3 SO 2 ) 2 , LiN (CF 3 CF 2 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C Perfluoroalkanesulfonylimide salts such as 4 F 9 SO 9 ); perfluoroalkanesulfonylmethide salts such as LiC (CF 3 SO 2 ) 3 ; Li [PF 5 (CF 2 CF 2 CF 3 )], Li [PF 4 (CF 2 CF 2 CF 3 ) 2 ], Li [PF 3 (CF 2 CF 2 CF 3 ) 3 ], Li [PF 5 (CF 2 CF 2 CF 2 CF 3 )], Li [PF 4 (CF 2 CF 2 CF 2 CF 3 )], Li [PF 4 (CF 2 CF 2 CF 2 CF 3 ), Li [PF 3 (CF 2 CF 2 CF 3 )], Li [PF
  • oxalatoborate salt examples include lithium bis (oxalato) borate and lithium difluorooxalatoborate.
  • 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 the combined use 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 electrical conductivity of the electrolyte 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 secondary 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 secondary battery.
  • a non-aqueous solvent that can be used as an electrolyte solvent for a lithium ion secondary battery.
  • the following cyclic carbonate, chain carbonate, chain ester, cyclic ether, and chain And ethers for example, the following cyclic carbonate, chain carbonate, chain ester, cyclic ether, and chain And ethers.
  • 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.
  • chain esters examples include methyl acetate, ethyl acetate, propyl acetate, and methyl propionate. Among them, it is preferable to use methyl acetate from the viewpoint of improving the low temperature characteristics.
  • cyclic ether examples include tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran and the like. Of these, tetrahydrofuran is preferably used from the viewpoint of improving input / output characteristics.
  • chain ethers examples include dimethoxyethane and dimethoxymethane.
  • 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, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate And ethyl methyl carbonate, ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.
  • 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.
  • those containing asymmetric chain carbonates as chain carbonates are more preferable.
  • Specific examples include a combination of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
  • Such a combination of ethylene carbonate, symmetric chain carbonates and asymmetric chain carbonates can improve cycle characteristics and large current discharge characteristics.
  • the asymmetric chain carbonate is preferably ethyl methyl carbonate
  • the alkyl group constituting the dialkyl carbonate is preferably one having 1 to 2 carbon atoms.
  • preferred mixed solvents are those containing a chain ester.
  • those containing a chain ester in the mixed solvent of the cyclic carbonates and the chain carbonates are preferable from the viewpoint of improving the low-temperature characteristics of the battery.
  • the chain ester methyl acetate and ethyl acetate are particularly preferable.
  • the lower limit of the capacity of the chain ester in the non-aqueous solvent is 5% or more, preferably 8% or more, more preferably 15% or more, and the upper limit is 50% or less, preferably 35% or less, more preferably 30 % Or less, more preferably 25% or less.
  • non-aqueous solvents examples include one organic solvent selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate, or a mixed solvent consisting of two or more organic solvents selected from this group.
  • the volume of the mixed solvent in the non-aqueous solvent is 60% by volume or more.
  • These mixed solvents are preferably adjusted by selecting various solvents so that the flash point is 50 ° C. or higher, and more preferably adjusted so that the flash point is 70 ° C. or higher.
  • a non-aqueous electrolyte using such a mixed solvent is less likely to evaporate or leak when used at high temperatures.
  • the total of ethylene carbonate and propylene carbonate in the non-aqueous solvent is 80% by volume or more, preferably 90% by volume or more, and the volume ratio of ethylene carbonate to propylene carbonate is 30:70 to 60:40. If some are used, cycle characteristics, large current discharge characteristics, and the like can be improved.
  • the additive is not particularly limited as long as it is an additive for a non-aqueous electrolyte solution of a lithium ion secondary battery.
  • nitrogen, sulfur or a heterocyclic compound containing nitrogen and sulfur, a cyclic carboxylic acid ester, fluorine examples thereof include cyclic carbonates and other compounds having an unsaturated bond in the molecule.
  • the heterocyclic compound containing nitrogen, sulfur or nitrogen and sulfur is not particularly limited, but 1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-pyrrolidinone, 1,5-dimethyl-2-pyrrolidinone, Pyrrolidinones such as 1-ethyl-2-pyrrolidinone and 1-cyclohexyl-2-pyrrolidinone; Oxazolidinones such as 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone and 3-cyclohexyl-2-oxazolidinone; Piperidones such as methyl-2-piperidone and 1-ethyl-2-piperidone; imidazolidinones such as 1,3-dimethyl-2-imidazolidinone and 1,3-diethyl-2-imidazolidinone; sulfolane, Sulfolanes such as 2-methylsulfolane and 3-methylsulfolane; sulfolene; ethyl Sulf
  • 1-methyl-2-pyrrolidinone, 1-methyl-2-piperidone, 1,3-propane sultone, 1,4-butane sultone, 1,3-propene sultone, 1,4-butene sultone, etc. prolong the battery life.
  • the cyclic carboxylic acid ester is not particularly limited, but ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexalactone, ⁇ -heptalactone, ⁇ -octalactone, ⁇ -nonalactone, ⁇ -decalactone, and ⁇ -undecalactone.
  • ⁇ -dodecalactone ⁇ -methyl- ⁇ -butyrolactone, ⁇ -ethyl- ⁇ -butyrolactone, ⁇ -propyl- ⁇ -butyrolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -ethyl- ⁇ -valerolactone, ⁇ , ⁇ -dimethyl- ⁇ -butyrolactone, ⁇ , ⁇ -dimethyl- ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -hexalactone, ⁇ -octalactone, ⁇ -nonalactone, ⁇ -decalactone, ⁇ -undecalactone, ⁇ - Examples include dodecalactone. Among these, ⁇ -butyrolactone, ⁇ -valerolactone, and the like are particularly preferable from the viewpoint of extending the life of the battery.
  • the fluorine-containing cyclic carbonate is not particularly limited, and examples thereof include fluoroethylene carbonate, difluoroethylene carbonate, trifluoroethylene carbonate, tetrafluoroethylene carbonate, and trifluoropropylene carbonate. Among these, fluoroethylene carbonate and the like are particularly preferable from the viewpoint of extending the life of the battery.
  • Other compounds having an unsaturated bond in the molecule include vinylene carbonate, vinyl ethylene carbonate, divinyl ethylene carbonate, methyl vinyl carbonate, ethyl vinyl carbonate, propyl vinyl carbonate, divinyl carbonate, allyl methyl carbonate, allyl ethyl carbonate, allyl propyl.
  • Carbonates such as carbonate, diallyl carbonate, dimethallyl carbonate; vinyl acetate, vinyl propionate, vinyl acrylate, vinyl crotonate, vinyl methacrylate, allyl acetate, allyl propionate, methyl acrylate, ethyl acrylate, propyl acrylate , Esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate; divinyl sulfone, methyl vinyl sulfo , Sulfones such as ethyl vinyl sulfone, propyl vinyl sulfone, diallyl sulfone, allyl methyl sulfone, allyl ethyl sulfone, allyl propyl sulfone; sulfites such as divinyl sulfite, methyl vinyl sulfite, ethyl vinyl sulfite, diallyl sulfite
  • vinylene carbonate, dimethallyl carbonate, vinyl ethylene carbonate, divinyl ethylene carbonate, vinyl acetate, vinyl propionate, vinyl acrylate, divinyl sulfone, vinyl methanesulfonate, and the like are particularly preferable from the viewpoint of extending the life of the battery.
  • additives such as an overcharge preventing material, a negative electrode film forming material, a positive electrode protective material, and a high input / output material may be used depending on the required function.
  • 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
  • an inert gas for example, carbon dioxide
  • the material used for the above components include lithium carbonate and polyalkylene carbonate resin.
  • the polyalkylene carbonate resin include polyethylene carbonate, polypropylene carbonate, poly (1,2-dimethylethylene carbonate), polybutene carbonate, polyisobutene carbonate, polypentene carbonate, polyhexene carbonate, polycyclopentene carbonate, polycyclohexene carbonate, and polycyclohexane.
  • examples include heptene carbonate, polycyclooctene carbonate, and polylimonene carbonate.
  • lithium carbonate, polyethylene carbonate, and polypropylene carbonate are preferable.
  • the laminate type lithium ion secondary battery can be manufactured, for example, as follows. First, the positive electrode and the negative electrode are cut into squares, and tabs are welded to the respective electrodes to produce positive and negative electrode terminals. A laminated body in which the positive electrode, the insulating layer, and the negative electrode are laminated in this order is prepared, and in that state, accommodated in an aluminum laminate pack, and the positive and negative electrode terminals are taken out of the aluminum laminate pack and sealed. Next, the nonaqueous electrolyte is poured into the aluminum laminate pack, and the opening of the aluminum laminate pack is sealed. Thereby, a lithium ion secondary battery is obtained.
  • the lithium ion secondary battery 1 of the present embodiment has a configuration in which an electrode winding group 5 composed of a strip-like positive electrode plate 2, a negative electrode plate 3 and a separator 4 is accommodated in a battery container 6.
  • an electrode winding group 5 composed of a strip-like positive electrode plate 2, a negative electrode plate 3 and a separator 4 is accommodated in a battery container 6.
  • the positive electrode plate 2 and the negative electrode plate 3 are wound in a spiral shape in cross section through a separator 4 made of a polyethylene porous sheet.
  • the separator 4 is made of a polyethylene porous sheet, and has a width of 58 mm and a thickness of 30 ⁇ m, for example.
  • the battery container 6 is a bottomed cylindrical battery container made of steel plated with nickel.
  • a ribbon-like positive electrode tab terminal (positive electrode lead piece 7) made of aluminum and having one end fixed to the positive electrode plate 2 is led out.
  • the other end of the positive electrode tab terminal 7 is disposed on the upper side of the electrode winding group 5 and joined to the positive electrode external terminal 9 on the lower side of the disk-shaped battery lid 12 by ultrasonic welding.
  • a copper-made ribbon-like negative electrode tab terminal (a negative electrode plate lead piece 7 ') having one end fixed to the negative electrode plate 3 is led out.
  • the other end portion of the negative electrode tab terminal 7 ′ is disposed below the electrode winding group 5 and joined to the negative electrode external terminal 9 ′ by resistance welding on the upper side of the lid portion 4 ′ that constitutes the inner bottom portion of the battery container 6. ing. Therefore, the positive electrode tab terminal 7 and the negative electrode tab terminal 7 ′ are led out to the opposite sides of the both end faces of the electrode winding group 5. As shown in FIG. 2, an insulating coating 10 is applied to the entire outer peripheral surface of the electrode winding group 5.
  • the battery lids 12 and 12 ′ are caulked and fixed to the upper part of the battery container 6 through an insulating resin gasket (not shown). For this reason, the inside of the lithium ion secondary battery 1 is sealed.
  • a non-aqueous electrolyte solution (not shown) is injected into the battery container 6.
  • the capacity ratio of the negative electrode to the positive electrode is preferably 1 or more and less than 1.3 from the viewpoint of safety and energy density, more preferably 1.05 to 1.25, 1.1 to 1.2 is more preferable. If it is 1.3 or more, the positive electrode potential may be higher than 4.2 V during charging, which may reduce safety. (At this time, the positive electrode potential refers to the Li potential)
  • Negative electrode capacity represents “negative electrode discharge capacity”
  • positive electrode capacity represents “positive electrode initial charge capacity—negative electrode or positive electrode, whichever is greater”.
  • the discharge capacity of the negative electrode is defined as calculated by the charge / discharge device when the lithium ions inserted into the negative electrode active material are desorbed.
  • the “positive charge capacity of the positive electrode” is defined as calculated by the charge / discharge device when lithium ions are desorbed from the positive electrode active material.
  • the capacity ratio between the negative electrode and the positive electrode can be calculated from, for example, “discharge capacity of lithium ion secondary battery / discharge capacity of negative electrode”.
  • the discharge capacity of the lithium ion secondary battery is, for example, 4.2 V, 0.1 to 0.5 C, 0.1 to 0.5 C after performing constant current and constant voltage (CCCV) charging with a termination time of 2 to 5 hours. It can be measured under the conditions when a constant current (CC) discharge is performed up to 2.7 V at ⁇ 0.5 C.
  • the discharge capacity of the negative electrode was prepared by cutting a negative electrode having a measured discharge capacity of the lithium ion secondary battery into a predetermined area, using lithium metal as a counter electrode, and preparing a single electrode cell through a separator impregnated with an electrolyte. After constant current constant voltage (CCCV) charging at 0 V, 0.1 C, and a final current of 0.01 C, a constant current (CC) discharge at a constant current (CC) of up to 1.5 V at 0.1 C It can be calculated by measuring the discharge capacity and converting this to the total area used as the negative electrode of the lithium ion secondary battery.
  • CCCV constant current constant voltage
  • CC constant current
  • the direction in which lithium ions are inserted into the negative electrode active material is defined as charging, and the direction in which lithium ions inserted into the negative electrode active material are desorbed is defined as discharging.
  • C means “current value (A) / battery discharge capacity (Ah)”.
  • a mixture of positive electrode materials was obtained by sequentially adding and mixing acetylene black as a conductive material and polyvinylidene fluoride as a binder to the positive electrode active material mixture.
  • NMP N-methyl-2-pyrrolidone
  • This slurry was applied substantially evenly and uniformly to both surfaces of a 20 ⁇ m thick aluminum foil as a positive electrode current collector. Then, the drying process was performed and it consolidated by the press to the predetermined density.
  • the density of the positive electrode mixture was 2.5 g / cm 3, and the coating amount on one side of the positive electrode mixture was 150 g / m 2 .
  • the negative electrode plate was produced as follows.
  • a dispersion solvent N-methyl-2-pyrrolidone (NMP) was added thereto and kneaded to form a slurry.
  • 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 density of the negative electrode mixture was 1.15 g / cm 3 .
  • a lithium ion secondary battery was produced using the positive electrode plate and the negative electrode plate produced as described above.
  • the positive electrode plate 2 and the negative electrode plate 3 are wound with a polyethylene separator 4 having a thickness of 30 ⁇ m interposed therebetween so that they do not directly contact each other.
  • the lead pieces 7 and 7 ′ are placed so that the lead piece 7 of the positive electrode plate 2 and the lead piece 7 ′ of the negative electrode plate 3 are located on both end surfaces of the electrode winding group 5 facing each other. Deploy.
  • the length of the positive electrode plate 2, the negative electrode plate 3, and the separator 4 was adjusted so that the diameter dimension of the electrode winding group 5 might be set to 64 ⁇ 0.1 mm.
  • the lead pieces 7 led out from the positive electrode plate 2 are deformed, and all of them are gathered near the bottom of the flange 8 on the positive electrode side and brought into contact with each other.
  • the positive electrode side flange portion 8 is integrally formed so as to protrude from the periphery of the pole column (positive electrode external terminal 9) substantially on the extension line of the axis of the electrode winding group 5, and has a bottom portion and a side portion.
  • the lead piece 7 is connected and fixed to the bottom of the flange 8 by ultrasonic welding.
  • the negative electrode side flange portion 8 ' is integrally formed so as to protrude from the periphery of the pole column (negative electrode external terminal 9') substantially on the extension line of the axis of the electrode winding group 5, and the bottom portion and the side portion are formed.
  • the side portion of the flange portion 8 on the positive electrode external terminal 9 side and the side portion of the flange portion 8 ′ of the negative electrode external terminal 9 ′ were covered to form an insulating coating 10.
  • the insulating coating 10 was also formed on the outer periphery of the electrode winding group 5.
  • this adhesive tape is applied from the side of the flange 8 on the positive electrode external terminal 9 side to the outer peripheral surface of the electrode winding group 5, and further from the outer periphery of the electrode winding group 5 to the negative electrode external terminal 9 ′ side.
  • the insulating coating 10 is formed by winding several times over the side of the flange 8 '.
  • the insulating coating As the insulating coating (adhesive tape) 10, 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 10 (the number of windings of the adhesive tape) is adjusted so that the maximum diameter portion of the electrode winding group 5 is slightly smaller than the inner diameter of the battery container 6 made of stainless steel. It was inserted into the container 6.
  • the battery container 6 had an outer diameter of 67 mm and an inner diameter of 66 mm.
  • the ceramic washers 11 and 11 ′ are fitted into a pole column whose tip constitutes the positive electrode external terminal 9 and a pole column whose tip constitutes the negative electrode external terminal 9 ′, respectively.
  • the ceramic washers 11 and 11 ' are made of alumina, and the thickness of the portion in contact with the back surface of the battery lid 12 and 12' is 2 mm, the inner diameter is 16 mm, and the outer diameter is 25 mm.
  • the positive external terminal 9 is passed through another ceramic washer 13, and the ceramic washer 11 'is placed on the back surface of the battery lid 12'.
  • the negative external terminal 9 ' is passed through another ceramic washer 13'.
  • the ceramic washers 13, 13 ' are made of alumina and have 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 surfaces of the battery lids 12 and 12 ′ are fitted into the opening of the battery container 6, and the entire areas of both contact portions are laser-welded.
  • the positive electrode external terminal 9 and the negative electrode external terminal 9 ′ protrude through the hole (hole) in the center of the battery lids 12 and 12 ′ and project outside the battery lids 12 and 12 ′.
  • the battery lid 12 on the positive electrode external terminal 9 side is provided with a cleavage valve 14 that cleaves as the internal pressure of the battery increases.
  • the cleavage pressure of the cleavage valve 14 was 13 to 18 kgf / cm 2 .
  • the metal washers 15 and 15 ' are fitted into the positive external terminal 9 and the negative external terminal 9', respectively.
  • metal nuts 16 and 16 ' are screwed to the positive external terminal 9 and the negative external terminal 9', respectively, and are passed through ceramic washers 11 and 11 ', metal washers 15 and 15', and ceramic washers 13 and 13 '.
  • the battery lids 12 and 12 ' are fixed by tightening between the flange portions 8 and 8' and the nuts 16 and 16 '.
  • the tightening torque value at this time was 70 kgf ⁇ cm.
  • the metal washers 15 and 15 ′ did not rotate until the tightening operation was completed.
  • the power generation element inside the battery case 6 is compressed by compression of rubber (EPDM) O-rings 17 and 17 ′ interposed between the back surfaces of the battery lids 12 and 12 ′ and the flanges 8 and 8 ′. It is blocked from the outside air.
  • EPDM rubber
  • LiPF 6 lithium hexafluorophosphate
  • VC vinylene carbonate
  • the input characteristic is that after measuring the discharge capacity in the third cycle, constant current (CC) charging is performed with a current value of 3C and 4.2V as the upper limit voltage, and the charge capacity at this time is expressed as “charge capacity at current value 3C”.
  • the input characteristics were calculated by the following formula. Thereafter, constant current discharge with a final voltage of 2.0 V was performed at a current value of 0.2 C.
  • Input characteristics Charge capacity at a current value of 3C / Charge capacity at a current value of 0.2C
  • the input characteristics were 90% or more as A, 85% or more but less than 90% as B, and less than 85% as C.
  • the initial resistance was evaluated by charging and discharging as follows in an environment at 25 ° C. after measuring the discharge capacity at the third cycle. Charging was performed at a constant current and a constant voltage (CCCV) with 4.2 V as the upper limit voltage, a charging current of 0.5 C, and a termination condition of 3 hours. The discharge was performed as a constant current (CC) discharge with a lower limit voltage of 2.0 V and a discharge current of 0.5C, 1C, and 1.5C. In the figure where the vertical axis represents the difference between the discharge start voltage and the voltage after 10 seconds and the horizontal axis represents the discharge current value, the slope of the approximate line was calculated as the initial resistance.
  • the capacity maintenance rate is 90% or more as A, 85% or more and less than 90% as B, and less than 85% as C.
  • the resistance increase rate was determined by measuring the resistance after 500 cycles in the same manner as the initial resistance after measuring the cycle life, and calculating the resistance increase rate by the following equation.
  • Resistance increase rate resistance after 500 cycles / initial resistance The resistance increase rate was less than 105% as A, 105% to less than 110% as B, and 110% or more as C.
  • the battery was charged with an electric current value of 3C to an upper limit voltage of 5.2 V, and when the upper limit voltage was reached, the current was interrupted and allowed to stand for 30 minutes. At this time, the presence or absence of rupture and ignition of the battery was confirmed. Specifically, when ignition was not observed and the battery container did not rupture, it was evaluated as A (good), and when ignition was observed or the battery container ruptured, it was evaluated as B (bad).
  • Example 2 to Example 6> A battery was fabricated and evaluated under the same conditions as in Example 1 except that the mass ratio of the active material of the positive electrode mixture in Example 1 was changed to the mass ratio shown in Table 1.
  • Example 1 A battery was fabricated and evaluated under the same conditions as in Example 1 except that the mass ratio of the active material of the positive electrode mixture in Example 1 was the mass ratio described in Table 1 and the discharge lower limit voltage was 2.7 V.

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Abstract

L'invention concerne une batterie secondaire au lithium-ion dans laquelle le taux d'augmentation dans la résistance peut être supprimé, tout en ayant d'excellentes caractéristiques de cycle et de sécurité. La présente invention porte sur une batterie secondaire au lithium-ion comportant une électrode positive, une électrode négative et une solution d'électrolyte. L'électrode positive comprend un collecteur et un mélange d'électrode positive appliqué sur les deux surfaces du collecteur; et le mélange d'électrode positive contient, en tant que matériaux actifs d'électrode positive, un oxyde composite lithium-nickel-manganèse-cobalt, un oxyde composite de lithium ayant une structure de type olivine et un oxyde composite lithium-manganèse. L'électrode négative comprend un collecteur et un mélange d'électrode négative appliqué sur les deux surfaces du collecteur; et le mélange d'électrode négative contient, en tant que matériau actif d'électrode négative, un carbone amorphe.
PCT/JP2016/060354 2015-04-07 2016-03-30 Batterie secondaire au lithium-ion WO2016163282A1 (fr)

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CN113072889A (zh) * 2021-05-13 2021-07-06 芜湖徽氏新材料科技有限公司 一种圆柱电池专用厚度溶胀胶带及其制备方法
EP3859824A4 (fr) * 2019-12-05 2021-09-15 Contemporary Amperex Technology Co., Limited Batterie au lithium-ion, feuille d'électrode positive pour batterie au lithium-ion et dispositif
CN113839097A (zh) * 2021-08-24 2021-12-24 浙江超恒动力科技有限公司 一种电动自行车电池制备方法
JP2022019136A (ja) * 2020-07-17 2022-01-27 トヨタ自動車株式会社 非水電解質二次電池
EP4120408A4 (fr) * 2020-08-14 2023-06-07 Contemporary Amperex Technology Co., Limited Batterie secondaire et son procédé de préparation, et module de batterie, bloc-batterie et appareil comprenant une batterie secondaire
WO2023117492A3 (fr) * 2021-12-23 2023-08-17 Skeleton Technologies GmbH Compositions de matériau d'électrode pour électrodes d'accumulateurs d'énergie présentant des capacités de charge et de décharge rapides
US11973196B2 (en) 2019-08-08 2024-04-30 Contemporary Amperex Technology Co., Limited Positive electrode plate, and electrochemical apparatus and device associated therewith

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EP3859824A4 (fr) * 2019-12-05 2021-09-15 Contemporary Amperex Technology Co., Limited Batterie au lithium-ion, feuille d'électrode positive pour batterie au lithium-ion et dispositif
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EP4120408A4 (fr) * 2020-08-14 2023-06-07 Contemporary Amperex Technology Co., Limited Batterie secondaire et son procédé de préparation, et module de batterie, bloc-batterie et appareil comprenant une batterie secondaire
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CN113839097A (zh) * 2021-08-24 2021-12-24 浙江超恒动力科技有限公司 一种电动自行车电池制备方法
CN113839097B (zh) * 2021-08-24 2023-10-24 浙江超恒动力科技有限公司 一种电动自行车电池制备方法
WO2023117492A3 (fr) * 2021-12-23 2023-08-17 Skeleton Technologies GmbH Compositions de matériau d'électrode pour électrodes d'accumulateurs d'énergie présentant des capacités de charge et de décharge rapides

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