WO2006098216A1 - Batterie secondaire électrolytique non aqueuse - Google Patents

Batterie secondaire électrolytique non aqueuse Download PDF

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Publication number
WO2006098216A1
WO2006098216A1 PCT/JP2006/304597 JP2006304597W WO2006098216A1 WO 2006098216 A1 WO2006098216 A1 WO 2006098216A1 JP 2006304597 W JP2006304597 W JP 2006304597W WO 2006098216 A1 WO2006098216 A1 WO 2006098216A1
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battery
lithium
positive electrode
active material
electrode active
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PCT/JP2006/304597
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English (en)
Japanese (ja)
Inventor
Shinji Kasamatsu
Hajime Nishino
Hideharu Takezawa
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Matsushita Electric Industrial Co., Ltd.
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Publication of WO2006098216A1 publication Critical patent/WO2006098216A1/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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery, and in particular to a highly safe non-aqueous electrolyte secondary battery.
  • LiCoO is a positive electrode active material of a lithium ion secondary battery.
  • Lithium-containing composite oxides such as LiMn 2 o are used.
  • LiMn 2 o LiMn 2 o
  • LiNiO has a large theoretical capacity but on the other hand,
  • Li (NiMnCo) 0 is obtained, and this oxide is used as a positive electrode active material.
  • a separator used in a lithium ion secondary battery a porous film which is also a thermoplastic resin, for example, polyolefin, is often used from the viewpoint of safety.
  • a separator is also a force having a so-called shutdown function.
  • the shutdown function means that, for example, when an external short circuit occurs and the battery temperature rises sharply along with it, the separator softens, its pores are blocked, and the ion conductivity decreases. By doing this, it is a function to stop the current flow.
  • a large number of composite separators have been proposed that include a porous layer that is also made of polyolefin as described above and a layer made of a heat resistant resin.
  • a separator in which a layer comprising a heat-resistant nitrogen-containing aromatic polymer such as aramid or polyamideimide and a ceramic powder, and a porous film layer are laminated (see, for example, Patent Document 4). ).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-198051
  • Patent Document 2 Patent No. 3232943
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-31091
  • Patent Document 4 Patent No. 3175730
  • the safety of the battery can be enhanced.
  • the capacity reduction at the time of high temperature storage becomes large.
  • the aramid is obtained by polymerizing an organic substance having an amine group represented by paralep eradiamine and an organic substance having a chlorine group represented by terephthalic acid chloride, the aramid produced is Chlorine groups remain as end groups.
  • polyamideimide is obtained by reacting trimellitic anhydride monohydrate with diamine, a chlorine group remains as an end group in the formed polyamideimide. Such chlorine groups are liberated in the electrolyte under high temperature environment Do.
  • the main constituent elements (transition metals such as Co) of the positive electrode active material are easily eluted under the environment of high temperature and high potential.
  • a complex formation reaction between the transition metal eluted from the positive electrode active material and chlorine continues to occur.
  • a large amount of constituent elements are eluted from the positive electrode active material into the electrolytic solution, and the number of sites functioning as the positive electrode active material decreases, so that the battery capacity is considered to be significantly reduced.
  • the present invention has been made in view of the above problems, and has excellent safety.
  • An object of the present invention is to provide a non-aqueous electrolyte secondary battery capable of suppressing a decrease in capacity during high temperature storage.
  • the present invention comprises a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, a non-aqueous electrolytic solution, and a separator, and the separator has a heat resistant resin having a chlorine atom as an end group.
  • the present invention relates to a non-aqueous electrolyte secondary battery including a lithium-containing composite oxide in which the positive electrode active material has an aluminum atom in the composition.
  • the heat-resistant resin preferably contains at least one selected from the group consisting of aramid and polyamideimide.
  • the above-mentioned separator may have a film containing a heat resistant resin and a film containing a polyolefin laminated thereon.
  • the separator may have a film containing polyolefin and a layer containing a heat resistant resin and a filler formed on the film.
  • the lithium-containing composite oxide has the following formula:
  • M is preferably at least one selected from the group consisting of Co, Ni, Mn and Mg).
  • the above lithium-containing complex oxide is represented by the following formula:
  • the compound acid compound represented by (l ⁇ a ⁇ l. 05, 0. 005 ⁇ b ⁇ 0. 1, 0. 001 ⁇ c ⁇ 0.2) may be used.
  • Li Ni Co Al O (3) It is a complex acid compound represented by (l ⁇ a ⁇ l. 05, 0. l ⁇ b ⁇ 0. 35, 0. 001 ⁇ c ⁇ 0.2), and
  • FIG. 1 is a longitudinal sectional view schematically showing a cylindrical lithium secondary battery produced in an example.
  • the non-aqueous electrolyte secondary battery of the present invention comprises a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, a non-aqueous electrolyte, and a separator.
  • the positive electrode active material includes a lithium-containing composite oxide having an aluminum atom in the composition.
  • the separator contains a heat resistant resin having a chlorine atom as an end group.
  • the lithium-containing composite oxide which is a positive electrode active material, contains a predetermined amount of aluminum atoms.
  • the complex composed of an aluminum atom and a chlorine atom is more stable than the complex composed of a main constituent element (for example, a transition metal such as C, Ni, or Mn) of a lithium-containing composite acid complex and a chlorine atom.
  • the constant is high.
  • the aluminum atom tends to form a complex with the chlorine atom preferentially. Therefore, even if chlorine atoms which are terminal groups are liberated from the heat resistant resin contained in the separator during storage at high temperatures, the chlorine atoms are in preference to the aluminum atoms contained in the positive electrode active material. Form a complex.
  • the heat-resistant resin having a chlorine atom as a terminal group preferably contains at least one selected from a group consisting of aramid and polyamideimide. Since aramid and polyamideimide are soluble in polar organic solvents, porous films made of these immediately after film formation have extremely high retention and heat resistance of the non-aqueous electrolyte.
  • the heat-resistant resin preferably has a glass transition point, a melting point, and a sufficiently high thermal decomposition initiation temperature accompanied with a chemical change, more specifically, preferably has high mechanical strength under high heat.
  • the heat-resistant resin preferably has a heat distortion temperature of 260 ° C. or higher, which is determined by measurement of deflection temperature under load under test method ASTM-D 648, 1. 82 MPa of the American Society for Testing and Materials. This is because the shape of the separator can be maintained even when thermal contraction or the like occurs as the thermal deformation temperature is higher.
  • the heat distortion temperature is 260 ° C. or higher, the battery can exhibit sufficiently high thermal stability even when the battery temperature is further increased due to heat storage at the time of battery overheating (usually about 180 ° C.).
  • the amount of chlorine contained in the separator is preferably 300 to 3000 ⁇ g per 1 g of the separator.
  • the amount of chlorine contained in a given weight of heat resistant resin is affected by the degree of polymerization of the heat resistant resin. If the amount of chlorine is too low, the degree of polymerization of the heat-resistant resin becomes too high, and its flexibility decreases. For this reason, the processability of heat resistant resin falls. When the amount of chlorine is large, the heat distortion temperature of the heat resistant resin decreases as the degree of polymerization of the heat resistant resin decreases. Therefore, when the amount of chlorine is in the above-mentioned range, it is considered that the function of the heat-resistant resin is sufficiently achieved.
  • a porous film containing the above-mentioned heat-resistant resin may be used as a separator.
  • the separator may be a laminated film in which, for example, a porous film containing polyolefin such as polyethylene and polypropylene and a porous film containing the above-mentioned heat resistant resin are laminated.
  • the separator may be a laminate having a porous film containing polyolefin and a porous layer containing the above-mentioned heat resistant resin and filler formed thereon.
  • a porous film containing the above-mentioned heat resistant resin can be produced as follows.
  • the heat-resistant resin is dissolved in a polar solvent such as N-methyl pyrrolidone. Obtained The solution is applied onto a substrate such as a glass plate or stainless plate and dried. The obtained porous membrane is peeled off from the substrate. Thus, a porous film containing the above-mentioned heat resistant resin can be obtained.
  • a polar solvent such as N-methyl pyrrolidone.
  • a laminate having a porous film containing polyolefin and a porous layer containing the above-mentioned heat-resistant resin and filler formed thereon can be produced as follows.
  • the heat-resistant resin is dissolved in a polar solvent, and a filler is added to the solution.
  • the resulting mixture is coated on a porous membrane containing polyolefin and dried.
  • a laminate having a porous membrane containing polyolefin and a porous layer containing the above-mentioned heat-resistant resin and filler formed thereon can be obtained.
  • the filler used may be chemically stable and high in purity so as not to adversely affect the battery characteristics even under the immersion potential of the non-aqueous electrolyte and the redox potential of the active material.
  • Such fillers include, for example, inorganic acid filler.
  • inorganic inorganic fillers such as alumina, zeolite, silicon nitride, silicon carbide, silicon oxide, zirconium oxide, magnesium oxide, zinc oxide, zinc oxide, etc. Porous material is included.
  • a separator having a laminate having a porous film containing polyolefin and a porous layer containing the above-mentioned heat-resistant resin and filler, which is formed thereon, is used as a separator because it has higher heat resistance. Preferred to use.
  • the thickness of the heat resistant resin layer and the porous layer containing filler is Although it is not particularly limited, from the viewpoint of securing safety by prevention of internal short circuit and balance of battery capacity, it is more preferable to be 1 to 120 111, preferably 2 to 10 m. When the thickness is less than 1 m, in a high temperature environment, the porous layer containing heat resistant resin and filler becomes effective in suppressing the thermal contraction of the porous layer containing polyolefin.
  • the porous layer containing the heat resistant resin and the filler is The porosity is relatively low and its ion conductivity is reduced. As a result, the impedance may increase and the charge and discharge characteristics of the battery may be slightly reduced.
  • the porosity of the porous layer containing the heat resistant resin and the filler is preferably 20 to 70%.
  • the porosity can be controlled by adjusting the coating speed and drying conditions (temperature and air volume) of the mixture containing heat resistant resin and filler, and the particle diameter and shape of the filler.
  • the separator has a porous film containing polyolefin and a porous layer containing a heat resistant resin and a filler formed thereon
  • the total thickness of the separator is not particularly limited. If considering safety, various battery characteristics, and battery design capacity, it is preferred to be 5 to 35 ⁇ m! /.
  • the pore diameter of the porous membrane containing the polyolefin is preferably 0.01 to 10 / ⁇ ⁇ ⁇ .
  • the thickness of the separator is preferably 5 to 20 ⁇ m in order to ensure the safety by preventing the internal short circuit and the balance between the battery capacity and 10 to 20 ⁇ m. It is more preferable that The porosity of the separator containing heat resistant resin is preferably 20 to 70%. The porosity of the separator can be controlled by adjusting the coating speed and drying conditions of the heat resistant resin solution.
  • the chlorine atoms preferentially form complexes with aluminum atoms.
  • a lithium-containing composite oxide containing a predetermined amount of aluminum is used.
  • lithium-containing composite acid compounds the following formula:
  • An acid food can be used.
  • the lithium-containing composite acid oxide represented by the formula (1) has a large capacity and high voltage. In any case, it is possible to occlude and release lithium ions.
  • the molar ratio X of lithium be l ⁇ x 05l. 05.
  • the molar ratio X of lithium is less than 1, the amount of lithium salt in the raw material mixture for producing the lithium-containing composite oxide decreases. For this reason, electrochemically inactive impurities such as cobalt oxide and the like are present in the obtained product, which may lower the battery capacity.
  • the molar ratio of lithium X exceeds 1.05, an excess of lithium salt is present in the raw material mixture. For this reason, lithium salt may remain as an impurity in the product, and the battery capacity may be reduced.
  • the molar ratio X of lithium is a value immediately after preparation of the lithium-containing composite acid represented by the formula (1). However, the X value changes beyond the range of the above X value due to charge and discharge of the battery
  • the molar ratio y of aluminum is less than 0.001, a sufficient improvement effect beyond the above-mentioned action may not be expected.
  • the molar ratio y exceeds 0.2, the amount of metal atoms M contributing to the charge and discharge reaction decreases, so the battery capacity S may decrease.
  • the method for producing the lithium-containing composite oxide represented by the formula (1) is not particularly limited, and can be produced, for example, as follows.
  • At least one selected salt selected from cobalt salt, nickel salt, manganese salt and magnesium salt, lithium salt and magnesium salt are mixed in a predetermined ratio.
  • the lithium-containing composite oxide of the formula (1) can be obtained by calcining the obtained raw material mixture at a high temperature under an oxidizing atmosphere.
  • the lithium-containing composite acid represented by can be used.
  • the lithium-containing composite oxide represented by the formula (2) contains magnesium. Due to the inclusion of magnesium, even if the positive electrode active material repeatedly expands and contracts due to charge and discharge, distortion of the crystal lattice, its structure It is possible to suppress smashing or cracking of active material particles. This alleviates the decrease in discharge capacity and improves the cycle characteristics.
  • the molar ratio b of magnesium be in the range of 0.50 ⁇ b 1 0.1.
  • the molar ratio b is 0.
  • the ratio is less than 005, the above effect may not be obtained. If the molar ratio b exceeds 0.1, the battery capacity may decrease slightly.
  • the molar ratio c of aluminum is preferably in the range of 0.10 ⁇ c 2 0.2.
  • the molar ratio c is 0.
  • the preferred range of the molar ratio a of lithium and the reason why the range is preferred are the same as in the case of the lithium-containing composite oxide of the formula (1).
  • the method for producing the lithium-containing composite oxide represented by the formula (2) is not particularly limited, and can be produced, for example, as follows.
  • Lithium salt, magnesium salt, cobalt salt and aluminum salt are mixed in a predetermined ratio.
  • the lithium-containing composite acid oxide of the formula (2) can be obtained by calcining the obtained raw material mixture at a high temperature under an oxidizing atmosphere.
  • a composite salt containing two or more elements selected from the group consisting of complex, magnesium and aluminum may be used in place of the respective salts of the elements contained in the composite salt.
  • eutectic hydroxides containing cobalt, magnesium and aluminum or their eutectic oxides can be used.
  • LiNiO based material It is also possible to use a lithium-containing composite acid represented by The LiNiO based material is
  • the lithium-containing composite acid of the formula (3) further contains cobalt and aluminum in its composition.
  • Cobalt atom or aluminum nuclear, its complex acid, particularly lithium by being present in the lithium diffusion layer in its crystal structure At the time of force detachment, contraction of the crystal lattice is suppressed. Therefore, the amount of structural change at the time of charge and discharge can be reduced by / J.
  • the lithium-containing composite acid of formula (3) is less expensive than LiCoO-based materials.
  • the molar ratio b of cobalt is preferably in the range of 0.1 ⁇ b ⁇ 0.35. If the molar ratio b is less than 0.1, it is difficult to obtain the above-mentioned effects. If the molar ratio b exceeds 0.35, the battery capacity decreases slightly.
  • the preferable range of the molar ratio a of lithium and the molar ratio c of aluminum and the reason why the range is preferable are the same as in the case of the lithium-containing composite acid of the formula (1).
  • the lithium-containing composite oxide of the formula (3) can be produced, for example, as follows.
  • the nickel salt, cobalt salt and aluminum salt are dissolved in water at a predetermined mixing ratio.
  • the resulting aqueous solution is neutralized and coprecipitated to precipitate as a nickel-cobalt-aluminum ternary composite hydroxide.
  • the obtained composite hydroxide and lithium salt are mixed at a predetermined mixing ratio, and the mixture is fired to obtain a lithium-containing composite oxide of the formula (3).
  • a composite salt containing two or more elements selected from nickel, cobalt and aluminum may be used in place of the respective salts of the elements contained in the composite salt.
  • lithium-containing composite acid represented by The lithium-containing composite oxide represented by the formula (4) can maintain stable battery characteristics while being inexpensive.
  • the molar ratio b of manganese be in the range of 0.1.b ⁇ 0.5. If the molar ratio b is less than 0.1, the amount of manganese contained in the complex oxide is small, so cost reduction is difficult. When the molar ratio b exceeds 0.5, the battery capacity decreases slightly.
  • the molar ratio c of cobalt is preferably in the range of 0.1 0 c ⁇ 0.5. If the molar ratio c is less than 0.1, the crystals of the complex oxide may become somewhat unstable, the cycle characteristics may be degraded, and the safety of the battery may be somewhat degraded. If the molar ratio c exceeds 0.5, the battery capacity decreases slightly.
  • the preferable range of the molar ratio a of lithium and the molar ratio d of aluminum is the same as in the case of the lithium-containing composite oxide of the formula (1).
  • the lithium-containing composite oxide of the formula (4) is prepared, for example, by mixing lithium salt, nickel salt, cobalt salt, manganese salt, aluminum salt and the like in a predetermined mixing ratio, and oxidizing the resulting mixture. It can be obtained by firing at a high temperature under an atmosphere.
  • a complex salt containing two or more elements selected from the group consisting of nickel, cobalt, manganese and aluminum is used in place of the respective salts of the elements contained in the complex salt. It is also good.
  • eutectic hydroxides containing cobalt, magnesium, manganese and aluminum or their eutectic oxides can be used.
  • lithium carbonate, lithium hydroxide, lithium nitrate, lithium sulfate and lithium oxide can be used as a lithium salt used for the synthesis of the above lithium-containing composite acid complex.
  • magnesium salt for example, magnesium oxide, basic magnesium carbonate, magnesium chloride, magnesium fluoride, magnesium nitrate, magnesium sulfate, magnesium acetate, magnesium oxalate, magnesium sulfate, magnesium sulfate and hydroxide magnesium hydroxide are used. It can be done.
  • cobalt salt for example, cobalt oxide and cobalt hydroxide can be used.
  • aluminum salt for example, aluminum hydroxide, aluminum nitrate, aluminum oxide, aluminum fluoride and aluminum sulfate can be used.
  • nickel salt it is possible to use, for example, acid nickel and hydroxide nickel. Can.
  • manganese salt for example, manganese dioxide, manganese dioxide, manganese carbonate, manganese nitrate, manganese sulfate, manganese fluoride, manganese chloride, and hydroxyhydroxylated manganese can be used.
  • the effects of the present invention can be obtained by using the composite oxide contained therein alone or in combination of two or more. You can earn For example, a mixture containing two or more of lithium-containing composite acids represented by formulas (1) to (4) can be used as a positive electrode active material.
  • each composite oxide in the charge state is derived from the valence of the included transition metal.
  • the potentials of the respective complex oxides have different values. For this reason, in the mixture, variations in potential distribution are likely to occur. Therefore, when the chlorine atom contained as a terminal group in the heat resistant resin is liberated, there is a possibility that the main constituent elements (transition metals such as Co) of the positive electrode active material may be easily eluted in the non-aqueous electrolyte. . Furthermore, when the charging voltage is high, the transition metal contained in the positive electrode active material is easily oxidized in a high voltage environment, and in particular, the main constituent element (transition metal such as Co) is easily eluted.
  • the lithium-containing composite acid oxide used in the present invention contains A1, even if the chlorine atom contained in the heat-resistant resin is liberated in the non-aqueous electrolyte, the positive electrode can be selectively selected. A1 selectively elutes from the complex acid product of and the elution of the other main components is suppressed. Therefore, it is possible to obtain a battery which is excellent in safety and in which the capacity reduction at the time of high temperature storage is suppressed.
  • the positive electrode includes, for example, a positive electrode current collector and a positive electrode mixture layer supported thereon. / / ...
  • the positive electrode mixture layer contains a positive electrode active material, a conductive agent, a binder and the like.
  • the positive electrode active material includes a lithium-containing composite oxide having an aluminum atom in the composition.
  • binder used for the positive electrode examples include polytetrafluoroethylene and modified atari.
  • examples include oral-tolyl rubber particles (eg, BM-500B manufactured by Nippon Zeon Co., Ltd.), and polyfluorinated bi-idene having both binding property and thickening property and modified products thereof. These may be used alone or in combination of two or more.
  • polytetrafluoroethylene and modified acrylonitrile rubber particles are combined with carboxymethyl cellulose, polyethylene oxide, and soluble modified atari port 2 tolyl rubber (for example, BM-720H manufactured by Nippon Zeon Co., Ltd.) having a thickening effect. You may use it.
  • acetylene black, ketjen black, and various graphites can be used as the conductive agent. These may be used alone or in combination of two or more.
  • the negative electrode may also include a negative electrode current collector and a negative electrode mixture layer supported thereon.
  • the negative electrode mixture layer contains a negative electrode active material.
  • the negative electrode mixture layer may contain a binder, a conductive agent, and the like, as necessary.
  • lithium metal a material capable of alloying with lithium, various natural graphites and artificial graphites, silicon-based composite materials such as silicides, and a group force consisting of tin, aluminum, zinc and magnesium are also selected.
  • Lithium alloys containing one element and various alloy materials can be used. These may be used alone or in combination of two or more.
  • a single substance of silicon As materials that can be alloyed with lithium, a single substance of silicon, an oxide of silicon (for example, SiO (0 ⁇ x ⁇ 2)), a single substance of tin, an oxide of tin (for example, SnO), Ti, etc.
  • an oxide of silicon for example, SiO (0 ⁇ x ⁇ 2)
  • a single substance of tin for example, SnO
  • Ti etc.
  • the negative electrode mixture layer may be formed by direct deposition of the negative electrode active material on a current collector.
  • a negative electrode mixture layer may be formed by applying a mixture containing a negative electrode active material and a small amount of optional components on a current collector and drying.
  • the binder used in the negative electrode is, like the positive electrode, poly-biphenylidene difluoride and the like.
  • Various resin materials can be used including denatured products.
  • a water-soluble binder containing, for example, a styrene-butadiene copolymer or a modified product thereof and a cellulose-based resin such as carboxymethylcellulose.
  • a water-soluble binder containing, for example, a styrene-butadiene copolymer or a modified product thereof and a cellulose-based resin such as carboxymethylcellulose.
  • the non-aqueous electrolyte contains a non-aqueous solvent and a solute dissolved in the non-aqueous solvent.
  • solvents generally used in the relevant field can be used.
  • Such solvents include, for example, ethylene carbonate, dimethinole carbonate, getinole carbonate, and ethyl methyl carbonate. These may be used alone or in combination of two or more.
  • lithium salts As a solute, a lithium salt generally used in the relevant field can be used.
  • Such lithium salts include, for example, LiPF and LiBF. like this
  • the lithium salts may be used alone or in combination of two or more.
  • the non-aqueous electrolytic solution may also contain, for example, biphenyl carbonate, cyclohexyl benzene, and Z or their modified products in order to form a good film on the positive and negative electrodes.
  • the lithium-containing composite oxide was used as the positive electrode active material 11.
  • NMP N-methylpyrrolidone
  • a positive electrode mixture paint was prepared by stirring 1 kg of # 1320 (trade name), 90 g of acetylene black as a conductive agent, and an appropriate amount of NMP with a double-arm mixer.
  • This paint was applied to both sides of a 15 ⁇ m thick aluminum foil as a positive electrode current collector. At this time, the paint was not applied to the connection portion of the positive electrode lead.
  • the applied paint was dried and rolled with a roller to form a positive electrode mixture layer having an active material density (active material weight Z mixture layer volume) of 3.3 g Z cm 3 .
  • the total thickness of the positive electrode current collector and the positive electrode mixture layer was 160 m.
  • the obtained electrode plate precursor was slit into a width that can be inserted into a battery case of a cylindrical battery (diameter 18 mm, length 65 mm) to obtain a positive electrode plate.
  • An aqueous dispersion containing 3% of artificial graphite as a negative electrode active material and 40% by weight of a modified product of a styrene butadiene copolymer as a negative electrode binder ("BM-400B (trade name)" manufactured by Nippon Zeon Co., Ltd.)
  • a negative electrode mixture paint was prepared by stirring 75 g, carboxymethyl cellulose 30 g as a thickener, and an appropriate amount of water with a double-arm mill. The obtained paint was applied to both sides of a 10 m-thick copper foil as a negative electrode current collector. At this time, this paint was not applied to the connection portion of the negative electrode lead.
  • the applied paint was dried and rolled with a roller to form a negative electrode mixture layer with an active material density of 1.4 gZ cm 3 .
  • the total thickness of the copper foil and the negative electrode mixture layer was controlled to 180 m.
  • the obtained electrode plate precursor was slit to a width that can be inserted into the above-described battery can of the cylindrical battery, to obtain a negative electrode plate.
  • a laminated film including a 16 m thick polyethylene (PE) porous thin film and a film made of aramid resin which is a heat-resistant resin formed thereon was prepared, and this laminated film was used as a separator. . Below, the manufacturing method of the said laminated film is shown.
  • PE polyethylene
  • the resulting solution was allowed to cool to room temperature, and 3.2 weight parts of paraphenylene diamine was added to this solution to completely dissolve it.
  • the reaction vessel containing the solution containing paradylene diamine was placed in a thermostat at 20.degree. While maintaining the temperature at 20 ° C., 5.8 parts by weight of diphthalic acid terephthalic acid is added dropwise to the solution over 1 hour, and reacted to obtain polyparaphenylene terephthalate (hereinafter referred to as “PPTA”).
  • PPTA polyparaphenylene terephthalate
  • the solution containing PPTA was allowed to stand in a thermostat at 20 ° C. for 1 hour, and after completion of the reaction, the solution containing PTCA was put into a vacuum chamber and degassed for 30 minutes while stirring under reduced pressure.
  • the resulting polymerization solution further more the Shioi ⁇ calcium be diluted with ⁇ Ka ⁇ the NMP solution, PPTA concentration was prepared NMP solution of PTAA of 1.4 weight 0/0.
  • the NMP solution of PTAA thus obtained was thinly coated on a polyethylene porous thin film with a doctor blade, and dried with hot air at 80 ° C. (wind speed: 0.5 mZ seconds). Thereafter, the obtained PTAA membrane was thoroughly washed with pure water to remove calcium chloride, to make the membrane porous and then dried again. Thus, a laminated membrane including a polyethylene porous thin membrane and a PTAA porous membrane formed thereon was produced.
  • the amount of residual chlorine in this laminated film was measured by molecular analysis, and the amount of residual chlorine was 650 ⁇ g per 1 g of laminated film.
  • LiPF was dissolved at a concentration of ImolZL in a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate mixed in a volume ratio of 2: 3: 3.
  • a concentration of ImolZL in a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate mixed in a volume ratio of 2: 3: 3.
  • a cylindrical battery as shown in FIG. 1 was produced.
  • the positive electrode plate and the negative electrode plate obtained as described above are respectively cut into predetermined lengths, The positive electrode 11 and the negative electrode 12 were obtained.
  • One end of the positive electrode lead 14 was connected to the positive electrode lead connection portion of the positive electrode 11.
  • a separator 13 was disposed between the positive electrode 11 and the negative electrode 12 to which one end of the negative electrode lead was connected, and these were wound to fabricate a cylindrical electrode group.
  • the separator 13 was disposed between the positive electrode 11 and the negative electrode 12 so that the PTAA layer was disposed on the positive electrode side.
  • the outermost periphery of the electrode assembly was covered with the separator 13.
  • the obtained electrode group was sandwiched between the upper insulating ring 16 and the lower insulating ring 17, and these were accommodated in a battery can 18. Then, 5 g of the non-aqueous electrolyte (not shown) was injected into the battery can 18. After that, the inside of the battery can 18 was depressurized to 133 Pa, and the electrode group was impregnated with the non-aqueous electrolyte by leaving it until no residue of the non-aqueous electrolyte was observed on the surface of the electrode group.
  • the other end of the positive electrode lead 14 was welded to the back surface of the battery lid 19 having the insulating packing 20 at the periphery, and the other end of the negative electrode lead 15 was welded to the inner bottom surface of the battery can 18.
  • the open end of the battery can 18 was pressed onto the insulating packing 20 of the battery lid 19 to close the opening of the battery can 18, thereby completing the cylindrical lithium ion secondary battery.
  • the obtained battery was used as the battery of Example 1-1.
  • the concentration ratio of cobalt sulfate to aluminum sulfate is set to 0.95: 0.5, 0.50: 0.20, or 0.75: 0.25.
  • a battery was manufactured in the same manner as in the f-th row 1-1. The obtained batteries were used as the batteries of Examples 12 to 14, respectively.
  • Example 1-5 When synthesizing the precursor of the positive electrode active material, iron sulfate is further added, and the concentration ratio of cobalt sulfate to iron sulfate to aluminum sulfate is set to 0.9: 0. 05: 0. 05 except that A battery was produced in the same manner as Example 1-1. The obtained battery was used as the battery of Example 1-5.
  • a battery was produced in the same manner as in Example 1-2 except that a laminated film in which a film made of polyamideimide resin was formed instead of the PTAA film on a porous film made of polyethylene was used as a separator. The obtained battery was used as the battery of Example 110.
  • Trimellitic anhydride monochloride and diamine were added to NMP at room temperature and mixed to obtain an NMP solution of polyamic acid.
  • This NMP solution was thinly applied onto a polyethylene porous thin film by a doctor blade.
  • the coated film was dried with hot air at 80 ° C. (air velocity: 0.5 mZ seconds) to dehydrate the polyamic acid, cyclize it, and convert it to polyamidoimide.
  • a laminated film including a porous polyethylene thin film and a polyamideimide film formed thereon was produced.
  • the total thickness of this laminated film was 20 m.
  • the amount of residual chlorine in this laminated film was measured by molecular analysis, and the amount of residual chlorine was 830 ⁇ g per 1 g of laminated film.
  • a battery was fabricated in the same manner as in Example 1-2, except that a porous film which also had only aramid force was used as the separator.
  • the obtained battery is referred to as the battery of Example 1-11.
  • aramid resin As described above, a predetermined amount of aramid resin was dissolved in NMP. Next, the NMP solution was applied onto a smooth stainless steel plate using a doctor blade. The resulting coated film was dried with hot air at 80 ° C. (air velocity: 0.5 mZ seconds) to obtain a porous film in which only aramid was active. The thickness of this porous membrane was 20 m.
  • the amount of residual chlorine in this porous membrane was measured by molecular analysis, and the amount of residual chlorine was 1800 g per 1 g of the porous membrane.
  • Example 1 12 A battery was fabricated in the same manner as in Example 1-2, except that a layered product having a porous polyethylene thin film and a layer containing a filler and aramid resin formed thereon was used as a separator. did. The obtained battery was used as a battery of Example 112.
  • Alumina fine particles were added to the NMP solution of aramid resin prepared in the above Example 1-1 and stirred.
  • the amount of alumina fine particles added was 200 parts by weight per 100 parts by weight of the aramid resin contained in the NMP solution.
  • the obtained dispersion was thinly coated on a porous polyethylene thin film with a doctor blade, and the coated film was dried by hot air at 80 ° C. (wind velocity: 0.5 mZ seconds).
  • a laminate having a polyethylene porous membrane and a layer containing a filler and an aramid formed thereon was obtained.
  • the amount of residual chlorine in this laminate was measured by molecular analysis, and the amount of residual chlorine was 600 g per 1 g of separator.
  • Example 1-1 In the same manner as in Example 1-1, cobalt sulfate alone was used to synthesize cobalt hydroxide, and lithium carbonate and cobalt hydroxide were mixed so that the molar ratio force of lithium and cobalt was 1.02: 1.
  • the lithium-containing composite oxide was synthesized.
  • a battery was produced in the same manner as in Example 1-1 except that this lithium-containing composite oxide was used as a positive electrode active material. The obtained battery was used as the battery of Comparative Example 1.
  • a battery was fabricated in the same manner as in Example 1-2, except that a polyethylene porous film with a thickness of 20 m was used as the separator. The obtained battery was used as the battery of Comparative Example 2.
  • Each obtained battery is discharged at a constant current of 400 mA until the battery cell decreases to 3 V, and then, preliminary charging / discharging is performed until the battery voltage reaches 4.2 V at a constant current of 1400 mA. Served twice. The charged battery was then stored at 45 ° C. for 7 days. The following evaluation was performed on the battery after storage.
  • the battery After storage, the battery was charged at a constant voltage of 4.2 V at 20 ° C. until the current value decreased to 100 mA. Thereafter, the charged battery was placed in a 130 ° C. constant temperature bath, and the maximum temperature of the battery surface was measured. The results are shown in Table 1.
  • the initial discharge capacity was measured as described above. After this, the battery was charged at 20 ° C. with a constant voltage of 4.2 V until the current value decreased to 100 mA. Next, the battery after charging was placed in a thermostat of 90 ° C. and stored for 24 hours. After storage, the battery was discharged at a constant current of 2000 mA, and the discharge capacity after storage was determined. The ratio of the discharge capacity after storage to the initial discharge capacity as a percentage was taken as the capacity recovery rate. The results are shown in Table 1.
  • Table 1 also shows the composition of the positive electrode active material and the type of separator used in Examples and Comparative Examples.
  • Example 1-1 1.02 0.999 0 0.001 aramid + PE 2050 142 66 Example 1-2 1.02 0.95 0 0.05 aramid + PE 2020 139 70 Example 1-3 1.02 0.8 0 0.2 aramid + PE 2000 140 71 Example 4 1.02 0.75 0 0.25 Fara SD + PE 1890 139 73 Example 5 1.02 0.9 0.05 0.05 aramid + PE 2015 141 72 Example 1-6 0.98 0.95 0 0.05 aramid + PE 1900 144 71 Example 1-7 1 0.95 0 0.05 Aramid + PE 1950 143 70 Example 1-8 1.05 0.95 0 0.05 Aramid + PE 1970 141 72 Example 1-9 1.08 0.95 0 0.05 Aramid + PE 1880 142 70 Example 1-10 1.02 0.95 0 0.05 Polyamide imm 2020 144 69
  • Example 1-12 1.02 0.95 0 0.05 (aramid + flame 2020 142 71 ir) + PE
  • the separator contains a heat-resistant resin and a positive electrode active material containing an aluminum atom in the composition as in the batteries of Examples 1 1 to 1 12, the safety under high temperature environment is high. It can be seen that the integrity and preservation characteristics can be compatible.
  • the aluminum atom in the positive electrode active material forms a stable complex ion with the liberated chlorine from the aramid (or polyamide imide).
  • the positive electrode active material power is considered to be because the aluminum atoms were selectively eluted, and the elution of other components of the positive electrode active material was suppressed. Such an effect is the same as in the case of the battery of Example 15 when a positive electrode active material containing a metal such as iron in addition to cobalt in the composition is used.
  • Example 14 As shown in the results of Examples 1 to 14, as the amount of aluminum contained in the positive electrode active material increases, the maximum temperature of the battery decreases and the capacity recovery rate improves. However, as shown in Example 14, when the amount of aluminum is too large, the proportion of main constituent elements in the positive electrode active material is reduced, and the initial discharge capacity is reduced.
  • the initial discharge capacity is reduced if the amount of lithium contained in the positive electrode active material is small or large. If the amount of lithium in the positive electrode active material is small, it is considered that the amount of impurities does not contribute to the battery capacity, such as cobalt oxide, and the battery capacity decreases. If the amount of lithium is too large, it is considered that an excess of lithium remains as an impurity in the positive electrode active material and the initial discharge capacity is reduced.
  • Example 2 Each of the obtained batteries was subjected to the same preliminary charge and discharge as in Example 1 twice.
  • the charged battery was stored at 45 C for 7 days.
  • the initial discharge capacity, the maximum temperature of the battery surface and the capacity recovery rate were measured in the same manner as in Example 1 for the battery after storage. The results are shown in Table 2.
  • the capacity retention rate was further measured for the battery after storage at 45 ° C. for 7 days.
  • the capacity retention rate was measured as follows.
  • the first charge and discharge cycle was repeated 200 times at 5 ° C. for the battery after storage.
  • the ratio of the discharge capacity of the 200th cycle to the discharge capacity of the first cycle as a percentage value was taken as the capacity retention ratio.
  • the results are shown in Table 2.
  • the capacity retention rate of each battery is 80% or more. Therefore, when the h electrode active material contains magnesium, expansion and contraction of the positive electrode active material due to charge and discharge are alleviated, and a decrease in discharge capacity is suppressed.
  • Example 2-2 and 2-5 2-8 magnesium in the positive electrode active material was As the molar ratio b increases, the capacity retention rate is improved. However, in the case of Example 2-5 in which the molar ratio b is 0.01, the capacity retention ratio is 80%, and sufficient cycle characteristics can not be obtained.
  • Example 1 Further, with regard to the aluminum amounts and lithium amounts shown in Examples 2-1 to 2-4 and Examples 2-9 to 2-12, the same as Example 1 can be applied. Tend.
  • Example 1-1 When a precursor of a positive electrode active material is synthesized, nickel sulfate, cobalt sulfate and aluminum sulfate are used, and the concentration ratio of these is changed as shown in Table 3, to obtain Example 1-1 and In the same manner, precursors 3-1 to 3-12 were synthesized. In addition, the mixing ratio of the obtained precursor 3-1 to 3-12 and lithium carbonate is changed as shown in Table 3, and the positive electrode active material 3- is obtained in the same manner as in Example 1-1. 1 to 3-12 were synthesized. A battery was produced using these positive electrode active materials in the same manner as in Example 1-1. The obtained batteries were used as the batteries of Examples 3-1 to 12 respectively.
  • Example 3 Each battery thus obtained was subjected to the same preliminary charge and discharge as in Example 1 twice.
  • the charged battery was stored at 45 ° C. for 7 days.
  • the initial discharge capacity, the maximum temperature of the battery surface, the capacity recovery rate and the capacity retention rate were measured in the same manner as in Example 2. The results are shown in Table 3.
  • Example 3-1 1.01 0.849 0.15 0.001 2250 144 48 87
  • Example 3-2 1.01 0.8 0.15 0.05 2100 141 77 88
  • Example 3-3 1.01 0.65 0.15 0.2 2069 142 83 89
  • Example 3-4 1.01 0.64 0.15 0.21 2030 141 85 91
  • Example 3-5 1.01 0.945 0.005 0.05 2350 143 73 81
  • Example 3-6 6
  • Example 3-7 1.01 0.6 0.35 0.05 2100 145 73 91
  • Example 3-8 1.01 0.5 0.45 0.05 1950 143 74 93
  • Example 3-9 0.98 0.8 0.15 0.05 2009 141 82 87
  • Example 3-10 1 0.8 0.15 0.05 2082 142 83 88
  • Example 3-11 1.05 0.8 0.15 0.05 2054 142 84 89
  • Example 3-12 1.08 0.8 0.15 0.05 1917 141 81 88
  • Example 3-5 the initial discharge capacity increases as the amount of nickel contained in the positive electrode active material increases, that is, as the amount of cobalt decreases. It is however, in the case of Examples 3-8 in which the molar ratio b of cobalt is 0.45, sufficient initial discharge capacity may not be obtained.
  • Example 3-5 in which the molar ratio b of cobalt was 0.005, the capacity retention rate was slightly reduced. This is considered to be because expansion and contraction of the positive electrode active material due to charge and discharge can not be sufficiently relaxed.
  • Example 3- Furthermore, as shown in Example 3- :! to 3-4 and Example 3-9 to 3-12, the aluminum amount and the lithium amount also tend to be the same as in Example 1.
  • Example 4 (Example 4 1:! To 19)
  • Example 1-1 When a precursor of a positive electrode active material is synthesized, nickel sulfate, manganese sulfate, cobalt sulfate, and aluminum sulfate are used, and the concentration ratio thereof is changed as shown in Table 4 to obtain Example 1-1. In the same manner, precursors 4 1 to 4 19 were synthesized. In addition, the mixing ratio of the obtained precursor 4- 14 19 to lithium carbonate was changed as shown in Table 4, and the positive electrode active material 41 was prepared in the same manner as in Example 11. 4-19 were synthesized. A battery was produced using these positive electrode active materials in the same manner as in Example 1-1. The obtained batteries were used as the batteries of Example 4-14, respectively.
  • the resulting battery was subjected twice to the same preliminary charge and discharge as in Example 1.
  • the charged battery was stored at 45 ° C. for 7 days.
  • the initial discharge capacity, the maximum temperature of the battery surface, and the capacity recovery rate were measured in the same manner as in Example 1. The results are shown in Table 4.
  • Table 4 also shows the values of b + c + d.
  • Example 4-1 1.01 0.339 0.33 0.33 0.001 0.661 1890 141 69
  • Example 4-2 1.01 0.31 0.32 0.32 0.05 0.69 1862 133 73
  • Example 4-3 1.01 0.26 0.27 0.27 0.2 D.74 1710 139
  • Example 4-4 1.01 0.27 0.26 0.26 0.21 0.73 1690 138
  • Example 4-5 1.01 0.44 0.19 0.32 0.05 0.56 1950 141
  • Example 4-6 1.01 0.19 0.57 0.19 0.05 0.81 1650 143 73
  • Example -7 0.98 0.31 0.32 0.32 0.32 0.36 0
  • Example 4-8 1 0.31 0.32 0.32 0.05 0.69 1846 137 73
  • Example 4-9 1.05 0.31 0.32 0.32 0.05 0.69 1822 137
  • Example 4-10 1.08 0.31 0.32 0.32 0.32 0.32 137 138
  • Example 3 4-11 1.01 0.85 0.05 0.05 0.05 0.15 2100 148 T6
  • Example 4-12 1.01 0.75 0.10 0.10
  • a certain amount or more of manganese is required to reduce costs.
  • the maximum temperature of the battery surface is increased, and the battery safety is somewhat reduced.
  • the molar ratio b of the Gunn gun is 0.6, the initial discharge capacity decreases.
  • Example 4-11 when the molar ratio c of cobalt is 0.05, the maximum temperature of the battery surface is high. In Examples 4-17 and 419 in which the molar ratio c of cobalt is 0.6, the initial discharge capacity is reduced.
  • Examples 4-1 to 4-4 and Examples 4-7 to 4-10 the amounts of aluminum and lithium tend to be the same as in Example 1. .
  • Example 4-11 in which b + c + d force ⁇ ). 15, the maximum temperature on the battery surface was increased, and the battery safety tended to be slightly reduced. Thus, it can be seen that when 0.2 ⁇ b + c + d ⁇ 0.75, a battery with an excellent balance of the above three characteristics can be obtained.
  • Example 4-2 50 parts by weight of the positive electrode active material (Li Co Al 2 O 3) used in Example 1-2 and Example 4-2
  • Example 5-1 The resulting powder was designated as a positive electrode active material 5-1.
  • a battery was fabricated in the same manner as Example 1-1 except that this positive electrode active material was used. The obtained battery is referred to as the battery of Example 5-1.
  • Example 5-2 A battery was fabricated in the same manner as Example 1-1 except that this positive electrode active material was used. The obtained battery is referred to as the battery of Example 5-1.
  • Example 5-2 A battery was fabricated in the same manner as Example 1-1 except that this positive electrode active material was used. The obtained battery is referred to as the battery of Example 5-1.
  • Example 5-2 Example 5-2
  • a battery was fabricated in the same manner as in Example 1-2, except that the active material density of the positive electrode mixture layer was 3.3 gZ cm 3, and the thickness of the positive electrode plate was 144 m. The obtained battery was used as a battery of Example 5-1.
  • a battery was produced in the same manner as in Example 4-2 except that the active material density of the positive electrode mixture layer was 3.3 gZ cm 3, and the thickness of the positive electrode plate was 144 m. The obtained battery was used as the battery of Example 5-3.
  • Si silicon
  • BM-400B manufactured by Nippon Zeon Co., Ltd.
  • the negative electrode mixture paste was applied to both sides of a strip-shaped negative electrode current collector made of copper foil having a thickness of 10 m.
  • the applied negative electrode material mixture paste was dried and rolled by a rolling roll to produce a negative electrode plate.
  • a battery was produced in the same manner as in Example 3-2 except that this negative electrode plate was used. The obtained battery was used as the battery of Example 5-4.
  • a battery was fabricated in the same manner as in Example 5-4, except that SiO powder (median diameter 8 ⁇ m) was used instead of silica powder, and the dimensions of the positive electrode and the negative electrode were changed as appropriate. The obtained battery was used as the battery of Example 5-5.
  • the following negative electrode was produced using a vacuum evaporation system provided with a water-cooled roller in the vacuum chamber.
  • An electrolytic Cu foil (manufactured by Furukawa Circuit Oil Co., Ltd., thickness 20 ⁇ m) as a current collector was attached and fixed to a water-cooled roller in a vacuum deposition apparatus. Immediately below that, a graphite crucible in which a carbon (Flutch Chemical Co., Ltd., ingot having a purity of 99. 999%) was placed was placed. Between chopsticks and Cu foil The nozzle was installed in the vacuum chamber 1 so that oxygen gas was introduced into the chamber. The flow rate of oxygen gas (manufactured by Nippon Oxygen Co., Ltd., purity 99.7%) of the nozzle force was set to 20 sccm (flow rate of 20 cm 3 flow per minute). In order to prevent the deposition of excess carbon, a stainless steel shield plate having an opening was placed between the crucible and the water-cooled roller. In the direction of rotation of the roller
  • This opening was 10 mm. A shutter was placed at the opening of this shield to prevent evaporation and adhesion until the evaporation temperature was reached.
  • Electron beam acceleration voltage is 8k
  • the electron beam emission was 150 mA.
  • the degree of vacuum in the vacuum chamber was set to 1.5 ⁇ 10 ⁇ &, and the water-cooled roller was rotated at a speed of lOcmZ.
  • the surface temperature of the water-cooled roller was 20 ° C.
  • composition of the negative electrode active material was quantified by elemental analysis. As a result, the composition of the negative electrode active material was Si o.
  • a battery was produced in the same manner as in Example 5-4 except that the dimensions of the positive electrode and the negative electrode were appropriately changed using such a negative electrode. The obtained battery was used as the battery of Example 5-6.
  • Example 5-6 The batteries of Examples 5-1 and 5-4 to 5-6 were subjected twice to the same preliminary charge and discharge as in Example 1.
  • the charged battery was stored at 45 ° C. for 7 days.
  • the initial discharge capacity, the maximum temperature of the battery surface and the capacity recovery rate were measured in the same manner as in Example 1. The results are shown in Table 5.
  • the batteries of Examples 5-2 and 5-3 were subjected twice to the same preliminary charge and discharge as in Example 1 except that the charge termination voltage was changed to 4.4 V.
  • the charged battery was stored at 45 ° C. for 7 days. Next, the following evaluation was performed about the battery after preservation
  • the battery After storage, the battery was charged at a constant voltage of 4.4 V at 20 ° C. until the current value decreased to 100 mA. Thereafter, the charged battery was placed in a 130 ° C. constant temperature bath, and the maximum temperature of the battery surface was measured. The results are shown in Table 5.
  • the initial discharge capacity was measured as described above. After this, the battery was charged at 20 ° C. with a constant voltage of 4.4 V until the current value decreased to 100 mA. Then, after charging the battery, 90. It was placed in a thermostatic bath C and stored for 24 hours. After storage, the battery was discharged at a constant current of 2000 mA, and the discharge capacity after storage was determined. The ratio of the discharge capacity after storage to the initial discharge capacity as a percentage is taken as the capacity recovery rate. The results are shown in Table 5.
  • Example 5-1 When a mixture containing two lithium-containing composite oxides is used as a positive electrode active material (Example 5-1), when the positive electrode active material is exposed to a high voltage environment (Examples 5-2 to 5-5) — 3), Also in the case of using a high capacity negative electrode active material (Examples 5-4 to 5-6), it is understood that a battery excellent in safety and high temperature storage characteristics can be obtained.
  • the positive electrode active material contains an appropriate amount of aluminum, the main component of the positive electrode active material is obtained even if the chlorine atom contained as an end group in the heat resistant resin contained in the separator is liberated in the non-aqueous electrolyte. It is possible to suppress the elution of the component into the non-aqueous electrolyte. Therefore, it is possible to provide a non-aqueous electrolyte secondary battery having excellent safety and improved high-temperature storage characteristics. Such a battery can be used, for example, as a power source for devices that require excellent battery characteristics even in a high temperature environment.

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Abstract

L’invention concerne une batterie secondaire électrolytique non aqueuse où le séparateur contient une résine résistant à la chaleur ayant un atome de chlore comme groupe terminal et le matériau actif d’électrode positive contient un oxyde complexe contenant du lithium ayant un atome d’aluminium dans la composition. Dans cette batterie secondaire électrolytique non aqueuse, même si l’atome de chlore est libéré dans la solution électrolytique non aqueuse, l’aluminium contenu dans le matériau actif d’électrode positive est dissous de manière sélective dans la solution électrolytique non aqueuse, éliminant ainsi toute dissolution d’autres éléments constitutifs. En conséquence, on peut obtenir une batterie secondaire électrolytique non aqueuse qui est excellente en matière de sécurité et de stockage à haute température.
PCT/JP2006/304597 2005-03-17 2006-03-09 Batterie secondaire électrolytique non aqueuse WO2006098216A1 (fr)

Applications Claiming Priority (2)

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JP2005-076817 2005-03-17
JP2005076817 2005-03-17

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KR102189550B1 (ko) * 2014-06-11 2020-12-11 삼성에스디아이 주식회사 리튬 이차 전지
TWI651271B (zh) * 2016-05-27 2019-02-21 比利時商烏明克公司 小粒徑的鎳鋰金屬複合氧化物粉體的製造方法
CN108878827B (zh) * 2018-06-26 2021-06-25 天能帅福得能源股份有限公司 一种双氧化合物包覆的高镍三元正极材料及其制备方法

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CN101111956A (zh) 2008-01-23
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KR20070103074A (ko) 2007-10-22

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