WO2011071094A1 - Méthode de production d'un oxyde métallique composite du lithium, oxyde métallique composite du lithium et pile secondaire à électrolyte non aqueux - Google Patents

Méthode de production d'un oxyde métallique composite du lithium, oxyde métallique composite du lithium et pile secondaire à électrolyte non aqueux Download PDF

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WO2011071094A1
WO2011071094A1 PCT/JP2010/072070 JP2010072070W WO2011071094A1 WO 2011071094 A1 WO2011071094 A1 WO 2011071094A1 JP 2010072070 W JP2010072070 W JP 2010072070W WO 2011071094 A1 WO2011071094 A1 WO 2011071094A1
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metal oxide
composite metal
lithium composite
secondary battery
discharge capacity
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PCT/JP2010/072070
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English (en)
Japanese (ja)
Inventor
哲 島野
中根　堅次
セドリック ピテル
健二 高森
裕一郎 今成
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住友化学株式会社
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Priority to US13/513,885 priority Critical patent/US9822015B2/en
Priority to CN201080054435.4A priority patent/CN102639443B/zh
Publication of WO2011071094A1 publication Critical patent/WO2011071094A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric 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 method for producing a lithium composite metal oxide, a lithium composite metal oxide, and a nonaqueous electrolyte secondary battery.
  • Lithium composite metal oxides are used as positive electrode active materials for non-aqueous electrolyte secondary batteries such as lithium secondary batteries. Lithium secondary batteries have already been put into practical use as small power sources for cellular phones and laptop computers, and are also being applied to medium and large power sources such as automotive and power storage applications.
  • a method for producing a lithium composite metal oxide a method of firing a mixture obtained by mixing a composite hydroxide containing nickel and cobalt and lithium hydroxide has been proposed (for example, Patent Document 1). Such).
  • a method of firing a mixture obtained by mixing a composite hydroxide containing nickel, cobalt and manganese and lithium hydroxide has also been proposed (for example, Patent Document 2).
  • the average particle diameter of primary particles is 0.17 ⁇ m
  • the BET specific surface area is 4.67 m 2 / g
  • the median diameter of secondary particles is 11 ⁇ m.
  • a lithium composite metal oxide represented by the formula Li 1.05 Ni 0.45 Mn 0.45 Co 0.10 O 2 is described.
  • the lithium composite metal oxide is obtained by spray-drying a slurry containing Ni (OH) 2 , Mn 3 O 4 and Co (OH) 2 to obtain a granulated powder, and the granulated powder and the LiOH powder are mixed. To obtain a mixture and calcining the mixture.
  • JP-A-8-222220 JP 2007-091573 A Japanese Patent Laid-Open No. 2005-141983
  • the non-aqueous electrolyte secondary battery using the lithium composite metal oxide obtained by firing the mixture as described above has a charge / discharge behavior when the discharge capacity is repeatedly charged / discharged (hereinafter sometimes referred to as a cycle behavior).
  • a cycle behavior when the discharge capacity is repeatedly charged / discharged
  • An object of the present invention is to provide a non-aqueous electrolyte secondary battery with improved secondary battery characteristics such as cycle behavior, and to provide a lithium composite metal oxide suitable for the secondary battery and a method for producing the same. That is.
  • the present invention provides the following ⁇ 1> to ⁇ 20>.
  • ⁇ 1> A mixture of one or more compounds of M (wherein M is one or more elements selected from the group consisting of nickel, cobalt and manganese) and a lithium compound, a fluoride of A, A One or more selected from the group consisting of chloride of A, carbonate of A, sulfate of A, nitrate of A, phosphate of A, hydroxide of A, molybdate of A and tungstate of A And a step of firing in the presence of an inert melting agent (wherein A is one or more elements selected from the group consisting of Na, K, Rb, Cs, Ca, Mg, Sr and Ba).
  • a method for producing a lithium composite metal oxide A method for producing a lithium composite metal oxide.
  • ⁇ 2> The method of ⁇ 1>, wherein the produced lithium composite metal oxide is represented by the following formula (1).
  • Li a MO 2 (1) (Here, M represents one or more elements selected from the group consisting of nickel, cobalt and manganese, and 0.9 ⁇ a ⁇ 1.3.)
  • M represents one or more elements selected from the group consisting of nickel, cobalt and manganese, and 0.9 ⁇ a ⁇ 1.3.)
  • ⁇ 3> The method according to ⁇ 1> or ⁇ 2>, wherein the inert melting agent is A carbonate or A chloride or both.
  • ⁇ 4> The method according to any one of ⁇ 1> to ⁇ 3>, wherein A is Na, K, or both.
  • ⁇ 5> The method according to any one of ⁇ 1> to ⁇ 4>, wherein the lithium compound is lithium carbonate.
  • ⁇ 6> The method according to any one of ⁇ 1> to ⁇ 5>, wherein the one or more M compounds are one or more M hydroxides.
  • ⁇ 7> The method according to any one of ⁇ 1> to ⁇ 6>, wherein the inert melting agent is present in an amount of 0.1 to 400 parts by weight with respect to 100 parts by weight of the lithium compound at the start of firing.
  • ⁇ 8> The method according to any one of ⁇ 1> to ⁇ 7>, wherein the firing temperature is in the range of 200 to 1150 ° C.
  • ⁇ 9> The method according to ⁇ 1>, wherein at least one of the M compounds contains nickel, cobalt, and manganese as a whole.
  • ⁇ 13> A lithium composite metal oxide produced by any one of the methods ⁇ 1> to ⁇ 12>.
  • ⁇ 14> Lithium containing nickel, cobalt, and manganese, having a BET specific surface area of 3 m 2 / g or more and 15 m 2 / g or less, and an average particle size determined by a laser diffraction scattering method of 0.1 ⁇ m or more and less than 1 ⁇ m Composite metal oxide.
  • ⁇ 15> The lithium composite metal oxide according to ⁇ 14>, wherein the average primary particle diameter is 0.05 ⁇ m or more and 0.4 ⁇ m or less.
  • the first invention in the present invention is a mixture of one or more compounds of M (where M is one or more elements selected from the group consisting of nickel, cobalt and manganese) and a lithium compound.
  • M is one or more elements selected from the group consisting of nickel, cobalt and manganese
  • the group consisting of A fluoride, A chloride, A carbonate, A sulfate, A nitrate, A phosphate, A hydroxide, A molybdate and A tungstate The presence of one or more inert melting agents selected from (wherein A is one or more elements selected from the group consisting of Na, K, Rb, Cs, Ca, Mg, Sr and Ba). It is a manufacturing method of a lithium composite metal oxide including the process of baking below.
  • the manufactured lithium composite metal oxide preferably has a layered rock salt type crystal structure from the viewpoint of further increasing the discharge capacity of the obtained secondary battery, and more preferably represented by the following formula (1). .
  • Li a MO 2 (1) (Here, M represents one or more elements selected from the group consisting of nickel, cobalt and manganese, and 0.9 ⁇ a ⁇ 1.3.) M is one or more elements selected from the group consisting of nickel, cobalt and manganese. From the viewpoint of further increasing the discharge capacity of the obtained secondary battery, M preferably has nickel. Examples of the combination of M having nickel include (1) nickel, (2) nickel and cobalt, (3) nickel and manganese, and (4) nickel, cobalt and manganese.
  • the output characteristics of the obtained secondary battery are as follows. There is also an effect of higher.
  • M contains manganese, that is, when M is (3) nickel and manganese, and when M is (4) nickel, cobalt and manganese
  • the output characteristics of the obtained secondary battery are as follows. There is also an effect of higher.
  • the molar ratio of nickel to M is preferably 0.3 or more and 0.9 or less.
  • the molar ratio of lithium to M is preferably 0.9 or more and 1.3 or less.
  • the lithium composite metal oxide is represented by the following formula (2).
  • Li a (Ni 1- (x + y) Mn x Co y ) O 2 (2) (Here, 0.9 ⁇ a ⁇ 1.3, 0.3 ⁇ x ⁇ 0.6, 0.01 ⁇ y ⁇ 0.4, and 0.31 ⁇ x + y ⁇ 0.7.)
  • a in order to increase the capacity of the nonaqueous electrolyte secondary battery, a is more preferably 0.95 or more and 1.15 or less.
  • x is 0.35 or more and 0.00 in order to enhance the discharge capacity maintenance characteristics (hereinafter sometimes referred to as cycle characteristics) when the non-aqueous electrolyte secondary battery is repeatedly charged and discharged. More preferably, it is 55 or less.
  • y in order to increase the discharge capacity maintenance rate at a high current rate of the nonaqueous electrolyte secondary battery, y is more preferably 0.03 or more and 0.3 or less, and 0.05 or more and 0.00. Even more preferably, it is 2 or less.
  • the value of x + y in order to increase the capacity and cycle characteristics of the nonaqueous electrolyte secondary battery, is more preferably 0.4 or more and 0.6 or less, and 0.45 or more and 0.55 or less. Even more preferably.
  • Compounds of M are nickel, cobalt and manganese compounds, oxides, hydroxides (including oxyhydroxides, the same shall apply hereinafter), chlorides, carbonates, sulfates, nitrates, oxalic acid Examples thereof include salts and acetates, and hydroxides are preferably used.
  • the compound of M is preferably a composite metal compound containing two or more transition metal elements, that is, two or more selected from the group consisting of nickel, cobalt and manganese.
  • Such a composite metal compound of M can be obtained by coprecipitation.
  • the M composite metal compound that can be obtained by coprecipitation is preferably an M composite metal hydroxide.
  • one or more compounds of M contains nickel, cobalt and manganese as a whole means that one or more compounds of M are compounds containing nickel, cobalt and manganese, or nickel, It consists of two or more compounds containing one or more elements selected from the group consisting of cobalt and manganese, which means that these compounds as a whole contain nickel, cobalt and manganese.
  • a method for producing a nickel-containing composite metal compound (hereinafter sometimes referred to as a nickel-containing composite metal compound), which is a preferred embodiment of the M compound, will be described.
  • the nickel-containing composite metal compound is, for example, a coprecipitate of nickel and one or more elements other than nickel. A coprecipitate is manufactured through a coprecipitation method.
  • the coprecipitation method include a method including the following steps (1) and (2) in this order.
  • the aqueous solution containing nickel and one or more elements other than nickel hereinafter sometimes referred to as transition metal aqueous solution
  • transition metal aqueous solution is used when the element other than nickel is cobalt, manganese, or both. May be an aqueous solution containing nickel and one or more elements selected from the group consisting of cobalt and manganese.
  • the transition metal aqueous solution can be obtained by dissolving compounds such as chlorides, nitrates, acetates, formates and oxalates of the respective transition metal elements in water.
  • compounds such as chlorides, nitrates, acetates, formates and oxalates of the respective transition metal elements in water.
  • these raw materials are acid such as hydrochloric acid, sulfuric acid, nitric acid or an aqueous solution of these acids.
  • aqueous transition metal solution by dissolving in the step (1), as the precipitant, LiOH (lithium hydroxide), NaOH (sodium hydroxide), KOH (potassium hydroxide), Li 2 CO 3 (Lithium carbonate), Na 2 CO 3 (Sodium carbonate), K 2 CO 3 (Potassium carbonate), (NH 4 ) 2 CO 3 (Ammonium carbonate) and (NH 2 ) 2
  • the precipitating agent is preferably an aqueous precipitating agent dissolved in water.
  • step (1) the transition metal aqueous solution and the precipitant are brought into contact with each other by adding a precipitant (including an aqueous precipitant) to the transition metal aqueous solution.
  • a precipitant including an aqueous precipitant
  • examples thereof include a method of adding an aqueous metal solution and a method of adding an aqueous transition metal solution and a precipitant (including an aqueous precipitant) to water.
  • a coprecipitate slurry can be obtained by the above contact.
  • step (2) a coprecipitate is obtained from the coprecipitate slurry.
  • step (2) may be performed by any method, but from the viewpoint of operability, a method by solid-liquid separation such as filtration is preferably used.
  • the coprecipitate can also be obtained by a method of volatilizing the liquid by heating, such as spray drying, using the coprecipitate slurry.
  • the step (2) when the coprecipitate is obtained by solid-liquid separation, the step (2) is preferably the following step (2 ′). (2 ′) A step of solid-liquid separation of the coprecipitate slurry and then washing and drying the obtained solid to obtain a coprecipitate.
  • step (2 ′) by washing, if excessive impurities such as a precipitant and Cl are present in the solid content obtained after the solid-liquid separation, this can be removed.
  • water A water-soluble organic solvent such as alcohol or acetone may be added to the cleaning liquid as necessary.
  • the washing may be performed twice or more. For example, after washing with water, washing with a water-soluble organic solvent as described above may be performed again.
  • drying is performed to obtain a coprecipitate. Drying is usually performed by heat treatment (heating). You may perform ventilation drying, vacuum drying, etc.
  • the coprecipitate obtained by the above method is a nickel-containing composite metal compound.
  • the precipitant is an alkali such as an alkali metal or ammonia
  • the nickel-containing composite metal compound is a nickel-containing composite metal hydroxide.
  • the nickel-containing composite metal compound is preferably a nickel-containing composite metal hydroxide.
  • the lithium compound include lithium oxide, hydroxide, chloride, carbonate, sulfate, nitrate, oxalate, and acetate. Lithium oxides and hydroxides are easily changed to carbonates due to the presence of carbon dioxide in the air, and may be difficult to handle.
  • the lithium compound is preferably a lithium chloride, carbonate, sulfate, or nitrate, and more preferably lithium carbonate.
  • carbonates may inhibit the charge / discharge reaction in the nonaqueous electrolyte secondary battery and cause a reduction in discharge capacity.
  • lithium carbonate is used as the lithium compound.
  • the residual amount of carbonate can be further reduced by baking the mixture in the presence of a specific inert melting agent. The inert melting agent is difficult to react with the mixture during firing.
  • Inert melting agents include A fluoride, A chloride, A carbonate, A sulfate, A nitrate, A phosphate, A hydroxide, A molybdate and A 1 type or more chosen from the group which consists of these tungstates.
  • A is one or more elements selected from the group consisting of Na, K, Rb, Cs, Ca, Mg, Sr and Ba.
  • NaCl (melting point: 801 ° C.), KCl (melting point: 770 ° C.), RbCl (melting point: 718 ° C.), CsCl (melting point: 645 ° C.), CaCl 2 (Melting point: 782 ° C.), MgCl 2 (Melting point: 714 ° C.), SrCl 2 (Melting point: 857 ° C.) and BaCl 2 (Melting point: 963 ° C.).
  • Na 2 CO 3 (Melting point: 854 ° C.), K 2 CO 3 (Melting point: 899 ° C.), Rb 2 CO 3 (Melting point: 837 ° C), Cs 2 CO 3 (Melting point: 793 ° C.), CaCO 3 (Melting point: 825 ° C), MgCO 3 (Melting point: 990 ° C.), SrCO 3 (Melting point: 1497 ° C) and BaCO 3 (Melting point: 1380 ° C.).
  • Na 2 SO 4 (Melting point: 884 ° C.), K 2 SO 4 (Melting point: 1069 ° C.), Rb 2 SO 4 (Melting point: 1066 ° C.), Cs 2 SO 4 (Melting point: 1005 ° C.), CaSO 4 (Melting point: 1460 ° C), MgSO 4 (Melting point: 1137 ° C), SrSO 4 (Melting point: 1605 ° C.) and BaSO 4 (Melting point: 1580 ° C.).
  • NaNO 3 NaNO 3 (Melting point: 310 ° C), KNO 3 (Melting point: 337 ° C), RbNO 3 (Melting point: 316 ° C), CsNO 3 (Melting point: 417 ° C), Ca (NO 3 ) 2 (Melting point: 561 ° C.), Mg (NO 3 ) 2 , Sr (NO 3 ) 2 (Melting point: 645 ° C.) and Ba (NO 3 ) 2 (Melting point: 596 ° C.).
  • Na 2 MoO 4 (Melting point: 698 ° C.), K 2 MoO 4 (Melting point: 919 ° C.), Rb 2 MoO 4 (Melting point: 958 ° C.), Cs 2 MoO 4 (Melting point: 956 ° C.), CaMoO 4 (Melting point: 1520 ° C.), MgMoO 4 (Melting point: 1060 ° C.), SrMoO 4 (Melting point: 1040 ° C.) and BaMoO 4 (Melting point: 1460 ° C.).
  • the inert melting agent is preferably A carbonate or A chloride or both, and A is preferably Na or K or both. That is, the inert melting agent is particularly preferably NaCl, KCl, Na.
  • the inert melting agent is preferably potassium sulfate or sodium sulfate or both It is.
  • the particle shape of the obtained lithium composite metal oxide can be uniformly adjusted. What is necessary is just to select the abundance of an inert melting agent suitably. From the viewpoint of making the particle sizes of the obtained lithium composite metal oxide more uniform, it is preferable that the inert melting agent is present in an amount of 0.1 part by weight or more with respect to 100 parts by weight of the lithium compound at the start of firing. More preferably, it is present in an amount of at least part.
  • the inert melting agent is present in an amount of 400 parts by weight or less with respect to 100 parts by weight of the lithium compound at the start of firing. More preferably it is present.
  • an inert melting agent other than the inert melting agents listed above, for example, NH 4 Cl, NH 4 An ammonium salt such as F may be used in combination.
  • One or more M compounds and a lithium compound are mixed to obtain a mixture. Mixing may be either dry mixing or wet mixing. From the viewpoint of simplicity, dry mixing is preferred.
  • the mixing apparatus examples include a stirring mixer, a V-type mixer, a W-type mixer, a ribbon mixer, a drum mixer, a ball mill, and a Ladige mixer.
  • the inert melting agent may be mixed with the above mixture, and may be mixed together with one or more compounds of M and the lithium compound.
  • a mixture of one or more M compounds and a lithium compound can be fired in the presence of the inert melt.
  • the firing temperature affects the primary particle size, secondary particle size, and BET specific surface area of the resulting lithium composite metal oxide.
  • the firing temperature varies depending on the type of transition metal element used, the type of precipitant, and the type of inert melting agent.
  • the firing temperature is a melting point minus 100 ° C. in consideration of the melting point of the inert melting agent.
  • the melting point is preferably in the range of plus or minus 100 ° C.
  • Specific examples of the firing temperature include a range of 200 ° C. to 1150 ° C., preferably 300 ° C. to 1050 ° C., and more preferably 500 ° C. to 1000 ° C.
  • the firing temperature is obtained from the viewpoint of obtaining a uniform lithium composite oxide. Is preferably in the range of 650 ° C. or more and 950 ° C. or less.
  • an inert melting agent By firing the mixture in the presence of an inert melting agent, the reaction of the mixture is promoted.
  • the residue of the inert melting agent may remain in the fired lithium composite metal oxide, or may be removed by washing with water or the like after firing.
  • washing after firing is usually not performed. However, in the present invention, it is preferable to wash the lithium composite metal oxide after firing using water or the like.
  • the holding time at the firing temperature is usually 0.1 to 20 hours, preferably 0.5 to 10 hours.
  • the rate of temperature rise to the firing temperature is usually 50 to 400 ° C./hour, and the rate of temperature fall from the firing temperature to room temperature is usually 10 to 400 ° C./hour.
  • As the firing atmosphere air, oxygen, nitrogen, argon, or a mixed gas thereof can be used.
  • the lithium composite metal oxide obtained after firing may be pulverized using a ball mill, a jet mill or the like. You may repeat grinding
  • the lithium composite metal oxide can be washed or classified as necessary. With these, it is possible to adjust the bulk density of the lithium composite metal oxide, and the preferred bulk density is 1.0 to 3.5 g / cm. 3 It is.
  • the lithium composite metal oxide produced by the method of the present invention has a high discharge capacity per unit volume in a non-aqueous electrolyte secondary battery.
  • a compound different from the lithium composite metal oxide may be attached to the lithium composite metal oxide of the present invention.
  • the compound a compound containing at least one element selected from the group consisting of B, Al, Ga, In, Si, Ge, Sn, Mg and a transition metal element, preferably B, Al, Mg, Ga, A compound containing one or more elements selected from the group consisting of In and Sn, and more preferably an Al compound.
  • the compound include oxides, hydroxides, oxyhydroxides, carbonates, nitrates, and organic acid salts of the above elements, preferably oxides, hydroxides, and oxyhydroxides. It is. You may use these compounds in mixture. Among these compounds, a particularly preferred compound is alumina. You may heat after adhesion.
  • the second invention in the present invention contains nickel, cobalt and manganese and has a BET specific surface area of 3 m.
  • a lithium composite metal oxide having an average particle size (hereinafter, simply referred to as an average particle size) determined by a laser diffraction scattering method is 0.1 ⁇ m or more and less than 1 ⁇ m.
  • the BET specific surface area of lithium composite metal oxide is 3m 2 / M or less than 15m 2 When exceeding / g, the discharge capacity maintenance rate at a high current rate of the obtained non-aqueous electrolyte secondary battery is not sufficient. In order to further increase the discharge capacity maintenance ratio at a high current rate, the BET specific surface area of the lithium composite metal oxide is 5 m. 2 / G or more is preferable. In order to increase the filling property, preferably 10 m 2 / G or less. When the average particle size of the lithium composite metal oxide is less than 0.1 ⁇ m, the cycle characteristics of the obtained nonaqueous electrolyte secondary battery are not sufficient.
  • the average particle size of the lithium composite metal oxide is 1 ⁇ m or more, the discharge capacity maintenance rate at a high current rate of the obtained nonaqueous electrolyte secondary battery is not sufficient.
  • the average particle size of the lithium composite metal oxide is preferably 0.2 to 0.8 ⁇ m, more preferably 0.3 ⁇ m. ⁇ 0.7 ⁇ m.
  • the average primary particle diameter of the lithium composite metal oxide is preferably 0.05 ⁇ m or more and 0.4 ⁇ m or less, more preferably 0.07 to 0.35 ⁇ m. Even more preferably, it is 0.1 to 0.3 ⁇ m.
  • the lithium composite metal oxide is preferably represented by the following formula (A).
  • a is preferably 0.95 or more and 1.15 or less.
  • x is preferably 0.35 or more and 0.55 or less.
  • y is preferably 0.03 or more and 0.3 or less, and more preferably 0.05 or more and 0.2 or less.
  • the value of x + y is preferably 0.4 or more and 0.6 or less, and more preferably 0.45 or more and 0.55 or less.
  • a part of Co is selected from the group consisting of Al, Mg, Ba, Cu, Ca, Zn, V, Ti, Si, W, Mo, Nb and Zr.
  • the lithium composite metal oxide of the present invention comprises a mixture of primary particles and secondary particles formed by aggregation of the primary particles.
  • the average particle diameter of each of the primary particles and the secondary particles can be determined by observing with an SEM.
  • the average particle diameter of the lithium composite metal oxide composed of a mixture of primary particles and secondary particles formed by aggregation of the primary particles is determined by a laser diffraction scattering method.
  • the lithium composite metal oxide of the present invention is formed by ⁇ -NaFeO. 2 It is preferable to have a type crystal structure, that is, a crystal structure belonging to the R-3m space group.
  • the crystal structure can be identified from a powder X-ray diffraction pattern obtained by powder X-ray diffraction measurement of a lithium composite metal oxide using CuK ⁇ as a radiation source.
  • a compound different from the lithium composite metal oxide may be attached to the lithium composite metal oxide of the present invention as long as the effect of the discharge capacity maintenance rate at a high current rate is not impaired.
  • the compound a compound containing at least one element selected from the group consisting of B, Al, Ga, In, Si, Ge, Sn, Mg and a transition metal element, preferably B, Al, Mg, Ga, A compound containing one or more elements selected from the group consisting of In and Sn, and more preferably an Al compound.
  • the compound include oxides, hydroxides, oxyhydroxides, carbonates, nitrates, and organic acid salts of the above elements, preferably oxides, hydroxides, or oxyhydroxides. It is. You may use these compounds in mixture. Among these compounds, a particularly preferred compound is alumina. You may heat after adhesion. Next, a method for producing the lithium composite metal oxide in the second invention will be described.
  • the lithium composite metal oxide of the second invention can be produced by the first invention described above.
  • the lithium composite metal oxide of the second invention may be produced by the following method.
  • the lithium composite metal oxide of the second invention can be produced by firing a lithium composite metal oxide raw material containing nickel, cobalt, and manganese in a predetermined molar ratio.
  • the lithium composite metal oxide raw material is a mixture of a lithium compound and a transition metal compound raw material containing nickel, cobalt, and manganese.
  • nickel, cobalt and manganese transition metal compound raw materials include mixtures of nickel, cobalt and manganese metal compounds.
  • metal compounds include nickel, cobalt and manganese oxides, hydroxides (hydroxides include oxyhydroxides, the same shall apply hereinafter), chlorides, carbonates, sulfates, nitrates, oxalates, Examples thereof include acetate, and hydroxide is preferable.
  • the metal compound may be a compound containing two or more elements of nickel, cobalt, and manganese.
  • a compound containing two or more elements of nickel, cobalt and manganese can be obtained by coprecipitation, and preferably a hydroxide containing two or more elements selected from the group consisting of nickel, cobalt and manganese. It is a thing.
  • the transition metal compound raw material is more preferably a hydroxide containing nickel, cobalt and manganese.
  • the lithium compound include one or more compounds selected from the group consisting of lithium hydroxide, lithium chloride, lithium nitrate, and lithium carbonate. These lithium compounds may be anhydrides or hydrates. Of these lithium compounds, lithium hydroxide and / or lithium carbonate are preferably used.
  • the mixing method of the lithium compound and the transition metal compound raw material containing nickel, cobalt and manganese may be either dry mixing or wet mixing, and is preferably dry mixing from the viewpoint of simplicity. Examples of the mixing device include stirring and mixing, a V-type mixer, a W-type mixer, a ribbon mixer, a drum mixer, a ball mill, and the like.
  • the lithium composite metal oxide raw material is fired.
  • the raw material and a second inert melting agent may be mixed as necessary.
  • the second inert melting agent is preferably one that does not easily react with the lithium composite metal oxide raw material during firing.
  • the second inert melting agent are preferably NaCl, KCl, NH 4 Chlorides such as Cl, K 2 CO 3 , Na 2 CO 3 Carbonates such as K 2 SO 4 , Na 2 SO 4 Sulfates such as NaF, KF, NH 4
  • fluorides such as F, boric acid and the like, and the chlorides, carbonates and sulfates are more preferable.
  • the reactivity of the raw material may be controlled, and the average particle size and BET specific surface area of the resulting lithium composite metal oxide may be adjustable.
  • Two or more second inert melting agents may be used in combination.
  • the second inert melting agent may remain in the fired lithium composite metal oxide, or may be removed by washing of the fired lithium composite metal oxide or evaporation of the second inert melt agent. May be.
  • the temperature of calcination affects the average particle diameter and BET specific surface area of the obtained lithium composite metal oxide. Usually, the higher the firing temperature, the larger the average particle size tends to be, and the BET specific surface area tends to be smaller.
  • the firing temperature is preferably 650 ° C. or higher and 950 ° C. or lower.
  • the holding time at the baking temperature is usually 0.1 to 20 hours, preferably 0.5 to 8 hours.
  • the rate of temperature rise to the firing temperature is usually 50 to 400 ° C./hour, and the rate of temperature fall from the firing temperature to room temperature is usually 10 to 400 ° C./hour.
  • Examples of the firing atmosphere include air, oxygen, nitrogen, argon, and a mixed gas thereof, and an air atmosphere is preferable.
  • the lithium composite metal oxide obtained after the firing may be pulverized using a ball mill or a jet mill.
  • An electrode can be obtained as follows using a lithium composite metal oxide.
  • the electrode is manufactured by supporting an electrode mixture containing a lithium composite metal oxide, a conductive material and a binder on an electrode current collector.
  • the conductive material include carbon materials.
  • the carbon material include graphite powder, carbon black (for example, acetylene black), fibrous carbon material, and the like.
  • the ratio of the conductive material in the electrode mixture is usually 5 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the lithium composite metal oxide.
  • the conductive material is a fibrous carbon material such as graphitized carbon fiber or carbon nanotube, the ratio can be lowered.
  • binder examples include thermoplastic resins, and specific examples of the thermoplastic resin include polyvinylidene fluoride (hereinafter sometimes referred to as PVdF) and polytetrafluoroethylene (hereinafter referred to as PTFE). ), Fluoropolymers such as tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer, hexafluoropropylene / vinylidene fluoride copolymer, tetrafluoroethylene / perfluorovinyl ether copolymer, Examples thereof include polyolefin resins such as polyethylene and polypropylene. Two or more of these may be mixed and used.
  • Fluorine resin and polyolefin resin may be used as a binder, and the electrode mixture is such that the ratio of the fluorine resin to the electrode mixture is 1 to 10% by weight and the ratio of the polyolefin resin is 0.1 to 2% by weight.
  • the electrode current collector include Al, Ni, and stainless steel, and Al is preferable from the viewpoint of being easily processed into a thin film and being inexpensive.
  • a pressure molding method; or an electrode mixture paste is obtained by further using an organic solvent, and the paste is applied to the electrode current collector and dried.
  • the paste contains a lithium composite metal oxide, a conductive material, a binder, and an organic solvent.
  • organic solvents include amine solvents such as N, N-dimethylaminopropylamine and diethylenetriamine, ether solvents such as tetrahydrofuran, ketone solvents such as methyl ethyl ketone, ester solvents such as methyl acetate, dimethylacetamide, N- Examples thereof include amide solvents such as methyl-2-pyrrolidone (hereinafter sometimes referred to as NMP).
  • Examples of the method of applying the electrode mixture paste to the electrode current collector include a slit die coating method, a screen coating method, a curtain coating method, a knife coating method, a gravure coating method, and an electrostatic spray method.
  • an electrode can be manufactured.
  • Nonaqueous electrolyte secondary battery The electrode of the present invention is extremely useful as a positive electrode in a nonaqueous electrolyte secondary battery.
  • the electrode of the present invention is used as the positive electrode.
  • a nonaqueous electrolyte secondary battery can be manufactured as follows, for example.
  • Non-aqueous electrolyte secondary batteries such as lithium secondary batteries, contain a group of electrodes obtained by laminating or laminating and winding a separator, a negative electrode, a separator and a positive electrode in this order in a battery case such as a battery can. It can be manufactured by injecting an electrolyte into the case.
  • the shape of the electrode group include a shape in which a cross section when the electrode group is cut in a direction perpendicular to the winding axis is a circle, an ellipse, a rectangle, a rectangle with rounded corners, or the like. Can be mentioned.
  • Examples of the shape of the battery include a paper shape, a coin shape, a cylindrical shape, and a square shape.
  • the negative electrode only needs to be capable of being doped with lithium ions and dedoped at a lower potential than the positive electrode.
  • Examples of the negative electrode include an electrode in which a negative electrode mixture containing a negative electrode material is supported on a negative electrode current collector, or an electrode made of a negative electrode material alone.
  • the negative electrode material is a carbon material, a chalcogen compound such as an oxide or sulfide, a nitride, a metal or an alloy, and can be doped with lithium ions and dedoped at a lower potential than the positive electrode. Materials. You may mix and use these negative electrode materials.
  • the negative electrode material is exemplified below.
  • the carbon material include graphite such as natural graphite and artificial graphite, coke, carbon black, pyrolytic carbon, carbon fiber, and polymer fired body.
  • the oxide specifically, SiO 2 , SiO etc. formula SiO x (Wherein x is a positive real number) silicon oxide represented by: TiO 2 TiO, formula TiO x (Where x is a positive real number) titanium oxide; V 2 O 5 , VO 2 Etc. VO x (Where x is a positive real number) oxide of vanadium; Fe 3 O 4 , Fe 2 O 3 FeO and other formulas FeO x (Where x is a positive real number) iron oxide; SnO 2 , SnO etc.
  • Ti 2 S 3 TiS 2 TiS and other formula TiS x (Where x is a positive real number) titanium sulfide; V 3 S 4 , VS 2, VS and other expressions VS x (Where x is a positive real number) Vanadium sulfide; Fe 3 S 4 , FeS 2 FeS and other formulas x (Where x is a positive real number) iron sulfide; Mo 2 S 3 , MoS 2 Etc. MoS x (Where x is a positive real number) molybdenum sulfide; SnS 2, SnS etc.
  • These carbon materials, oxides, sulfides and nitrides may be used in combination of two or more. These may be either crystalline or amorphous. These carbon materials, oxides, sulfides, and nitrides are mainly supported on the negative electrode current collector and used as electrodes.
  • Specific examples of the metal include lithium metal, silicon metal, and tin metal.
  • Examples of the alloy include lithium alloys such as Li—Al, Li—Ni, and Li—Si; silicon alloys such as Si—Zn; Sn—Mn, Sn—Co, Sn—Ni, Sn—Cu, and Sn—La. Tin alloys such as Cu 2 Sb, La 3 Ni 2 Sn 7 And alloys thereof.
  • the negative electrode material is preferably carbon mainly composed of graphite such as natural graphite or artificial graphite.
  • the shape of the carbon material include flakes such as natural graphite, spheres such as mesocarbon microbeads, fibers such as graphitized carbon fibers, and fine powder aggregates.
  • the negative electrode mixture may contain a binder as necessary.
  • a thermoplastic resin is mentioned as a binder. Specific examples of the thermoplastic resin include PVdF, thermoplastic polyimide, carboxymethylcellulose, polyethylene, and polypropylene.
  • Examples of the negative electrode current collector include Cu, Ni, and stainless steel, and Cu is preferable from the viewpoint that it is difficult to form an alloy with lithium and it is easy to process into a thin film.
  • the method of supporting the negative electrode mixture on the negative electrode current collector is the same as in the case of the positive electrode, and is a method by pressure molding; or further using a solvent or the like to obtain a negative electrode mixture paste, and using the paste as the negative electrode current collector Examples thereof include a method of applying to a body, drying, pressing the obtained sheet, and fixing the negative electrode mixture to the current collector.
  • the separator examples include a member made of a material such as a polyolefin resin such as polyethylene or polypropylene, a fluororesin, or a nitrogen-containing aromatic polymer and having a form such as a porous film, a nonwoven fabric, or a woven fabric.
  • the separator may be made of two or more kinds of the materials, or may be a laminated separator in which the members are laminated. Examples of the separator include those described in JP 2000-30686 A, JP 10-324758 A, and the like.
  • the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 5 to 40 ⁇ m, from the viewpoint of increasing the volume energy density of the battery and reducing the internal resistance.
  • the separator is preferably thin as long as the mechanical strength is maintained.
  • the separator preferably has a porous film containing a thermoplastic resin.
  • the separator is disposed between the positive electrode and the negative electrode.
  • the separator preferably has a function of blocking (shutdown) an excessive current from flowing when an abnormal current flows in the battery due to a short circuit between the positive electrode and the negative electrode.
  • the shutdown is performed by closing the micropores of the porous film in the separator when the normal use temperature is exceeded.
  • a separator is a laminated film in which a heat resistant porous layer and a porous film are laminated together.
  • the heat resistant porous layer may be laminated on both surfaces of the porous film.
  • the heat resistant porous layer is a layer having higher heat resistance than the porous film, and the heat resistant porous layer may be formed of an inorganic powder or may contain a heat resistant resin.
  • the heat resistant porous layer contains a heat resistant resin
  • the heat resistant porous layer can be formed by an easy technique such as coating.
  • the heat resistant resin include polyamide, polyimide, polyamideimide, polycarbonate, polyacetal, polysulfone, polyphenylene sulfide, polyether ketone, aromatic polyester, polyether sulfone, and polyetherimide.
  • nitrogen-containing aromatic polymers such as aromatic polyamides (para-oriented aromatic polyamides, meta-oriented aromatic polyamides), aromatic polyimides, aromatic polyamideimides, and particularly preferred are aromatic polyamides and production surfaces.
  • para-oriented aromatic polyamide hereinafter sometimes referred to as para-aramid
  • examples of the heat resistant resin include poly-4-methylpentene-1 and cyclic olefin polymers.
  • the compatibility with the electrolytic solution may be good depending on the polarity in the molecule.
  • the electrolytic solution is retained in the heat-resistant porous layer.
  • rate of electrolyte solution becomes high, and the charge / discharge capacity of a nonaqueous electrolyte secondary battery also increases more.
  • the thermal film breaking temperature of the laminated film depends on the type of heat-resistant resin, and is selected and used according to the use scene and purpose of use. More specifically, as the heat resistant resin, the cyclic olefin polymer is used at about 400 ° C.
  • the thermal film breaking temperature can be controlled to about 300 ° C., respectively.
  • the thermal film breaking temperature can be controlled to 500 ° C. or higher, for example.
  • the para-aramid is obtained by polycondensation of a para-oriented aromatic diamine and a para-oriented aromatic dicarboxylic acid halide, and the amide bond is in the para position of the aromatic ring or an oriented position equivalent thereto (for example, 4,4′-biphenylene, It consists essentially of repeating units that are bound together in an opposite orientation, such as 1,5-naphthalene, 2,6-naphthalene, etc.
  • para-aramid having a structure according to the type.
  • the aromatic polyimide is preferably a wholly aromatic polyimide produced by condensation polymerization of an aromatic dianhydride and a diamine.
  • the dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic And acid dianhydride, 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the like.
  • diamine examples include oxydianiline, paraphenylenediamine, benzophenonediamine, 3,3′-methylenedianiline, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylsulfone, 1,5 -Naphthalene diamine etc. are mentioned.
  • a polyimide soluble in a solvent can be preferably used. Examples of such a polyimide include a polycondensate polyimide of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and an aromatic diamine.
  • aromatic polyamideimide examples include those obtained by condensation polymerization of aromatic dicarboxylic acid and aromatic diisocyanate, and those obtained by condensation polymerization of aromatic diacid anhydride and aromatic diisocyanate.
  • aromatic dicarboxylic acid examples include isophthalic acid and terephthalic acid.
  • aromatic dianhydride examples include trimellitic anhydride.
  • aromatic diisocyanate examples include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, orthotolylene diisocyanate, m-xylene diisocyanate, and the like.
  • the heat-resistant porous layer is preferably thin, specifically, preferably 1 ⁇ m to 10 ⁇ m, more preferably 1 ⁇ m to 5 ⁇ m, and particularly preferably 1 ⁇ m to 4 ⁇ m. It is.
  • the heat-resistant porous layer has fine pores, and the size (diameter) of the pores is usually 3 ⁇ m or less, preferably 1 ⁇ m or less.
  • the heat-resistant porous layer can also contain a filler described later.
  • the porous film in the laminated film has micropores.
  • the porous film preferably has a shutdown function, and in this case, contains a thermoplastic resin.
  • the size (diameter) of the micropores in the porous film is usually 3 ⁇ m or less, preferably 1 ⁇ m or less.
  • the porosity of the porous film is usually 30 to 80% by volume, preferably 40 to 70% by volume.
  • the porous film can close the micropores by softening the thermoplastic resin constituting the porous film.
  • the thermoplastic resin one that does not dissolve in the electrolyte solution in the nonaqueous electrolyte secondary battery is selected.
  • specific examples of such a thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, and thermoplastic polyurethane resins, and two or more thermoplastic resins may be mixed and used.
  • the porous film preferably contains polyethylene.
  • polyethylene include polyethylene such as low density polyethylene, high density polyethylene, and linear polyethylene, and ultrahigh molecular weight polyethylene having a molecular weight of 1,000,000 or more.
  • the porous film preferably contains ultrahigh molecular weight polyethylene.
  • the thermoplastic resin may preferably contain a wax made of polyolefin having a low molecular weight (weight average molecular weight of 10,000 or less).
  • the thickness of the porous film in the laminated film is usually 3 to 30 ⁇ m, preferably 3 to 25 ⁇ m, more preferably 3 to 19 ⁇ m.
  • the thickness of the laminated film is usually 40 ⁇ m or less, preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less.
  • the value of A / B is preferably 0.1 or more and 1 or less.
  • the heat resistant porous layer may contain one or more fillers.
  • the filler may be one or more selected from organic powder, inorganic powder, or a mixture thereof as the material.
  • the particles constituting the filler preferably have an average particle size of 0.01 ⁇ m or more and 1 ⁇ m or less.
  • the organic powder include styrene, vinyl ketone, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, and methyl acrylate, or a copolymer of two or more types; polytetrafluoroethylene, 4 fluorine, and the like.
  • Fluorine resins such as fluorinated ethylene-6 fluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, and polyvinylidene fluoride; melamine resin; urea resin; polyolefin; polymethacrylate; It is done.
  • These organic powders may be used alone or in combination of two or more.
  • polytetrafluoroethylene powder is preferable from the viewpoint of chemical stability.
  • the inorganic powder include powders made of inorganic substances such as metal oxides, metal nitrides, metal carbides, metal hydroxides, carbonates and sulfates. Among these, a powder made of an inorganic material having low conductivity is preferable.
  • preferable inorganic powder include powder made of alumina, silica, titanium dioxide, calcium carbonate, or the like.
  • An inorganic powder may be used independently and may be used in mixture of 2 or more types.
  • alumina powder is preferable from the viewpoint of chemical stability. More preferably, all of the particles constituting the alumina powder are alumina particles, and even more preferably, all of the particles constituting the filler are alumina particles, and some or all of the alumina particles are substantially omitted. It is spherical.
  • the heat-resistant porous layer is formed from an inorganic powder, the inorganic powder exemplified above may be used, and may be mixed with a binder as necessary.
  • the filler content depends on the specific gravity of the filler material.
  • the filler content is usually 5 or more and 95 or less, preferably 20 or more and 95 or less, with respect to the total weight 100 of the heat-resistant porous layer. More preferably, it is 30 or more and 90 or less. These ranges can be appropriately set depending on the specific gravity of the filler material.
  • the shape of the filler include a substantially spherical shape, a plate shape, a columnar shape, a needle shape, a whisker shape, a fiber shape, and the like.
  • the shape is preferably a substantially spherical shape.
  • the substantially spherical particles include particles having a particle aspect ratio (long particle diameter / short particle diameter) of 1 or more and 1.5 or less. The aspect ratio of the particles can be measured by an electron micrograph.
  • the separator preferably has a gas permeability by the Gurley method of 50 to 300 seconds / 100 cc, more preferably 50 to 200 seconds / 100 cc.
  • the separator has a porosity of usually 30 to 80% by volume, preferably 40 to 70% by volume.
  • the separator may be a laminate of separators having different porosity.
  • the electrolytic solution usually contains an electrolyte and an organic solvent.
  • electrolytes include LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiN (SO 2 CF 3 ) (COCF 3 ), Li (C 4 F 9 SO 3 ), LiC (SO 2 CF 3 ) 3 , Li 2 B 10 Cl 10 , LiBOB (where BOB is bis (oxalato) borate), lower aliphatic carboxylic acid lithium salt, LiAlCl 4
  • the lithium salt include two or more kinds of electrolytes.
  • organic solvent examples include propylene carbonate, ethylene carbonate (hereinafter sometimes referred to as EC), dimethyl carbonate (hereinafter sometimes referred to as DMC), diethyl carbonate, and ethyl methyl carbonate (hereinafter, referred to as “ECC”).
  • a mixed solvent in which two or more of these organic solvents are mixed is used.
  • a mixed solvent containing carbonates is preferable, and a mixed solvent of cyclic carbonate and acyclic carbonate or a mixed solvent of cyclic carbonate and ethers is more preferable.
  • the mixed solvent of cyclic carbonate and acyclic carbonate has a wide operating temperature range, excellent load characteristics, and is hardly decomposable even when a graphite material such as natural graphite or artificial graphite is used as the negative electrode active material.
  • a mixed solvent containing EC, DMC and EMC is preferable.
  • LiPF has the advantage of improving safety.
  • an electrolytic solution containing an organic solvent having a fluorine-containing lithium salt and a fluorine substituent is preferable to use.
  • Mixed solvents containing ethers having fluorine substituents such as pentafluoropropyl methyl ether and 2,2,3,3-tetrafluoropropyl difluoromethyl ether and DMC are excellent in large current discharge characteristics, and more preferable.
  • a solid electrolyte may be used instead of the above electrolytic solution.
  • an organic polymer electrolyte such as a polyethylene oxide polymer, a polymer containing at least one of a polyorganosiloxane chain or a polyoxyalkylene chain can be used.
  • a so-called gel type in which an electrolyte is held in a polymer can also be used.
  • An inorganic solid electrolyte containing a sulfide such as may be used. Using these solid electrolytes, safety may be further improved.
  • the solid electrolyte when a solid electrolyte is used, the solid electrolyte may serve as a separator, and in that case, the separator may not be required.
  • the evaluation method of the lithium composite metal oxide, and the production and evaluation methods of the electrode and the nonaqueous electrolyte secondary battery are as follows.
  • the average particle size of the lithium composite metal oxide was determined by a laser diffraction scattering method. Lithium composite metal oxide (powder) (0.1 g) was added to 50 ml of a 0.2 wt% sodium hexametaphosphate aqueous solution, and a dispersion in which the powder was dispersed was used as a measurement sample. Using the measurement sample, the particle size distribution of the powder was measured using a master sizer 2000 (laser diffraction scattering particle size distribution measuring apparatus) manufactured by Malvern, and a volume-based cumulative particle size distribution curve was obtained.
  • master sizer 2000 laser diffraction scattering particle size distribution measuring apparatus manufactured by Malvern
  • the average particle diameter of the lithium composite metal oxide is the particle diameter at the time of 50% accumulation from the fine particle side in the curve (D 50 ).
  • (1-5) Measurement of average primary particle diameter of lithium composite metal oxide A lithium composite metal oxide is placed on a conductive sheet affixed on a sample stage, and an electron beam with an acceleration voltage of 20 kV is irradiated using JSM-5510 manufactured by JEOL Ltd. SEM observation of the constituting primary particles was performed. The average primary particle size was determined by arbitrarily extracting 50 primary particles from an image (SEM photograph) obtained by SEM observation, measuring each particle size, and calculating the average value.
  • Electrode production method 1 As the conductive material, a material in which acetylene black and graphite were mixed at 1: 9 (weight ratio) was used.
  • a binder solution a solution obtained by dissolving PVdF (manufactured by Kureha Co., Ltd., PolyVinylideneDiFluoride) in NMP (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.
  • Lithium composite metal oxide: conductive agent: binder 87: 10: 3 (weight ratio)
  • the lithium composite metal oxide and the conductive material are mixed so as to have a composition, and a binder solution is added thereto, and these are kneaded. As a result, an electrode mixture paste was obtained.
  • Electrode production method 2 As the conductive material, a material in which acetylene black and graphite were mixed at a weight ratio of 9: 1 was used.
  • binder solution a solution obtained by dissolving PVdF (manufactured by Kureha Co., Ltd., PolyVinylideneDiFluoride) in NMP (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.
  • Lithium composite metal oxide: conductive agent: binder 87: 10: 3 (weight ratio)
  • the lithium composite metal oxide and the conductive material are mixed so as to have a composition, and a binder solution is added thereto, and these are kneaded.
  • an electrode mixture paste was obtained.
  • the paste was applied to an Al foil having a thickness of 40 ⁇ m as a current collector and dried at 60 ° C. for 2 hours to obtain an electrode sheet.
  • the electrode sheet is rolled at a pressure of 0.5 MPa, punched into a size of 14.5 mm ⁇ with a punching machine, and vacuum dried at 150 ° C. for 8 hours to obtain an electrode. It was.
  • (3) Preparation of non-aqueous electrolyte secondary battery The electrode obtained by (2-1) or (2-2) was used as the positive electrode.
  • As the separator a laminated film (thickness is 16 ⁇ m) in which a heat-resistant porous layer is laminated on a polyethylene porous film described later is used.
  • Electrolyte 1 was prepared by dissolving the electrolyte in a mixed solvent so as to be 1 mol / liter.
  • Metallic lithium was used as the negative electrode.
  • a positive electrode was placed on the lower lid of a coin cell (manufactured by Hosen Co., Ltd.) with the aluminum foil surface facing downward, a separator was placed thereon, and 300 ⁇ l of electrolyte solution 1 was injected.
  • the negative electrode was placed on the upper side of the separator, the top cover of the coin cell was placed through a gasket, and the resulting product was caulked with a caulking machine to produce a nonaqueous electrolyte secondary battery (coin type battery R2032).
  • the battery was assembled in an argon atmosphere glove box.
  • Lithium composite metal oxide C 101 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide C 101 As a result of the compositional analysis, the molar ratio of Li: Ni: Co was 1.15: 0.85: 0.15. Lithium composite metal oxide C 101 And using the non-aqueous electrolyte secondary battery C as described above 101 was made. Electrode preparation method 1 was selected.
  • Nonaqueous electrolyte secondary battery C 101 A cycle test was conducted to confirm the cycle behavior, and it was confirmed that the discharge capacity at the second cycle was slightly larger than the discharge capacity at the first cycle.
  • Non-aqueous electrolyte secondary battery C 101 When the discharge rate test 1 was performed using the above, the discharge capacities (mAh / g) at 0.2C and 5C were 181 and 28, respectively, and the discharge capacity retention rate (%) at 5C was 15. It was.
  • Example 1-1 ininert melting agent: KCl
  • potassium chloride (KCl) was added to the mixture in Comparative Example 1-1 and mixed.
  • the molar ratio of Li: Ni: Co: KCl in the resulting inert melt-containing mixture was 1.30: 0.85: 0.15: 0.10 (100 parts by weight of lithium compound in the mixture)
  • the amount of the inert melting agent is 15 parts by weight).
  • the mixture is then placed in an alumina firing vessel, fired in an oxygen atmosphere at 650 ° C. for 1 hour, cooled to room temperature, the fired product obtained is pulverized, and then decanted with distilled water. Washing by filtration, filtering, drying at 100 ° C. for 8 hours, lithium composite metal oxide R 101 Got.
  • Lithium composite metal oxide R 101 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 101 As a result of the compositional analysis, the molar ratio of Li: Ni: Co was 1.12: 0.85: 0.15. Lithium composite metal oxide R 101 And using the non-aqueous electrolyte secondary battery R as described above 101 was made. Electrode preparation method 1 was selected. Nonaqueous electrolyte secondary battery R 101 The cycle test was conducted and the cycle behavior was confirmed.
  • Example 1-2 inert melting agent: NaCl
  • NaCl Sodium chloride
  • the molar ratio of Li: Ni: Co: NaCl in the resulting inert melt-containing mixture was 1.30: 0.85: 0.15: 0.10 (100 parts by weight of lithium compound in the mixture)
  • the amount of inert melting agent present is 12 parts by weight).
  • the mixture is then placed in an alumina firing vessel, fired in an oxygen atmosphere at 650 ° C.
  • Lithium composite metal oxide R 102 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 102 As a result of the compositional analysis, the molar ratio of Li: Ni: Co was 1.13: 0.85: 0.15.
  • Lithium composite metal oxide R 102 And using the non-aqueous electrolyte secondary battery R as described above 102 was made. Electrode preparation method 1 was selected. Nonaqueous electrolyte secondary battery R 102 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Example 1-3 in addition to the mixture in Comparative Example 1-1, potassium carbonate (K 2 CO 3 ) was added and mixed.
  • Li: Ni: Co: K in the resulting inert melt-containing mixture 2 CO 3 The molar ratio was 1.30: 0.85: 0.15: 0.10 (in the mixture, the amount of the inert melting agent relative to 100 parts by weight of the lithium compound was 28 parts by weight). .
  • the mixture is then placed in an alumina firing vessel, fired at 650 ° C. for 1 hour in an oxygen atmosphere using an electric furnace, cooled to room temperature, the fired product obtained is pulverized, and then decanted with distilled water. Washing by filtration, filtering, drying at 100 ° C. for 8 hours, lithium composite metal oxide R 103 Got.
  • Lithium composite metal oxide R 103 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 103 As a result of the compositional analysis, the molar ratio of Li: Ni: Co was 1.13: 0.85: 0.15. Lithium composite metal oxide R 103 And using the non-aqueous electrolyte secondary battery R as described above 103 was made. Electrode preparation method 1 was selected. Nonaqueous electrolyte secondary battery R 103 The cycle test was conducted and the cycle behavior was confirmed.
  • Example 1-4 in addition to the mixture in Comparative Example 1-1, potassium carbonate (Na 2 CO 3 ) was added and mixed. Li: Ni: Co: Na in the resulting inert melt-containing mixture 2 CO 3 The molar ratio was 1.30: 0.85: 0.15: 0.10 (the amount of the inert melting agent present in 100 parts by weight of the lithium compound in the mixture was 22 parts by weight). The mixture is then placed in an alumina firing vessel, fired at 650 ° C.
  • Lithium composite metal oxide R 104 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 104 As a result of the compositional analysis, the molar ratio of Li: Ni: Co was 1.10: 0.85: 0.15.
  • Lithium composite metal oxide R 104 And using the non-aqueous electrolyte secondary battery R as described above 104 was made. Electrode preparation method 1 was selected. Nonaqueous electrolyte secondary battery R 104 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed. Comparative Example 1-2 The lithium composite metal oxide C was prepared in the same manner as in Comparative Example 1-1 except that the mixture was placed in an alumina firing container and fired by holding it in an oxygen atmosphere at 750 ° C. for 1 hour using an electric furnace. 102 Got.
  • Lithium composite metal oxide C 102 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide C 102 As a result of the compositional analysis, the molar ratio of Li: Ni: Co was 1.10: 0.85: 0.15. Lithium composite metal oxide C 102 And using the non-aqueous electrolyte secondary battery C as described above 102 was made. Electrode preparation method 1 was selected.
  • Nonaqueous electrolyte secondary battery C 102 When the cycle test was performed and the cycle behavior was confirmed, a behavior was observed in which the discharge capacity at the second cycle was slightly larger than the discharge capacity at the first cycle.
  • Non-aqueous electrolyte secondary battery C 102 When the discharge rate test 1 was conducted using the above, the discharge capacities (mAh / g) at 0.2C and 5C were 93 and 7, respectively, and the discharge capacity retention rate (%) at 5C was 8. It was.
  • Example 1-5 Inert melting agent: Na 2 CO 3
  • the lithium composite metal oxide R was obtained in the same manner as in Example 1-4, except that the mixture was placed in an alumina firing container and fired using an electric furnace at 750 ° C. for 1 hour in an oxygen atmosphere. 105 Got.
  • Lithium composite metal oxide R 105 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 105 As a result of the compositional analysis, the molar ratio of Li: Ni: Co was 1.11: 0.85: 0.15. Lithium composite metal oxide R 105 And using the non-aqueous electrolyte secondary battery R as described above 105 was made. Electrode preparation method 1 was selected. Nonaqueous electrolyte secondary battery R 105 The cycle test was conducted and the cycle behavior was confirmed.
  • a potassium hydroxide aqueous solution was added as an alkali metal aqueous solution and co-precipitated to produce a precipitate, thereby obtaining a slurry.
  • the obtained slurry was subjected to solid-liquid separation and washed with distilled water to obtain a transition metal composite hydroxide.
  • Coprecipitate B dried at 150 ° C 103 Got. Coprecipitate B 103 And lithium carbonate were mixed with a mortar to obtain a mixture. Next, the mixture is placed in an alumina firing container, and fired by holding it at 1000 ° C.
  • Lithium composite metal oxide C 103 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide C 103 As a result of the compositional analysis, the molar ratio of Li: Ni: Mn: Co was 1.15: 0.50: 0.30: 0.20.
  • Lithium composite metal oxide C 103 And using the non-aqueous electrolyte secondary battery C as described above 103 was made.
  • the electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery C 103 A cycle test was conducted to confirm the cycle behavior, and it was confirmed that the discharge capacity at the second cycle was slightly larger than the discharge capacity at the first cycle.
  • Non-aqueous electrolyte secondary battery C 103 When the discharge rate test 1 was performed using, the discharge capacities (mAh / g) at 0.2 C and 5 C were 133 and 85, respectively, and the discharge capacity retention rate (%) at 5 C was 64. It was.
  • Example 1-6 ininert melting agent: K 2 SO 4 ) ⁇ Perform the same operation as in Comparative Example 1-3, 106 Got.
  • the mixture is placed in an alumina firing container and fired by holding it in an air atmosphere at 850 ° C. for 6 hours using an electric furnace, cooled to room temperature to obtain a fired product, pulverized, and distilled water. Wash with decantation, filter, dry at 300 ° C. for 6 hours, and powder lithium composite metal oxide R 106 Got. R 106
  • a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • Lithium composite metal oxide R 106 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.13: 0.50: 0.30: 0.20. Lithium composite metal oxide R 106 And using the non-aqueous electrolyte secondary battery R as described above 106 was made. The electrode production method 2 was selected. Nonaqueous electrolyte secondary battery R 106 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Non-aqueous electrolyte secondary battery R 106 When the discharge rate test 1 was performed using the above, the discharge capacities (mAh / g) at 0.2C and 5C were 170 and 151, respectively, and the discharge capacity retention rate (%) at 5C was 89. The discharge capacity maintenance rate at a high current rate was high.
  • Example 1-7 ininert melting agent: K 2 SO 4 ) Except that the molar ratio of Ni: Mn: Co was 0.60: 0.30: 0.10, the same operation as in Example 1-6 was performed, and the lithium composite metal oxide R 107 Got.
  • Lithium composite metal oxide R 107 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 107 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.10: 0.60: 0.30: 0.10. Lithium composite metal oxide R 107 And using the non-aqueous electrolyte secondary battery R as described above 107 was made. The electrode production method 2 was selected. Nonaqueous electrolyte secondary battery R 107 The cycle test was conducted and the cycle behavior was confirmed.
  • Non-aqueous electrolyte secondary battery R 107 When the discharge rate test 1 was performed using, the discharge capacities (mAh / g) at 0.2C and 5C were 174 and 139, respectively, and the discharge capacity retention rate (%) at 5C was 80. The discharge capacity maintenance rate at a high current rate was high.
  • Example 1-8 ininert melting agent: K 2 SO 4 ) Except that the molar ratio of Ni: Mn: Co was 0.60: 0.20: 0.20, the same operation as in Example 1-6 was performed, and the lithium composite metal oxide R 108 Got.
  • Lithium composite metal oxide R 108 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 108 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.09: 0.60: 0.20: 0.20. Lithium composite metal oxide R 108 And using the non-aqueous electrolyte secondary battery R as described above 108 was made. The electrode production method 2 was selected. Nonaqueous electrolyte secondary battery R 108 The cycle test was conducted and the cycle behavior was confirmed.
  • Non-aqueous electrolyte secondary battery R 108 When the discharge rate test 1 was performed using the above, the discharge capacity (mAh / g) at 0.2C and 5C was 175 and 140, respectively, and the discharge capacity maintenance rate (%) at 5C was 80. The discharge capacity maintenance rate at a high current rate was high.
  • Example 1-9 ininert melting agent: K 2 SO 4 ) Except for the firing temperature of 800 ° C., the same operation as in Example 1-6 was performed, and the lithium composite metal oxide R 109 Got.
  • Lithium composite metal oxide R 109 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 109 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.12: 0.50: 0.30: 0.20. Lithium composite metal oxide R 109 And using the non-aqueous electrolyte secondary battery R as described above 109 was made. The electrode production method 2 was selected. Nonaqueous electrolyte secondary battery R 109 The cycle test was conducted and the cycle behavior was confirmed.
  • Non-aqueous electrolyte secondary battery R 109 The discharge rate test 1 was performed using 0.25, and the discharge capacities (mAh / g) at 0.2C and 5C were 168 and 149, respectively, and the discharge capacity retention rate (%) at 5C was 88. The discharge capacity maintenance rate at a high current rate was high.
  • Example 1-10 ininert melting agent: K 2 SO 4 ) Except that the molar ratio of Ni: Mn: Co was 0.33: 0.34: 0.33, the same operation as in Example 1-6 was performed, and the lithium composite metal oxide R 110 Got.
  • Lithium composite metal oxide R 110 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 110 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.07: 0.33: 0.34: 0.33. Lithium composite metal oxide R 110 And using the non-aqueous electrolyte secondary battery R as described above 110 was made. The electrode production method 2 was selected. Nonaqueous electrolyte secondary battery R 110 The cycle test was conducted and the cycle behavior was confirmed.
  • Non-aqueous electrolyte secondary battery R 110 When the discharge rate test 1 was performed using the above, the discharge capacities (mAh / g) at 0.2C and 5C were 161 and 149, respectively, and the discharge capacity retention rate (%) at 5C was 92. The discharge capacity maintenance rate at a high current rate was high.
  • Example 1-11 ininert melting agent: K 2 CO 3 ) Except that potassium carbonate was used as the inert melting agent, the same operation as in Example 1-6 was performed, and the lithium composite metal oxide R 111 Got.
  • Lithium composite metal oxide R 111 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 111 As a result of the compositional analysis, the molar ratio of Li: Ni: Mn: Co was 1.11: 0.50: 0.30: 0.20. Lithium composite metal oxide R 111 And using the non-aqueous electrolyte secondary battery R as described above 111 was made. The electrode production method 2 was selected. Nonaqueous electrolyte secondary battery R 111 The cycle test was conducted and the cycle behavior was confirmed.
  • Non-aqueous electrolyte secondary battery R 111 When the discharge rate test 1 was performed using the above, the discharge capacities (mAh / g) at 0.2C and 5C were 167 and 149, respectively, and the discharge capacity retention rate (%) at 5C was 89. The discharge capacity maintenance rate at a high current rate was high.
  • Example 1-12 ininert melting agent: K 2 CO 3 ) Except that the molar ratio of Ni: Mn: Co was 0.33: 0.34: 0.33, the same operation as in Example 1-11 was performed, and the lithium composite metal oxide R 112 Got.
  • Lithium composite metal oxide R 112 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 112 As a result of the compositional analysis, the molar ratio of Li: Ni: Mn: Co was 1.11: 0.33: 0.34: 0.33. Lithium composite metal oxide R 112 And using the non-aqueous electrolyte secondary battery R as described above 112 was made. The electrode production method 2 was selected. Nonaqueous electrolyte secondary battery R 112 The cycle test was conducted and the cycle behavior was confirmed.
  • Non-aqueous electrolyte secondary battery R 112 When the discharge rate test 1 was performed using, the discharge capacities (mAh / g) at 0.2C and 5C were 160 and 140, respectively, and the discharge capacity retention rate (%) at 5C was 88. The discharge capacity maintenance rate at a high current rate was high.
  • Example 1-13 ininert melting agent: K 2 CO 3 ) Except that the molar ratio of Ni: Mn: Co was 0.60: 0.30: 0.10, the same operation as in Example 1-11 was performed, and the lithium composite metal oxide R 113 Got.
  • Lithium composite metal oxide R 113 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 113 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.10: 0.60: 0.30: 0.10. Lithium composite metal oxide R 113 And using the non-aqueous electrolyte secondary battery R as described above 113 Was made. The electrode production method 2 was selected. Nonaqueous electrolyte secondary battery R 113 The cycle test was conducted and the cycle behavior was confirmed.
  • Non-aqueous electrolyte secondary battery R 113 When the discharge rate test 1 was performed using, the discharge capacities (mAh / g) at 0.2C and 5C were 174 and 139, respectively, and the discharge capacity retention rate (%) at 5C was 80. The discharge capacity maintenance rate at a high current rate was high.
  • Example 1-14 ininert melting agent: K 2 CO 3 ) Except that the molar ratio of Ni: Mn: Co was 0.60: 0.20: 0.20, the same operation as in Example 1-11 was performed, and the lithium composite metal oxide R 114 Got.
  • Lithium composite metal oxide R 114 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern. Lithium composite metal oxide R 114 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.09: 0.60: 0.20: 0.20. Lithium composite metal oxide R 114 And using the non-aqueous electrolyte secondary battery R as described above 114 was made. The electrode production method 2 was selected. Nonaqueous electrolyte secondary battery R 114 The cycle test was conducted and the cycle behavior was confirmed.
  • Non-aqueous electrolyte secondary battery R 114 When the discharge rate test 1 was performed using, the discharge capacity (mAh / g) at 0.2C and 5C were 177 and 143, respectively, and the discharge capacity maintenance rate (%) at 5C was 80. The discharge capacity maintenance rate at a high current rate was high.
  • Example 1-15 (inert melting agent: K 2 SO 4 ) Nickel sulfate hexahydrate as the water-soluble salt of nickel, manganese sulfate monohydrate as the water-soluble salt of manganese, cobalt sulfate heptahydrate as the water-soluble salt of cobalt, and the molar ratio of Ni: Mn: Co is 0.33: 0.34: 0.33 were each weighed and dissolved in pure water to obtain a transition metal aqueous solution containing Ni, Mn and Co. Further, an aqueous ammonium sulfate solution was used as a complexing agent, and an aqueous sodium hydroxide solution was used as an alkali metal aqueous solution.
  • the transition metal aqueous solution, the complexing agent, and the alkali metal aqueous solution were simultaneously introduced into the reaction tank to perform coprecipitation, thereby generating a precipitate, thereby obtaining a coprecipitate slurry.
  • the amount of sodium hydroxide aqueous solution was adjusted so that the pH in the reaction vessel was maintained at 12, and the temperature in the reaction vessel was adjusted to 45 ° C.
  • the inside of the reaction vessel was stirred with a stirring blade.
  • the obtained coprecipitate slurry is subjected to solid-liquid separation and washed with distilled water to obtain a transition metal composite hydroxide, which is dried at 100 ° C. to obtain a coprecipitate Q. 115 Got.
  • Coprecipitate Q 115 Lithium hydroxide monohydrate and potassium sulfate were mixed with a mortar to obtain a mixture. Next, the mixture is put into an alumina firing vessel, and fired by holding it in an air atmosphere at 800 ° C. for 6 hours using an electric furnace, cooled to room temperature to obtain a fired product, pulverized, distilled water Wash with decantation, filter, dry at 300 ° C. for 6 hours, and powder lithium composite metal oxide R 115 Got. R 115 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • Powder R 115 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.09: 0.33: 0.34: 0.33. Lithium composite metal oxide R 115 And using the non-aqueous electrolyte secondary battery R as described above 115 was made. The electrode production method 2 was selected. Nonaqueous electrolyte secondary battery R 115 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Non-aqueous electrolyte secondary battery R 115 When the discharge rate test 1 was performed using the above, the discharge capacities (mAh / g) at 0.2C and 5C were 154 and 127, respectively, and the discharge capacity retention rate (%) was 82 and high. The discharge capacity maintenance rate at the current rate was high.
  • Example 1-16 ininert melting agent: K 2 SO 4 ) Except that the molar ratio of Ni: Mn: Co was 0.47: 0.48: 0.05, the same operation as in Example 1-6 was performed, and the powdered lithium composite metal oxide R 116 Got.
  • R 116 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 116 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.05: 0.47: 0.48: 0.05, and the BET specific surface area was 8.1 m. 2 / G.
  • the R 211 The average particle size was 0.2 ⁇ m, and the average primary particle size was 0.2 ⁇ m.
  • Lithium composite metal oxide R 116 And using the non-aqueous electrolyte secondary battery R as described above 116 Was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 116 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed. Non-aqueous electrolyte secondary battery R 116 When the discharge rate test 1 was performed using, the discharge capacities (mAh / g) at 0.2C and 5C were 149 and 133, respectively, and the discharge capacity retention rate (%) at 5C was 89. The discharge capacity maintenance rate at a high current rate was high.
  • Example 1-17 (inert melting agent: K 2 SO 4 ) Except that the molar ratio of Ni: Mn: Co was 0.40: 0.50: 0.10, the same operation as in Example 1-6 was performed, and the powdered lithium composite metal oxide R 117 Got.
  • R 117 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • the molar ratio of Li: Ni: Mn: Co is 1.04: 0.40: 0.50: 0.10, and the BET specific surface area is 8.4 m. 2 / G.
  • the R 117 The average particle size was 0.2 ⁇ m, and the average primary particle size was 0.2 ⁇ m. Lithium composite metal oxide R 117 And using the non-aqueous electrolyte secondary battery R as described above 117 was made. The electrode production method 2 was selected. Nonaqueous electrolyte secondary battery R 117 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Non-aqueous electrolyte secondary battery R 117 When the discharge rate test 1 was performed using the above, the discharge capacities (mAh / g) at 0.2C and 5C were 152 and 137, respectively, and the discharge capacity retention rate (%) at 5C was 90. The discharge capacity maintenance rate at a high current rate was high.
  • the transition metal aqueous solution, the complexing agent, and the alkali metal aqueous solution were simultaneously introduced into the reaction tank to perform coprecipitation, thereby generating a precipitate, thereby obtaining a coprecipitate slurry.
  • the amount of sodium hydroxide aqueous solution was adjusted so that the pH in the reaction vessel was maintained at 12, and the temperature in the reaction vessel was adjusted to 45 ° C.
  • the inside of the reaction vessel was stirred with a stirring blade.
  • the obtained coprecipitate slurry is subjected to solid-liquid separation and washed with distilled water to obtain a transition metal composite hydroxide, which is dried at 100 ° C. to obtain a coprecipitate B. 201 Got.
  • B 201 And lithium hydroxide monohydrate were mixed with a mortar to obtain a mixture.
  • the mixture is put into an alumina firing vessel, and fired by holding it in an air atmosphere at 800 ° C. for 6 hours using an electric furnace, cooled to room temperature to obtain a fired product, pulverized, distilled water Wash with decantation, filter, dry at 300 ° C. for 6 hours, and powder lithium composite metal oxide C 201 Got.
  • C 201 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • Non-aqueous electrolyte secondary battery C 201 When the discharge rate test 2 was performed using, the discharge capacities (mAh / g) at 0.2C and 10C were 154 and 91, respectively, and the discharge capacity retention rate (%) at 10C was 59. It was. Comparative Example 2-2 The same operation as in Comparative Example 2-1 was performed except that the molar ratio of Ni: Mn: Co was 0.33: 0.34: 0.33. 202 And the same operation as in Comparative Example 2-1 was performed to obtain a powdered lithium composite metal oxide C. 202 Got.
  • C 202 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • C 202 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.05: 0.33: 0.34: 0.33, and the BET specific surface area was 0.4 m. 2 / G.
  • the R 2 The average particle size of was 9.1 ⁇ m, and the average primary particle size was 1.5 ⁇ m.
  • Lithium composite metal oxide C 202 And using the non-aqueous electrolyte secondary battery C as described above 202 Was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery C 202 A cycle test was conducted to confirm the cycle behavior, and it was confirmed that the discharge capacity at the second cycle was slightly larger than the discharge capacity at the first cycle.
  • Non-aqueous electrolyte secondary battery C 202 When discharge rate test 2 was performed using the above, the discharge capacities (mAh / g) at 0.2C and 10C were 158 and 101, respectively, and the discharge capacity retention rate (%) at 10C was 64. It was.
  • Example 2-A Nickel sulfate hexahydrate is used as the water-soluble salt of nickel, manganese sulfate monohydrate is used as the water-soluble salt of manganese, cobalt sulfate heptahydrate is used as the water-soluble salt of cobalt, and the molar ratio of Ni: Mn: Co is Each was weighed so as to be 0.50: 0.30: 0.20 and dissolved in pure water to obtain a transition metal aqueous solution containing Ni, Mn and Co. To this transition metal aqueous solution, a potassium hydroxide aqueous solution was added as an alkali metal aqueous solution to perform coprecipitation to produce a precipitate, thereby obtaining a coprecipitate slurry.
  • coprecipitate slurry was subjected to solid-liquid separation and washed with distilled water to obtain a transition metal composite hydroxide.
  • Coprecipitate Q after drying at 150 ° C 20A Got. Q 20A And lithium carbonate and potassium sulfate as an inert melting agent were mixed with a mortar to obtain a mixture.
  • the mixture is then placed in an alumina firing vessel and fired at 1000 ° C. for 6 hours in an air atmosphere using an electric furnace, cooled to room temperature to obtain a fired product, pulverized, and distilled water. Wash with decantation, filter, dry at 300 ° C. for 6 hours, and powder lithium composite metal oxide R 20A Got.
  • R 20A As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 20A As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co is 1.10: 0.50: 0.30: 0.20, and the BET specific surface area is 0.3 m. 2 / G.
  • the R 20A The average particle size was 4.2 ⁇ m, and the average primary particle size was 3.2 ⁇ m.
  • Lithium composite metal oxide R 20A And using the non-aqueous electrolyte secondary battery R as described above 20A Was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 20A The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Non-aqueous electrolyte secondary battery R 20A When the discharge rate test 2 was performed using the above, the discharge capacities (mAh / g) at 0.2C and 10C were 138 and 54, respectively, and the discharge capacity retention rate (%) at 10C was 39. It was. Comparative Example 2-3 The same operation as in Example 2-A was carried out except that the molar ratio of Ni: Mn: Co was 0.33: 0.34: 0.33. 203 Got.
  • Non-aqueous electrolyte secondary battery C 203 When the discharge rate test 2 was performed using the above, the discharge capacities (mAh / g) at 0.2C and 10C were 141 and 59, respectively, and the discharge capacity retention rate (%) at 10C was 42. It was.
  • Example 2-B Using nickel sulfate hexahydrate as the water-soluble salt of nickel and manganese sulfate monohydrate as the water-soluble salt of manganese, the molar ratio of Ni: Mn is 0.70: 0.30, and the firing temperature is Except that the temperature was 850 ° C., the same operation as in Example 2-A was performed, and the powdered lithium composite metal oxide R 20B Got.
  • R 20B As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 20B As a result of the composition analysis, the molar ratio of Li: Ni: Mn was 1.10: 0.70: 0.30, and the BET specific surface area was 6.9 m. 2 / G.
  • the R 20B The average particle size was 0.2 ⁇ m, and the average primary particle size was 0.2 ⁇ m.
  • Lithium composite metal oxide R 20B And using the non-aqueous electrolyte secondary battery R as described above 20B Was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 20B The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Non-aqueous electrolyte secondary battery R 20B When discharge rate test 2 was performed using the above, the discharge capacities (mAh / g) at 0.2C and 10C were 80 and 3, respectively, and the discharge capacity retention rate (%) at 10C was 4. It was.
  • Example 2-C Co-precipitate Q as in Comparative Example 2-2 20C Got. Coprecipitate Q 20C And lithium carbonate and potassium sulfate as an inert melting agent were mixed with a mortar to obtain a mixture.
  • the mixture is placed in an alumina firing container and fired by holding it in an air atmosphere at 850 ° C. for 6 hours using an electric furnace, cooled to room temperature to obtain a fired product, pulverized, and distilled water. Wash with decantation, filter, dry at 300 ° C. for 6 hours, and powder lithium composite metal oxide R 20C Got. R 20C
  • a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • Non-aqueous electrolyte secondary battery R 20C When the discharge rate test 2 was performed using the above, the discharge capacities (mAh / g) at 0.2C and 10C were 152 and 94, respectively, and the discharge capacity retention rate (%) at 10C was 62. It was.
  • the powder After weighing out to 03, the powder was obtained by grinding and mixing for 4 hours (peripheral speed 0.7 m / s) by a dry ball mill using 15 mm ⁇ alumina balls as media.
  • This powder was put into a tunnel-type continuous furnace and fired in air at 1040 ° C. for 4 hours to obtain a fired product.
  • the fired product is pulverized for 7 hours (peripheral speed 0.7 m / s) with a dry-type ball mill using 15 mm ⁇ alumina balls as media, and coarse particles are removed with a sieve having a mesh opening of 45 ⁇ m.
  • Product S was obtained.
  • a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • the molar ratio of Li: Ni: Mn: Co is 1.04: 0.35: 0.44: 0.21, and the BET specific surface area is 3.3 m. 2 / G.
  • the average particle size of the S was 1.3 ⁇ m, and the average primary particle size was 1.3 ⁇ m.
  • Example 2-1 Except that the molar ratio of Ni: Mn: Co was 0.50: 0.30: 0.20, the same operation as in Example 2-B was performed, and the powdered lithium composite metal oxide R 201 Got.
  • R 201 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 201 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.13: 0.50: 0.30: 0.20, and the BET specific surface area was 6.0 m. 2 / G.
  • the R 201 The average particle size was 0.2 ⁇ m, and the average primary particle size was 0.2 ⁇ m.
  • Lithium composite metal oxide R 201 And using the non-aqueous electrolyte secondary battery R as described above 201 was made.
  • the electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 201 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Non-aqueous electrolyte secondary battery R 201 When the discharge rate test 2 was performed using, the discharge capacities (mAh / g) at 0.2 C and 10 C were 170 and 138, respectively, and the discharge capacity retention rate (%) at 10 C was 82. The discharge capacity and the discharge capacity maintenance rate were high.
  • Example 2-2 Except that the molar ratio of Ni: Mn: Co was 0.60: 0.30: 0.10, the same operation as in Example 2-1 was performed, and the powdered lithium composite metal oxide R 202 Got. R 202 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • Non-aqueous electrolyte secondary battery R 202 When the discharge rate test 2 was performed using, the discharge capacities (mAh / g) at 0.2C and 10C were 174 and 124, respectively, and the discharge capacity retention rate (%) at 10C was 71. The discharge capacity and the discharge capacity maintenance rate were high.
  • Example 2-3 Except that the molar ratio of Ni: Mn: Co was 0.60: 0.20: 0.20, the same operation as in Example 2-1 was performed, and the powdered lithium composite metal oxide R 203 Got. R 203 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • Non-aqueous electrolyte secondary battery R 203 When the discharge rate test 2 was performed using, the discharge capacities (mAh / g) at 0.2 C and 10 C were 175 and 124, respectively, and the discharge capacity retention rate (%) at 10 C was 71. The discharge capacity and the discharge capacity maintenance rate were high.
  • Example 2-4 The same procedure as in Example 2-1 was performed except that the molar ratio of Ni: Mn: Co was 0.50: 0.30: 0.20 and the firing temperature was 800 ° C. Lithium composite metal oxide R 204 Got.
  • R 204 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 204 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.12: 0.50: 0.30: 0.20, and the BET specific surface area was 6.3 m. 2 / G. In addition, the B 4 The average particle size was 0.2 ⁇ m, and the average primary particle size was 0.2 ⁇ m. Lithium composite metal oxide R 204 And using the non-aqueous electrolyte secondary battery R as described above 204 was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 204 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Non-aqueous electrolyte secondary battery R 204 When the discharge rate test 2 was performed using, the discharge capacities (mAh / g) at 0.2C and 10C were 168 and 121, respectively, and the discharge capacity retention rate (%) at 10C was 72. The discharge capacity and the discharge capacity maintenance rate were high.
  • Example 2-5 Except that the molar ratio of Ni: Mn: Co was 0.33: 0.34: 0.33, the same operation as in Example 2-1 was performed, and the powdered lithium composite metal oxide R 205 Got.
  • R 205 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 205 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.07: 0.33: 0.34: 0.33, and the BET specific surface area was 6.1 m. 2 / G.
  • the R 205 The average particle size was 0.3 ⁇ m, and the average primary particle size was 0.2 ⁇ m.
  • Lithium composite metal oxide R 205 And using the non-aqueous electrolyte secondary battery R as described above 205 Was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 205 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Non-aqueous electrolyte secondary battery R 205 When the discharge rate test 2 was performed using, the discharge capacities (mAh / g) at 0.2C and 10C were 161 and 129, respectively, and the discharge capacity retention rate (%) at 10C was 80. The discharge capacity and the discharge capacity retention rate were high.
  • Example 2-6 Except that the inert flux was potassium carbonate, the same operation as in Example 2-1 was performed, and the powdered lithium composite metal oxide R 206 Got.
  • R 206 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 206 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co is 1.11: 0.50: 0.30: 0.20, and the BET specific surface area is 5.9 m. 2 / G.
  • the R 206 The average particle size was 0.2 ⁇ m, and the average primary particle size was 0.2 ⁇ m.
  • Lithium composite metal oxide R 206 And using the non-aqueous electrolyte secondary battery R as described above 206 Was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 206 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Non-aqueous electrolyte secondary battery R 206 When the discharge rate test 2 was performed using, the discharge capacities (mAh / g) at 0.2 C and 10 C were 167 and 140, respectively, and the discharge capacity retention rate (%) at 10 C was 83. The discharge capacity and the discharge capacity maintenance rate were high.
  • Example 2-7 Except that the molar ratio of Ni: Mn: Co was 0.33: 0.34: 0.33, the same operation as in Example 2-6 was performed, and the powdered lithium composite metal oxide R 207 Got.
  • R 207 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 207 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.11: 0.33: 0.34: 0.33, and the BET specific surface area was 5.6 m. 2 / G.
  • the R 207 The average particle size was 0.6 ⁇ m, and the average primary particle size was 0.2 ⁇ m. Lithium composite metal oxide R 207 And using the non-aqueous electrolyte secondary battery R as described above 207 was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 207 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Non-aqueous electrolyte secondary battery R 207 When the discharge rate test 2 was performed using, the discharge capacities (mAh / g) at 0.2C and 10C were 160 and 130, respectively, and the discharge capacity retention rate (%) at 10C was 81. The discharge capacity and the discharge capacity maintenance rate were high.
  • Example 2-8 Except that the molar ratio of Ni: Mn: Co was 0.60: 0.30: 0.10, the same operation as in Example 2-6 was performed, and the powdered lithium composite metal oxide R 208 Got.
  • R 208 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 208 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.10: 0.60: 0.30: 0.10, and the BET specific surface area was 5.1 m. 2 / G.
  • the R 208 The average particle size was 0.2 ⁇ m, and the average primary particle size was 0.2 ⁇ m.
  • Lithium composite metal oxide R 208 And using the non-aqueous electrolyte secondary battery R as described above 208 Was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 208 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed. Non-aqueous electrolyte secondary battery R 208 When the discharge rate test 2 was performed using, the discharge capacities (mAh / g) at 0.2C and 10C were 174 and 121, respectively, and the discharge capacity retention rate (%) at 10C was 70. The discharge capacity and the discharge capacity maintenance rate were high. Example 2-9 Except that the molar ratio of Ni: Mn: Co was 0.60: 0.20: 0.20, the same operation as in Example 2-6 was performed, and the powdered lithium composite metal oxide R 209 Got.
  • R 209 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 209 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.09: 0.60: 0.20: 0.20, and the BET specific surface area was 3.5 m. 2 / G.
  • the R 209 The average particle size was 0.2 ⁇ m, and the average primary particle size was 0.2 ⁇ m.
  • Lithium composite metal oxide R 209 And using the non-aqueous electrolyte secondary battery R as described above 209 Was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 209 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed. Non-aqueous electrolyte secondary battery R 209 When the discharge rate test 2 was performed using, the discharge capacities (mAh / g) at 0.2C and 10C were 177 and 125, respectively, and the discharge capacity retention rate (%) at 10C was 71. The discharge capacity and the discharge capacity maintenance rate were high. Example 2-10 Except that the molar ratio of Ni: Mn: Co was 0.50: 0.40: 0.10, the same operation as in Example 2-1 was performed, and the powdered lithium composite metal oxide R 210 Got.
  • R 210 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 210 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co is 1.08: 0.50: 0.40: 0.10, and the BET specific surface area is 8.0 m. 2 / G.
  • the R 210 The average particle size was 0.2 ⁇ m, and the average primary particle size was 0.2 ⁇ m.
  • Lithium composite metal oxide R 210 And using the non-aqueous electrolyte secondary battery R as described above 210 Was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 210 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Non-aqueous electrolyte secondary battery R 210 When the discharge rate test 2 was performed using, the discharge capacities (mAh / g) at 0.2 C and 10 C were 168 and 122, respectively, and the discharge capacity retention rate (%) at 10 C was 73. The discharge capacity and the discharge capacity maintenance rate were high.
  • Example 2-11 Except that the molar ratio of Ni: Mn: Co was 0.47: 0.48: 0.05, the same operation as in Example 2-1 was performed, and the powdered lithium composite metal oxide R 211 Got.
  • R 211 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 211 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co was 1.05: 0.47: 0.48: 0.05, and the BET specific surface area was 8.1 m. 2 / G.
  • the R 211 The average particle size was 0.2 ⁇ m, and the average primary particle size was 0.2 ⁇ m.
  • Lithium composite metal oxide R 211 And using the non-aqueous electrolyte secondary battery R as described above 211 Was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 211 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed.
  • Non-aqueous electrolyte secondary battery R 211 When the discharge rate test 2 was performed using, the discharge capacities (mAh / g) at 0.2 C and 10 C were 149 and 117, respectively, and the discharge capacity retention rate (%) at 10 C was 79. The discharge capacity and the discharge capacity maintenance rate were high.
  • Example 2-12 Except that the molar ratio of Ni: Mn: Co was 0.40: 0.50: 0.10, the same operation as in Example 2-1 was performed, and the powdered lithium composite metal oxide R 212 Got.
  • R 212 As a result of the powder X-ray diffraction measurement, a peak of the lithium composite metal oxide belonging to the R-3m space group having a layered rock salt type crystal structure was confirmed in the powder X-ray diffraction pattern.
  • R 212 As a result of the composition analysis, the molar ratio of Li: Ni: Mn: Co is 1.04: 0.40: 0.50: 0.10, and the BET specific surface area is 8.4 m. 2 / G.
  • the R 212 The average particle size was 0.2 ⁇ m, and the average primary particle size was 0.2 ⁇ m.
  • Lithium composite metal oxide R 212 And using the non-aqueous electrolyte secondary battery R as described above 212 Was made. The electrode production method 2 was selected.
  • Nonaqueous electrolyte secondary battery R 212 The cycle test was conducted and the cycle behavior was confirmed. The discharge capacity in the first cycle and the discharge capacity in the second cycle were almost the same, and the discharge capacity monotonously decreased even after repeated cycles. The problem was not confirmed. Non-aqueous electrolyte secondary battery R 212 When the discharge rate test 2 was performed using the above, the discharge capacities (mAh / g) at 0.2C and 10C were 152 and 110, respectively, and the discharge capacity retention rate (%) at 10C was 72. The discharge capacity and the discharge capacity maintenance rate were high.
  • Production Example 1 (Production of laminated film) (1) Production of coating slurry After dissolving 272.7 g of calcium chloride in 4200 g of NMP, 132.9 g of paraphenylenediamine was added thereto and completely dissolved. To the obtained solution, 243.3 g of terephthalic acid dichloride was gradually added for polymerization to obtain para-aramid, and further diluted with NMP to obtain a para-aramid solution (A) having a concentration of 2.0% by weight.
  • alumina powder (a) (Nippon Aerosil Co., Ltd., Alumina C, average particle size 0.02 ⁇ m) and alumina powder (b) 2 g (Sumitomo Chemical Co., Ltd. Sumiko Random, AA03, average particle) 4 g in total as a filler was added and mixed, treated three times with a nanomizer, further filtered through a 1000 mesh wire net and degassed under reduced pressure to produce a coating slurry (B).
  • the weight of alumina powder (filler) with respect to the total weight of para-aramid and alumina powder is 67% by weight.
  • porous film As the porous film, a polyethylene porous film (film thickness 12 ⁇ m, air permeability 140 sec / 100 cc, average pore diameter 0.1 ⁇ m, porosity 50%) was used.
  • the polyethylene porous film was fixed on a PET film having a thickness of 100 ⁇ m, and the coating slurry (B) was applied onto the porous film with a bar coater manufactured by Tester Sangyo Co., Ltd.
  • the PET film and the coated porous film are integrated and immersed in water to precipitate a para-aramid porous film (heat resistant porous layer), and then the solvent is dried to form the heat resistant porous layer and the porous film.
  • a laminated film 1 laminated with a film was obtained.
  • the thickness of the laminated film 1 was 16 ⁇ m, and the thickness of the para-aramid porous film (heat resistant porous layer) was 4 ⁇ m.
  • the air permeability of the laminated film 1 was 180 seconds / 100 cc, and the porosity was 50%.
  • SEM scanning electron microscope
  • Porosity (volume%) 100 ⁇ ⁇ 1 ⁇ (W1 / true specific gravity 1 + W2 / true specific gravity 2 + ⁇ + Wn / true specific gravity n) / (10 ⁇ 10 ⁇ D) ⁇
  • a nonaqueous electrolyte secondary battery with improved secondary battery characteristics such as cycle behavior can be provided. Furthermore, a non-aqueous electrolyte secondary battery exhibiting a high discharge capacity maintenance rate at a high current rate can also be obtained. It is extremely useful for non-aqueous electrolyte secondary batteries for power tools such as power tools.

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Abstract

La présente invention concerne : une méthode de production d'un oxyde métallique composite du lithium ; un oxyde métallique composite du lithium ; et une pile secondaire à électrolyte non aqueux. La méthode comprend une étape de calcination d'un mélange d'un composé du lithium et d'un ou de plusieurs composés de M (M représente un ou plusieurs éléments choisis dans le groupe constitué par le nickel, le cobalt et le manganèse) en présence d'un ou de plusieurs agents de fusion inertes choisis dans le groupe constitué par les fluorures de A, les chlorures de A, les carbonates de A, les sulfates de A, les nitrates de A, les phosphates de A, les hydroxydes de A, les molybdates de A et les tungstates de A (A représente un ou plusieurs éléments choisis dans le groupe constitué par Na, K, Rb, Cs, Ca, Mg, Sr et Ba). L'oxyde métallique composite du lithium contient du nickel, du cobalt et du manganèse, et présente une surface spécifique BET comprise entre 3 et 15 m²/g (inclus) ainsi qu'une granulométrie moyenne déterminée par diffraction/diffusion laser de 0,1 µm ou plus, tout en restant inférieure à 1 µm.
PCT/JP2010/072070 2009-12-07 2010-12-02 Méthode de production d'un oxyde métallique composite du lithium, oxyde métallique composite du lithium et pile secondaire à électrolyte non aqueux WO2011071094A1 (fr)

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