WO2014175191A1 - Composé composite, oxyde composite contenant du lithium et leurs procédés respectifs de production - Google Patents

Composé composite, oxyde composite contenant du lithium et leurs procédés respectifs de production Download PDF

Info

Publication number
WO2014175191A1
WO2014175191A1 PCT/JP2014/061081 JP2014061081W WO2014175191A1 WO 2014175191 A1 WO2014175191 A1 WO 2014175191A1 JP 2014061081 W JP2014061081 W JP 2014061081W WO 2014175191 A1 WO2014175191 A1 WO 2014175191A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
positive electrode
composite oxide
compound
producing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/061081
Other languages
English (en)
Japanese (ja)
Inventor
河里　健
昌彦 田村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=51791769&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2014175191(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2015513733A priority Critical patent/JP6510402B2/ja
Publication of WO2014175191A1 publication Critical patent/WO2014175191A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-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
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2006/11—Powder tap density
    • 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
    • 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 composite compound useful as a precursor of a lithium-containing composite oxide, and a method for producing the same, a lithium-containing composite oxide, and a method for producing the same, a method for producing a positive electrode for a lithium ion secondary battery, and a lithium ion secondary
  • the present invention relates to a battery manufacturing method.
  • Lithium ion secondary batteries are widely used in portable electronic devices such as mobile phones and notebook computers.
  • the positive electrode active material for the lithium ion secondary battery include composite oxides of lithium and transition metals such as LiCoO 2 , LiNiO 2 , LiNi 0.8 Co 0.2 O 2 , and LiMn 2 O 4 (hereinafter, "Sometimes referred to as" lithium-containing composite oxide ").
  • the positive electrode active material has a further improvement in the discharge capacity per unit volume and the characteristics that the discharge capacity does not decrease after repeated charge / discharge cycles (hereinafter, sometimes referred to as “cycle characteristics”), and safety.
  • cycle characteristics the characteristics that the discharge capacity does not decrease after repeated charge / discharge cycles
  • safety There is a need for compatibility with sex.
  • the cycle characteristics are insufficient, for example, in a portable electronic device, the usable time in one charge decreases with time, so the commercial value of the portable electronic device decreases. Therefore, improvement in cycle characteristics is strongly demanded.
  • the discharge capacity per unit volume is determined by the discharge capacity per unit mass and the packing density of the positive electrode active material. Therefore, in order to improve the packing density of the positive electrode active material in the positive electrode (hereinafter sometimes referred to as “electrode density”), it has been studied to control the particle size and particle size distribution of the positive electrode active material. In addition, in order to improve the packing density of the positive electrode active material in the positive electrode, it has been studied to control the shape of the positive electrode active material particles into a spherical shape or a plate shape.
  • Patent Document 1 proposes a technique for improving the press density by setting the ratio of particles of 10 ⁇ m or less to 26 to 60% by volume in the volume-based particle size distribution of the positive electrode active material.
  • this proposed technique has a problem that the average particle size of the positive electrode active material is large, so that the diffusion of lithium is delayed, the rate characteristics are lowered, and the proportion of fine particles is increased, so that the safety is lowered.
  • Patent Document 2 proposes a technique for mixing large and small positive electrode active material particles having different compositions and particle sizes.
  • this proposed technique requires a step of individually synthesizing two kinds of positive electrode active materials and a step of mixing them, and there is a problem that the manufacturing process is complicated.
  • Patent Document 3 discloses that a positive electrode is obtained by thermally decomposing particles having a ratio of a short axis particle diameter to a long axis particle diameter (short axis particle diameter / long axis particle diameter) in the range of 0.5 to 1.0.
  • a technique has been proposed in which crystallites and particles in an active material are three-dimensionally approximately isotropic.
  • this proposed technique has a problem that the obtained particles are not sufficiently spherical and a sufficient packing density cannot be obtained.
  • Patent Document 4 proposes a technique for improving the filling properties by including particles having a positive correlation between the particle diameter of the positive electrode active material and the average circularity.
  • particles with a high average circularity and particles with a low average circularity coexist, so the volume change due to lithium insertion / extraction is not isotropic.
  • the cycle characteristics such as the occurrence.
  • the presence of small particles having a large specific surface area increases the reactivity, which poses a safety problem.
  • Japanese Unexamined Patent Publication No. 2012-121805 Japanese Unexamined Patent Publication No. 2012-74246 Japanese Unexamined Patent Publication No. 2003-346809 Japanese Unexamined Patent Publication No. 2009-283353
  • the present invention is capable of producing a high-density electrode even when the pressing pressure when forming the positive electrode active material-containing layer is low, and is excellent in discharge capacity per unit volume, rate characteristics, and extremely excellent cycle characteristics. It is an object of the present invention to provide a composite compound that is useful as a precursor of a contained composite oxide, and a production method thereof. Moreover, this invention makes it a subject to provide the lithium containing complex oxide using the said complex compound, and its manufacturing method. Furthermore, this invention makes it a subject to provide the manufacturing method of the positive electrode for lithium ion secondary batteries using the said lithium containing complex oxide, and the manufacturing method of a lithium ion secondary battery using the said positive electrode.
  • the present invention provides a composite compound having the following configuration, a method for producing the same, a lithium-containing composite oxide, a method for producing the same, a method for producing a positive electrode for a lithium ion secondary battery, and a method for producing a lithium ion secondary battery. To do.
  • the content of nickel in the composite compound is 44 to 68 mol%, the content of manganese is 22 to 44 mol%, and the content of cobalt is 4 to 28 mol based on the total of nickel, manganese and cobalt. % Of the composite compound according to the above [4].
  • a method for producing a composite compound according to any one of [1] to [5] above An aqueous solution containing nickel and manganese and an alkali are continuously added to the first reaction vessel to precipitate the core particles, and a core particle-containing liquid preparation step for obtaining a core particle-containing liquid containing the core particles; A moving step of continuously transferring a part of the core particle-containing liquid in the first reaction vessel from the first reaction vessel to the second reaction vessel; To the second reaction vessel containing the core particle-containing liquid, an aqueous solution containing nickel and manganese and an alkali are continuously added to grow the core particles, and a part of water is obtained from the obtained reaction liquid.
  • a positive electrode manufacturing step of manufacturing a positive electrode A laminate production step of producing a laminate by laminating the positive electrode, the separator, and the negative electrode; Including a nonaqueous electrolyte application step of containing a nonaqueous electrolyte in the laminate,
  • the method for producing a lithium ion secondary battery, wherein the positive electrode preparation step is the method for producing a positive electrode for a lithium ion secondary battery according to the above [12] or [13].
  • the conventional problems can be solved, and even when the press pressure when forming the positive electrode active material-containing layer is low, a high-density electrode can be produced, the discharge capacity per unit volume, and It is possible to provide a composite compound useful as a precursor of a lithium-containing composite oxide that has excellent rate characteristics and extremely excellent cycle characteristics, and a method for producing the same.
  • the lithium containing complex oxide using the said complex compound and its manufacturing method can be provided.
  • the manufacturing method of the positive electrode for lithium ion secondary batteries using the said lithium containing complex oxide and the manufacturing method of a lithium ion secondary battery using the said positive electrode can be provided.
  • FIG. 1 is a volume particle size distribution curve of the composite compound of Example 1 and Comparative Example 1.
  • FIG. 2 is a graph showing the relationship between the tap density of the composite compound in Examples 1 to 5 and Comparative Examples 1 to 6 and the tap density of the lithium-containing composite oxide.
  • the “precursor” refers to a compound capable of obtaining a lithium-containing composite oxide by mixing and baking with a lithium compound described later.
  • the composite compound of the present invention contains at least nickel (Ni) and manganese (Mn), and further contains other components as necessary.
  • This composite compound has a ratio (D 90 / D 10 ) of a volume-based cumulative 90% diameter (D 90 ) and a volume-based cumulative 10% diameter (D 10 ) in laser scattering particle size distribution measurement of 2.00 or less,
  • the tap density is 1.9 g / cm 3 or more, and the average circularity is 0.960 or more.
  • this composite compound is a precursor of lithium containing composite oxide, Comprising: It is a compound which does not contain lithium.
  • the molar ratio of Ni and Mn (Ni / Mn) in the composite compound is preferably 1.5 to 3.0, and more preferably 1.65 to 2.05.
  • the composite compound preferably further contains cobalt (Co) in order to improve rate characteristics.
  • Co cobalt
  • the content of Ni is preferably 44 to 68 mol% and more preferably 48 to 58 mol% with respect to the total of Ni, Mn and Co in the composite compound.
  • Mn does not contribute to the charge / discharge capacity, but maintains a layered structure. Therefore, the content of Mn is preferably 22 to 44 mol% and more preferably 26 to 36 mol% with respect to the total of Ni, Mn and Co of the present composite compound.
  • the Co content is preferably 4 to 28 mol% and more preferably 16 to 24 mol% with respect to the total of Ni, Mn and Co in the present composite compound.
  • the contents of Ni, Mn and Co in the composite compound can be measured, for example, by dissolving the composite compound in an acid and measuring the obtained liquid by ICP (high frequency inductively coupled plasma).
  • the other component contained in the composite oxide is at least one selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), aluminum (Al), and zirconium (Zr). Is preferred.
  • the composite compound include carbonates, acetates, hydroxides, oxyhydroxides, and mixtures thereof.
  • the composite compound is preferably a hydroxide because the tap density can be increased.
  • (D 90 / D 10 ) of the composite compound is 2.00 or less, preferably 1.70 to 1.98, more preferably 1.80 to 1.95.
  • a lithium-containing composite oxide obtained using the complex compound is excellent in cycle characteristics. If (D 90 / D 10 ) is within the above preferred range, it is advantageous because the electrode density can be increased.
  • the volume-based cumulative 50% diameter (D 50 ) in the laser scattering particle size distribution measurement of the composite compound is preferably 5.0 to 13.0 ⁇ m, more preferably 6.0 to 12.0 ⁇ m, from the viewpoint of rate characteristics.
  • a thickness of 0.0 to 10.0 ⁇ m is particularly preferable.
  • D 10 , D 50 , and D 90 are particle size distributions obtained on a volume basis, and in the cumulative curve with the total volume of 100%, the cumulative curve is 10%, 50%, And the particle diameter at the point of 90%.
  • D 10, D 50, and D 90 are, for example, can be determined using the frequency distribution and cumulative volume distribution curve measured by a laser scattering particle size distribution measuring apparatus. The measurement is performed by sufficiently dispersing the powder in an aqueous medium by ultrasonic treatment or the like.
  • Examples of the device include a laser diffraction / scattering particle size distribution measuring device (device name: MT-3300EX) manufactured by Nikkiso Co., Ltd., a laser diffraction / scattering particle size distribution measuring device Partica LA-950VII manufactured by Horiba, Ltd., Nikkiso For example, Microtrac HRA (X-100) manufactured by KK
  • the tap density of the composite compound is 1.9 g / cm 3 or more, preferably 1.9 ⁇ 2.8g / cm 3, more preferably 2.0 ⁇ 2.4g / cm 3, 2.0 ⁇ 2 .2 g / cm 3 is particularly preferred. Since this composite compound has a tap density of 1.9 g / cm 3 or more, the lithium-containing composite oxide obtained using this composite oxide is excellent in cycle characteristics. It is advantageous that the tap density is within the above-described preferable range because the electrode density can be increased.
  • the tap density can be obtained by dividing the mass of the sample filled in the container by the volume of the sample after tapping a predetermined number of times. The tap density is obtained by tapping 700 times, for example.
  • the tap density can be measured using, for example, a tap denser KYT-4000 manufactured by Seishin Enterprise Co., Ltd.
  • the average circularity of the composite compound is 0.960 or more, preferably 0.960 to 0.990, and more preferably 0.960 to 0.980. Since this composite compound has an average circularity of 0.960 or more, the lithium-containing composite oxide obtained using this composite compound is excellent in cycle characteristics. If the average circularity is within the above-described preferable range, it is advantageous because the electrode density can be increased.
  • the circularity is obtained by photographing a particle and dividing the circumference of a circle equivalent to the projected particle projection area by the circumference of the photographed particle image.
  • the average circularity is an average value of circularity of photographed particles.
  • the average circularity is measured, for example, by dispersing the particles in an aqueous medium by ultrasonic treatment or the like, and irradiating the particles passing through the flow cell with stroboscopic light so that the particles are photographed as a still image and analyzed. Is done.
  • the average circularity can be obtained, for example, by analyzing a particle image obtained using a flow type particle image analyzer (manufactured by Malvern, FPIA-3000).
  • the specific surface area of the complex compound is preferably 3.0 ⁇ 12.0m 2 / g, more preferably 4.0 ⁇ 10.0m 2 / g, particularly preferably 5.0 ⁇ 8.0m 2 / g. If the specific surface area is 3.0 m 2 / g or more, the capacity per mass is excellent, and if it is 12.0 m 2 / g or less, the electrode density can be increased. When the specific surface area is within the above-mentioned preferable range, it is advantageous in that the rate characteristics are excellent.
  • the specific surface area can be measured by, for example, the BET method using nitrogen gas.
  • the method for producing a composite compound of the present invention includes at least a core particle-containing liquid preparation step, a transfer step, and a particle growth step, and further includes other steps as necessary.
  • an aqueous solution containing Ni and Mn (hereinafter referred to as an aqueous solution (1)) and an alkali are continuously added to the first reaction vessel to precipitate the core particles, Is a step of obtaining a core particle-containing liquid containing
  • Ni, Mn, and Co have different solubility when the pH is changed, and thus may segregate when the core particles are precipitated.
  • Examples of a method for continuously adding the aqueous solution (1) and the alkali to the first reaction vessel include dropping and a method of pumping from a pipe inserted into the reaction solution.
  • the aqueous solution (1) is further preferably an aqueous solution containing Co.
  • the aqueous solution (1) can be obtained by dissolving a nickel compound and a manganese compound, and preferably a cobalt compound, in an aqueous medium.
  • the aqueous medium may contain only water or components other than water in addition to water. Examples of components other than water include methanol, ethanol, 1-propanol, 2-propanol, and polyol. Examples of the polyol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, butanediol, glycerin and the like.
  • Components other than water are preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 1% by mass or less, and most preferably not contained with respect to the aqueous medium. If there are few ratios of components other than water, it is excellent in terms of an environment, handleability, and cost.
  • the nickel compound, manganese compound, and cobalt compound include inorganic salts, oxides, hydroxides, and organic compounds containing each element.
  • inorganic salts include sulfates, nitrates, and carbonates.
  • the oxide include NiO, Mn 3 O 4 , Mn 2 O 3 , MnO 2 , CoO, Co 2 O 3 , and Co 3 O 4 .
  • hydroxide examples include Ni (OH) 2 , Mn (OH) 2 , and Co (OH) 2 .
  • examples of the organic compound include fatty acid nickel, manganese citrate, fatty acid manganese, Co (OAc) 2 and the like. Among these, sulfate is preferable because of its high solubility and low corrosiveness to equipment.
  • the nickel compound, manganese compound, and cobalt compound may be the same type of compound or different types of compounds.
  • the content of the nickel compound in the aqueous solution (1) is preferably 1.0 to 4.0 mol / L, more preferably 1.5 to 3.5 mol / L, and particularly preferably 2.0 to 3.0 mol / L. .
  • the manganese compound content in the aqueous solution (1) is preferably 0.3 to 2.0 mol / L, more preferably 0.5 to 1.5 mol / L, and particularly preferably 0.7 to 1.3 mol / L. .
  • the content of the cobalt compound in the aqueous solution (1) is preferably 0.5 to 3.0 mol / L, more preferably 1.0 to 2.5 mol / L. 2 to 2.0 mol / L is particularly preferable.
  • the addition amount when the aqueous solution (1) is continuously added to the first reaction vessel is preferably 0.1 to 3.0 L / hour, more preferably 0.5 to 2.0 L / hour. Particularly preferred is 0 to 1.5 L / hour.
  • the alkali examples include a hydroxide or carbonate containing an alkali metal element. Specific examples include sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate and the like.
  • the alkali is preferably used in the form of an aqueous solution, that is, as an alkaline aqueous solution.
  • the concentration of the alkaline aqueous solution is preferably 1 to 12 mol / kg, more preferably 6 to 12 mol / kg.
  • the amount of alkali added continuously to the first reaction vessel is preferably 0.01 to 0.5 L / hour, more preferably 0.02 to 0.1 L / hour as an aqueous alkali solution.
  • any compound that forms a complex with Ni and Mn may be used, and examples thereof include ammonia, ammonium sulfate, ammonium bicarbonate, and ammonium bicarbonate.
  • the amount (molar ratio) of the complexing agent with respect to the total amount of Ni, Co, Mn and the other components is preferably 0.01 to 10, and preferably 0.1 to 1 in order to suppress segregation of the metal in the particles. More preferred.
  • the core particle-containing liquid preparation step is preferably performed while maintaining the pH in the first reaction vessel at 11.0 to 13.5, and more preferably at 12.0 to 13.0. If the pH in the reaction vessel is maintained at 11.0 to 13.5, the contact between the aqueous solution (1) and the alkali occurs quickly, and the generation of core particles is dominant, which is preferable.
  • the core particles are preferably hydroxides.
  • the core particle-containing liquid preparation step is preferably performed at a temperature in the first reaction vessel of 45 to 70 ° C.
  • water may be placed in the first reaction vessel before the aqueous solution (1) and alkali are continuously added to the first reaction vessel.
  • examples of water include ion exchange water.
  • the moving step is a step of continuously transferring a part of the core particle-containing liquid in the first reaction vessel from the first reaction vessel to the second reaction vessel.
  • a specific method of the transfer step a method of transferring the nuclear particle-containing liquid overflowing from the first reaction vessel to the second reaction vessel, a pipe is provided in the upper part of the first reaction vessel, and the nucleus is passed through the pipe. Examples thereof include a method of transferring the particle-containing liquid to the second reaction vessel.
  • the method of transferring the core particle-containing liquid overflowing from the first reaction vessel to the second reaction vessel is preferable because it is simple.
  • aqueous solution (2) an aqueous solution containing Ni and Mn (hereinafter referred to as aqueous solution (2)) and an alkali are continuously added to a second reaction vessel containing the nuclear particle-containing liquid to grow the nuclear particles. Meanwhile, this is a step of removing a part of the supernatant from the obtained reaction solution. Also in the particle growth step, it is preferable to continuously add a complexing agent for the same reason as in the core particle-containing liquid preparation step.
  • the aqueous solution (2) may be the same aqueous solution as the aqueous solution (1) used in the core particle-containing liquid preparation step.
  • the method and amount of continuous addition are the same.
  • the alkali is the same as the alkali used in the core particle-containing liquid preparation step, and the method and amount of continuous addition are also the same.
  • the complexing agent is the same as the complexing agent used in the core particle-containing liquid preparation step.
  • the aqueous solution (2) and alkali are continuously added to the second reaction vessel to grow the core particles.
  • a part of water is removed from the obtained reaction liquid while growing the core particles.
  • Examples of the method for removing water include filtration.
  • the particle growth step is preferably performed while maintaining the pH in the second reaction vessel at 9.0 to 11.5, and more preferably at 9.5 to 10.5. If the pH in the reaction vessel is maintained at 9.0 to 11.5, it is preferable that the particle growth reaction proceeds easily.
  • the particle growth step is preferably performed at a temperature in the second reaction vessel of 20 to 40 ° C.
  • the growth of the formed core particles is suppressed, and the solid content concentration of the core particle-containing liquid is set to the core particle in order to suppress the bonding between the core particles. It is maintained to such an extent that bonding between them can be suppressed.
  • the supernatant liquid is partially removed from the reaction liquid to gradually increase the solid content concentration of the reaction liquid to increase the average circularity of the particles, and the particle size is uniform and has a sharp particle size distribution. Particles of the composite compound of the invention can be obtained.
  • the method for producing a lithium-containing composite oxide of the present invention includes at least a mixing step and a firing step.
  • the lithium-containing composite oxide of the present invention is obtained by the method for producing a lithium-containing composite oxide of the present invention.
  • the lithium-containing composite oxide is a composite oxide that can be used as a positive electrode active material of a lithium ion secondary battery.
  • the lithium-containing composite oxide obtained by the method for producing a lithium-containing composite oxide of the present invention is manufactured using this composite compound. Since this composite compound has a large tap density and a high average circularity of the particles, the lithium-containing composite oxide has a high tap density and an average circularity. As a result, the coating slurry containing the lithium-containing composite oxide has a low viscosity. Therefore, handling is easy and the solid content concentration in the slurry can be increased. Furthermore, a battery having a large electrode density formed on a current collector substrate and a large capacity per unit volume can be produced.
  • the cycle characteristics are very excellent.
  • the mixing step is a step of obtaining a mixture by mixing the lithium compound and the present composite compound.
  • the lithium compound serves as a lithium source for the lithium-containing composite oxide, and lithium hydroxide, lithium carbonate, lithium nitrate, and the like can be used.
  • the lithium compound used in the mixing step is a compound different from the lithium-containing composite oxide.
  • the amount of the lithium compound in the mixing is such that the molar ratio of lithium (Li) contained in the lithium compound (Li / Ni + Mn + Co) is 1.02 to 1.12 with respect to the total of Ni, Mn and Co contained in the composite compound. Is preferable, and an amount of 1.03 to 1.07 is more preferable.
  • a baking process is a process of baking the said mixture.
  • the firing temperature is preferably 870 to 970 ° C, more preferably 890 to 940 ° C.
  • the firing atmosphere is preferably an oxygen-containing atmosphere. Examples of the oxygen-containing atmosphere include an air atmosphere.
  • the lithium-containing composite oxide is preferably a compound represented by the following general formula (1).
  • Me is composed of Mg, Ca, Sr, Ba, Al, and Zr It is at least one selected from the group.
  • lithium-containing composite oxide examples include LiMn 0.5 Ni 0.5 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , Li 1.02 Ni 0.49 Co 0.196 Mn 0.294 O 2, Li 1.04 Ni 0.480 Co 0.192 Mn 0.288 O 2, LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 1.99 F 0.01 and the like.
  • the kind and ratio of the metal element in the lithium-containing composite oxide can be measured, for example, by ICP measurement in the same manner as the composite compound.
  • the volume-based cumulative 50% diameter (D 50 ) in laser scattering particle size distribution measurement of the lithium-containing composite oxide is preferably 5 to 20 ⁇ m, more preferably 6 to 13 ⁇ m, and particularly preferably 7 to 10 ⁇ m.
  • D 50 is equal to or 5 ⁇ m or more, the electrode density is sufficiently high, if 20 ⁇ m or less, it is advantageous from the viewpoint of excellent charge-discharge efficiency and rate characteristics.
  • the ratio (D 90 / D 10 ) of the volume-based cumulative 90% diameter (D 90 ) and the volume-based cumulative 10% diameter (D 10 ) in the laser scattering particle size distribution measurement of the lithium-containing composite oxide is 2.10 or less. Preferably, 2.00 or less is more preferable. If (D 90 / D 10 ) of the lithium-containing composite oxide is 2.10 or less, it is advantageous in that the tap density is improved and the filling property is improved.
  • the tap density of the lithium-containing composite oxide is preferably 1.9 ⁇ 3.0g / cm 3, more preferably 2.0 ⁇ 2.7g / cm 3. If the tap density is 1.9 g / cm 3 or more, the electrode density is sufficiently high, and if the tap density is 3.0 g / cm 3 or less, the electrolyte easily penetrates into the particles, and battery characteristics such as rate characteristics are obtained. This is advantageous in terms of improvement.
  • the average circularity of the lithium-containing composite oxide is preferably 0.950 or more, and more preferably 0.960 or more. If the average circularity is 0.950 or more, it is advantageous in that the tap density is excellent, the filling property, and the expansion and contraction of the electrode are isotropic.
  • the specific surface area of the lithium-containing composite oxide is preferably 0.10 ⁇ 10m 2 / g, more preferably 0.20 ⁇ 1.0m 2 / g. If the specific surface area is within a preferred range, it is advantageous in that a high positive electrode active material-containing layer having a high discharge capacity is obtained and cycle characteristics are excellent.
  • the residual alkali amount of the lithium-containing composite oxide is preferably 1.50 mol% or less, and more preferably 1.30 mol% or less. If the residual alkali amount is 1.50 mol% or less, it is advantageous in that gelation of the slurry can be suppressed during electrode coating.
  • the residual alkali amount is a value (mol%) representing the amount of alkali eluted in water from 1 mol of Li in the lithium-containing composite oxide when the lithium-containing composite oxide is dispersed in water.
  • the manufacturing method of the positive electrode for lithium ion secondary batteries of this invention contains a positive electrode active material content layer formation process at least, Preferably a pressurization process is included.
  • the positive electrode active material-containing layer forming step is a step of forming a positive electrode active material-containing layer containing a lithium-containing composite oxide, a binder, and a conductive material. Specifically, there is a method in which a coating liquid containing a lithium-containing composite oxide, a binder, a conductive material, and a solvent is applied onto the positive electrode current collector.
  • binder examples include fluororesins, polyolefins, polymers and copolymers having an unsaturated bond, acrylic acid polymers and copolymers, and the like.
  • fluororesin examples include polyvinylidene fluoride and polytetrafluoroethylene.
  • polyolefin examples include polyethylene and polypropylene.
  • polymer having an unsaturated bond examples include styrene / butadiene rubber, isoprene rubber, and butadiene rubber.
  • acrylic acid polymers examples include acrylic acid polymers and methacrylic acid polymers.
  • Examples of the conductive material include carbon black, graphite, and carbon fiber.
  • Examples of the carbon black include acetylene black and ketjen black.
  • Examples of the solvent in the coating solution include N-methylpyrrolidone.
  • Examples of the material of the positive electrode current collector include stainless steel, aluminum, aluminum alloy, copper, and nickel.
  • Application methods include doctor blade coating.
  • the thickness of the positive electrode active material-containing layer is preferably 20 to 80 ⁇ m, more preferably 30 to 50 ⁇ m.
  • the pressurizing step is a step of pressurizing the positive electrode active material-containing layer formed on the positive electrode current collector with a roll press or the like in the positive electrode active material-containing layer forming step.
  • the pressurizing pressure is preferably 1 t (ton) / cm or less, and more preferably 0.5 t / cm or less.
  • the pressurizing pressure is preferably 0.1 t / cm or more.
  • the lithium-containing composite oxide of the present invention provides a positive electrode active material-containing layer having a high electrode density even when the pressure applied is low in the production of the positive electrode. Since the pressurizing pressure is low, a strong manufacturing facility that can withstand the high pressure is unnecessary. Moreover, it is thought that the decrease in the yield due to the damage of the positive electrode when manufacturing the positive electrode can be suppressed and the decrease in the safety when used for the lithium ion secondary battery can be suppressed because the pressurization pressure is low. .
  • the method for producing a lithium ion secondary battery of the present invention includes at least a positive electrode preparation step, a laminate preparation step, and a nonaqueous electrolyte application step.
  • a positive electrode preparation process is a process of producing a positive electrode, and is a manufacturing method of the positive electrode for lithium ion secondary batteries of this invention.
  • the laminate production step is not particularly limited as long as it is a step of producing a laminate by laminating the positive electrode, the separator, and the negative electrode, and can be appropriately selected according to the purpose.
  • Examples of the material for the separator include paper, cellophane, polyolefin nonwoven fabric, polyamide nonwoven fabric, glass fiber nonwoven fabric, and porous polypropylene.
  • Examples of the paper include kraft paper, vinylon mixed paper, and synthetic pulp mixed paper.
  • the shape of the separator is a sheet shape.
  • the structure of the separator may be a single layer structure or a laminated structure.
  • the negative electrode contains at least a negative electrode current collector and a negative electrode active material-containing layer.
  • Examples of the material of the negative electrode current collector include nickel, copper, and stainless steel.
  • the negative electrode active material-containing layer contains at least a negative electrode active material. Furthermore, a binder is contained as necessary.
  • the negative electrode active material may be any material that can occlude and release lithium ions, such as lithium metal, lithium alloy, lithium compound, carbon material, silicon carbide compound, silicon oxide compound, titanium sulfide, boron carbide compound, or silicon. , Tin, or an alloy mainly composed of cobalt.
  • Examples of carbon materials include non-graphitizable carbon, artificial graphite, natural graphite, pyrolytic carbons, cokes, graphites, glassy carbons, organic polymer compound fired bodies, carbon fibers, activated carbon, carbon blacks, etc. Can be mentioned.
  • Examples of the cokes include pitch coke, needle coke, and petroleum coke.
  • Examples of the fired organic polymer compound include those obtained by firing and carbonizing a phenol resin, a furan resin, or the like at an appropriate temperature.
  • Other materials that can occlude and release lithium ions at a relatively low potential include, for example, iron oxide, ruthenium oxide, molybdenum oxide, tungsten oxide, titanium oxide, tin oxide, and Li 2.6 Co 0.4 N. Can also be used as the negative electrode active material.
  • the binder is the same as the binder used in the positive electrode active material-containing layer forming step.
  • a slurry is prepared by mixing a negative electrode active material, a binder, and a solvent, and the prepared slurry is applied onto a negative electrode current collector, followed by drying and then pressing.
  • the method etc. are mentioned.
  • Nonaqueous electrolyte application process As a nonaqueous electrolyte provision process, what is necessary is just the process of making the said laminate contain a nonaqueous electrolyte, The method of inject
  • non-aqueous electrolyte examples include a non-aqueous electrolyte, an inorganic solid electrolyte, and a solid or gel polymer electrolyte in which an electrolyte salt is mixed or dissolved.
  • non-aqueous electrolyte examples include those prepared by appropriately combining an organic solvent and an electrolyte salt.
  • Organic solvents include cyclic carbonate, chain carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, diglyme, triglyme, ⁇ -butyrolactone, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, acetate ester, butyrate ester And propionic acid esters.
  • Examples of the cyclic carbonate include propylene carbonate and ethylene carbonate.
  • Examples of the chain carbonate include diethyl carbonate and dimethyl carbonate.
  • cyclic carbonates and chain carbonates are preferable, and propylene carbonate, dimethyl carbonate, and diethyl carbonate are more preferable. These may be used individually by 1 type and may use 2 or more types together.
  • electrolyte salt contained in the non-aqueous electrolyte include LiClO 4 , LiPF 6 , LiBF 4 , CF 3 SO 3 Li, LiCl, and LiBr.
  • Examples of the inorganic solid electrolyte include lithium nitride and lithium iodide.
  • Examples of the polymer compound used in the solid polymer electrolyte in which the electrolyte salt is mixed or dissolved include polyethylene oxide, polypropylene oxide, polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol, polyvinylidene fluoride, polyhexafluoropropylene, And their derivatives, mixtures, and complexes.
  • Examples of the polymer compound used in the gel polymer electrolyte in which the electrolyte salt is mixed or dissolved include a fluorine polymer compound, polyacrylonitrile, a copolymer of polyacrylonitrile, polyethylene oxide, a copolymer of polyethylene oxide, and the like. Can be mentioned.
  • Examples of the fluorine-based polymer compound include poly (vinylidene fluoride) and poly (vinylidene fluoride-co-hexafluoropropylene).
  • the matrix of the gel electrolyte is preferably a fluorine-based polymer compound from the viewpoint of stability against redox reaction.
  • ⁇ Particle size distribution measurement> The composite compound or lithium-containing composite oxide is dispersed in water using ultrasonic waves, and measured with a laser diffraction / scattering particle size distribution measurement device (device name: MT-3300EX) manufactured by Nikkiso Co., Ltd., frequency distribution and accumulation A volume distribution curve was obtained. From the obtained cumulative volume distribution curve, D 10 , D 50 , and D 90 were calculated to obtain D 90 / D 10 .
  • SSA Specific surface area
  • ⁇ Tap density> The tap density of the composite compound and the lithium-containing composite oxide was measured using a tap density measuring device (device name: Tap Denser KYT-4000K) manufactured by Seishin Enterprise Co., Ltd.
  • the positive electrode active material was filled in a 20 mL plastic tapping cell, and the tap density was calculated from the volume after tapping 700 times with a stroke of 20 mm.
  • ⁇ Average circularity> The average circularity of the composite compound and the lithium-containing composite oxide was measured using a flow type particle image analyzer (FPIA-3000, manufactured by Malvern).
  • Example 1 ⁇ Production of complex compound> Nickel sulfate (nickel sulfate (II) hexahydrate, manufactured by Wako Pure Chemical Industries, Ltd.), cobalt sulfate (cobalt sulfate (II) heptahydrate, manufactured by Wako Pure Chemical Industries, Ltd.), and manganese sulfate (manganese sulfate (II).
  • Nickel sulfate nickel sulfate (II) hexahydrate, manufactured by Wako Pure Chemical Industries, Ltd.
  • cobalt sulfate cobalt sulfate (II) heptahydrate, manufactured by Wako Pure Chemical Industries, Ltd.
  • manganese sulfate manganese sulfate
  • the solution obtained by dissolving pentahydrate, manufactured by Wako Pure Chemical Industries, Ltd.) in ion-exchanged water is filtered to obtain 2.5 mol / L nickel sulfate,
  • ion-exchanged water 500 g was put into a first reaction tank having a capacity of 1 L, and stirred at 400 rpm while being kept at 60 ° C. while bubbling with nitrogen gas.
  • the aqueous solution (1) was continuously supplied at a rate of 1.2 L / hour and a 28% by mass aqueous ammonia solution at a rate of 0.03 L / hour at the same time.
  • the pH in the reaction vessel was maintained at 12.5.
  • the core particle-containing liquid obtained in the first reaction tank was stored in the second reaction tank (capacity: 2 L) until the volume reached 80% due to overflow from the first reaction tank.
  • the core particle-containing liquid was stirred at 400 rpm while being kept at 30 ° C. while bubbling with nitrogen gas in the second reaction tank.
  • the aqueous solution (1) was continuously added at 1.2 L / hour and a 28% by weight aqueous ammonia solution at 0.03 L / hour at the same time, while the 18 mol / L aqueous sodium hydroxide solution was used.
  • the pH in the second reaction tank was kept at 10.
  • the supernatant liquid was extracted from the reaction liquid by suction filtration through a filter, the amount of liquid in the reaction system was adjusted, and particles were grown at 30 ° C. for 72 hours. Thereafter, the reaction solution was filtered and then washed with water to obtain a composite compound.
  • the obtained composite compound was dried at 120 ° C. for 12 hours to obtain a composite compound powder.
  • Table 1 shows the particle size distribution (D 10 , D 50 , D 90 , D 90 / D 10 ), specific surface area, tap density, and average circularity of this composite compound.
  • FIG. 1 shows the particle size distribution of this composite compound.
  • lithium-containing composite oxide 200.00 g of the composite compound and 83.67 g of lithium carbonate (Li 2 CO 3 , manufactured by SQM) having a Li content of 26.96 mol / kg are mixed and fired at 910 ° C. for 8 hours in an air atmosphere.
  • Li 2 CO 3 lithium carbonate
  • the composition ratio of the obtained lithium-containing composite oxide coincided with the preparation ratio.
  • Table 2 shows the particle size distribution (D 10 , D 50 , D 90 , D 90 / D 10 ), specific surface area, tap density, and average circularity of the obtained lithium-containing composite oxide powder.
  • Example 2 ⁇ Production of lithium-containing composite oxide> 200.00 g of the composite compound obtained in the same manner as in the method described in Example 1, 83.59 g of lithium carbonate (Li 2 CO 3 , manufactured by SQM) having a Li content of 26.96 mol / kg, lithium fluoride ( (LiF, manufactured by Wako Pure Chemical Industries, Ltd.) and 0.06 g were mixed, and charged composition Li 1.014 Ni 0.495 in the same manner as in Example 1 except that the mixture was baked at 910 ° C. for 8 hours in the air atmosphere. A lithium-containing composite oxide of Co 0.197 Mn 0.294 O 1.999 F 0.001 was obtained. The composition ratio of the obtained lithium-containing composite oxide coincided with the preparation ratio. About the obtained lithium containing complex oxide, it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Table 2.
  • Example 3 ⁇ Production of complex compound>
  • Example 1 a composite compound was obtained in the same manner as in Example 1 except that the conditions of the particle growth step in the second reaction vessel were changed to 30 hours at 96C. About the obtained composite compound, it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Table 1.
  • Example 1 ⁇ Production of lithium-containing composite oxide>
  • the lithium-containing composite oxidation of Li 1.014 Ni 0.491 Co 0.198 Mn 0.297 O 2 was performed in the same manner as in Example 1 except that the composite compound obtained above was used. I got a thing.
  • the composition ratio of the obtained lithium-containing composite oxide coincided with the preparation ratio.
  • Example 4 Provide of complex compound>
  • a composite compound was obtained in the same manner as in Example 1 except that the conditions of the particle growth step in the second reaction tank were changed to 30 hours at 120 ° C.
  • the obtained composite compound it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Table 1.
  • Example 5 ⁇ Production of complex compound>
  • the holding temperature of the first reaction vessel was changed to 70 ° C.
  • the conditions of the particle growth step in the second reaction vessel were changed to 30 hours at 60 ° C., and in the same manner as in Example 1.
  • a composite compound was obtained.
  • Example 1 ⁇ Production of lithium-containing composite oxide>
  • the lithium-containing composite oxidation of Li 1.014 Ni 0.493 Co 0.198 Mn 0.295 O 2 was performed in the same manner as in Example 1 except that the composite compound obtained above was used. I got a thing.
  • the composition ratio of the obtained lithium-containing composite oxide coincided with the preparation ratio.
  • ion-exchanged water 500 g was put into the reaction vessel, and stirred at 400 rpm while being kept at 60 ° C. while bubbling with nitrogen gas.
  • the aqueous solution (1) was continuously supplied at a rate of 1.2 L / hour and a 28% by mass aqueous ammonia solution at a rate of 0.03 L / hour simultaneously, while 18 mol / L aqueous sodium hydroxide solution was used.
  • the pH in the reaction vessel was maintained at 12.5.
  • the supernatant liquid was removed from the reaction solution by suction filtration through a filter to adjust the amount of liquid in the reaction system, and particles were grown at 60 ° C. for 72 hours. Thereafter, the obtained reaction solution was filtered and then washed with water to obtain a composite compound.
  • the obtained composite compound was dried at 120 ° C. for 12 hours to obtain composite compound powder.
  • the particle size distribution of the composite compound was measured in an aqueous solvent. The results are shown in Table 1.
  • FIG. 1 shows the particle size distribution of this composite compound. The tap density, specific surface area, and average circularity of the composite compound were measured. The results are shown in Table 1.
  • lithium-containing composite oxide 200.00 g of the composite compound and 83.67 g of lithium carbonate (Li 2 CO 3 , manufactured by SQM) having a Li content of 26.96 mol / kg are mixed, and the mixture is baked at 910 ° C. for 8 hours in an air atmosphere.
  • the composition ratio of the obtained lithium-containing composite oxide coincided with the preparation ratio.
  • About the obtained lithium containing complex oxide it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Table 2.
  • Comparative Example 2 ⁇ Production of composite compound and lithium-containing composite oxide> A composite compound was obtained in the same manner as in Comparative Example 1 except that the reaction conditions in Comparative Example 1 were changed to 72 hours at pH 10.0 and 30 ° C. Furthermore, a lithium-containing composite oxide having a charging composition Li 1.014 Ni 0.493 Co 0.196 Mn 0.297 O 2 was obtained. The composition ratio of the obtained lithium-containing composite oxide coincided with the preparation ratio. About the obtained complex compound and lithium containing complex oxide, it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Tables 1 and 2.
  • Comparative Example 3 ⁇ Production of composite compound and lithium-containing composite oxide>
  • a composite compound was obtained in the same manner as in Comparative Example 1 except that the conditions of the particle growth process were changed to 30 ° C. for 60 hours.
  • a lithium-containing composite oxide having a charging composition Li 1.014 Ni 0.495 Co 0.197 Mn 0.294 O 2 was obtained.
  • the composition ratio of the obtained lithium-containing composite oxide coincided with the preparation ratio.
  • About the obtained complex compound and lithium containing complex oxide it carried out similarly to Example 1, and evaluated various characteristics. The results are shown in Tables 1 and 2.
  • positive electrode active materials As positive electrode active materials, positive electrode active materials (lithium-containing composite oxides) of Examples 1 to 5 and Comparative Examples 1 to 6, respectively, and acetylene black (conductive material, trade name: Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.) And a polyvinylidene fluoride solution (solvent: N-methylpyrrolidone) containing 12.1% by mass of polyvinylidene fluoride (binder, trade name: KFL # 1120, manufactured by Kureha Chemical Industry Co., Ltd.), and N-methylpyrrolidone Addition to make a slurry.
  • solvent N-methylpyrrolidone
  • the ratio of the positive electrode active material, acetylene black, and polyvinylidene fluoride during mixing was 90/5/5 in mass ratio (positive electrode active material / acetylene black / polyvinylidene fluoride).
  • the slurry was applied to one side of an aluminum foil having an average thickness of 20 ⁇ m (positive electrode current collector, trade name: E-FOIL, manufactured by Toyo Aluminum Co., Ltd.) using a doctor blade. It dried at 120 degreeC and produced the positive electrode sheet by performing roll press rolling (0.3t / cm) twice.
  • the positive electrode sheets obtained from the positive electrode active materials of Examples 1 to 5 were respectively positive electrode sheets 1 to 5 and the positive electrode sheets obtained from the positive electrode active materials of Comparative Examples 1 to 6 were respectively positive electrode sheets 6 to 11. And
  • Lithium foil with an average thickness of 500 ⁇ m Lithium foil, manufactured by Honjo Chemical Co., Ltd.
  • Negative electrode current collector Stainless steel plate with an average thickness of 1 mm
  • Separator Porous polypropylene with an average thickness of 25 ⁇ m (Celguard # 2500, manufactured by Celgard)
  • Lithium ion secondary batteries using the positive electrode sheets 1 to 11 are referred to as lithium batteries 1 to 11, respectively.
  • Electrode density is measured by punching an electrode coated on an aluminum foil into a disk having a diameter of 1.8 cm, measuring the mass with an electronic balance, and measuring the thickness with a micrometer. Next, an aluminum foil not coated with an electrode is punched out to a diameter of 1.8 cm, and the mass and thickness are similarly measured.
  • the electrode density was calculated by the following formula (2). (Thickness of coated electrode ⁇ thickness of aluminum foil) ⁇ 0.9 2 ⁇ ⁇ (circumferential ratio) / (mass of coated electrode ⁇ mass of aluminum foil) Formula (2)
  • Examples 1 to 5 even if the press pressure for forming the positive electrode active material-containing layer is low, a higher electrode density than Comparative Examples 1 to 6 can be obtained, and good initial characteristics, rate characteristics, and cycle characteristics can be obtained. It was. The initial capacity, initial efficiency, initial voltage, and rate characteristics of Examples 1 to 5 were excellent results together with Comparative Examples 1 to 6.
  • the cycle characteristics of Examples 1 to 5 were 1.0% or more superior to the cycle characteristics of 93.1% of Comparative Example 5 that showed the best results among the comparative examples.
  • the cycle characteristics empirically tend to be proportional to the half power of the number of cycles.
  • 94.0% in 50 cycles is 73.0%
  • 93.0% in 50 cycles is 69.0%.
  • 94.0% in 50 cycles is 40%
  • 93.0% is 30%. Therefore, it was confirmed that Examples 1 to 5 were very excellent in terms of cycle characteristics as compared with Comparative Examples 1 to 6.
  • the cycle characteristic was 96.4%, which was a very good result.
  • the composite compound of the present invention can obtain a high electrode density even when the pressing pressure during production is low, has high safety, is excellent in discharge capacity per unit volume, and rate characteristics, and is very excellent in cycle characteristics. It can be suitably used as a precursor of a lithium-containing composite oxide.
  • the lithium-containing composite oxide of the present invention can obtain a high electrode density even when the pressing pressure during production is low, has high safety, excellent discharge capacity per unit volume, and rate characteristics, and further has cycle characteristics. Since it is very excellent, it can be suitably used for a lithium ion secondary battery. It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2013-092486 filed on April 25, 2013 are cited here as disclosure of the specification of the present invention. Incorporated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

La présente invention concerne un composé composite utilisable en tant que précurseur d'un oxyde composite contenant du lithium caractérisé par une grande densité d'électrode même quand la pression de pressage appliquée durant la production est faible, qui présente une remarquable capacité de décharge électrique par unité de surface et de remarquables propriétés en matière d'intensité, ainsi que des propriétés extrêmement intéressantes en matière de cycle; et autres. L'invention concerne un composé composite contenant du nickel et du manganèse, et qui présente un rapport entre le diamètre de 90 % de son volume cumulé (D90) et le diamètre de 10 % de son volume cumulé (D10), c'est-à-dire D90/D10, inférieur ou égal à 2,00 comme indiqué par une mesure de sa répartition granulométrique par diffusion laser, une masse volumique tassée supérieure ou égale à 1,9 g/cm3 et un degré de circularité moyen supérieur ou égal à 0,960.
PCT/JP2014/061081 2013-04-25 2014-04-18 Composé composite, oxyde composite contenant du lithium et leurs procédés respectifs de production Ceased WO2014175191A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2015513733A JP6510402B2 (ja) 2013-04-25 2014-04-18 複合化合物、リチウム含有複合酸化物、及びそれらの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013092486 2013-04-25
JP2013-092486 2013-04-25

Publications (1)

Publication Number Publication Date
WO2014175191A1 true WO2014175191A1 (fr) 2014-10-30

Family

ID=51791769

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/061081 Ceased WO2014175191A1 (fr) 2013-04-25 2014-04-18 Composé composite, oxyde composite contenant du lithium et leurs procédés respectifs de production

Country Status (2)

Country Link
JP (1) JP6510402B2 (fr)
WO (1) WO2014175191A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015115547A1 (fr) * 2014-01-31 2015-08-06 住友金属鉱山株式会社 Particules d'hydroxyde de composite nickel-manganèse, son procédé de fabrication, matériau actif d'électrode positive pour batteries rechargeables à électrolyte non aqueux, procédé de production d'un matériau actif d'électrode positive pour batteries rechargeables à électrolyte non aqueux, et batterie rechargeable à électrolyte non aqueux
JP2016095934A (ja) * 2014-11-12 2016-05-26 トヨタ自動車株式会社 二次電池
JP2016184528A (ja) * 2015-03-26 2016-10-20 日産自動車株式会社 非水電解質二次電池用正極およびこれを用いた非水電解質二次電池
JP2017525090A (ja) * 2014-06-12 2017-08-31 ユミコア 充電式バッテリー用のリチウム遷移金属酸化物カソード材料の前駆体
EP3225592A1 (fr) * 2016-03-31 2017-10-04 Honda Motor Co., Ltd. Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux
JP2017188443A (ja) * 2016-03-31 2017-10-12 日亜化学工業株式会社 非水系電解質二次電池用正極活物質の製造方法
WO2017204164A1 (fr) * 2016-05-24 2017-11-30 住友化学株式会社 Matériau actif d'électrode positive, son procédé de production, et électrode positive pour batteries rechargeables au lithium-ion
JP2018198132A (ja) * 2017-05-23 2018-12-13 本田技研工業株式会社 リチウムイオン二次電池用正極及びそれを用いるリチウムイオン二次電池
CN109244450A (zh) * 2018-10-24 2019-01-18 湖南海利锂电科技股份有限公司 一种用于混掺三元材料的高压实高容量型锰酸锂复合正极材料的制备方法
WO2020220662A1 (fr) * 2019-04-28 2020-11-05 宁德时代新能源科技股份有限公司 Matériau actif d'électrode positive, pôle d'électrode positive, batterie secondaire au lithium-ion et appareil
WO2021025101A1 (fr) 2019-08-06 2021-02-11 株式会社田中化学研究所 Particules d'hydroxyde composite de nickel, matériau actif d'électrode positive ayant des particules d'hydroxyde composite de nickel en tant que précurseurs, et procédé de production de matériau actif d'électrode positive
JPWO2021040033A1 (fr) * 2019-08-30 2021-03-04
CN113474296A (zh) * 2019-02-22 2021-10-01 住友金属矿山株式会社 锂离子二次电池用正极活性物质、锂离子二次电池用正极活性物质的制造方法、锂离子二次电池
JP2022120400A (ja) * 2021-02-05 2022-08-18 プライムプラネットエナジー＆ソリューションズ株式会社 非水電解質二次電池
CN115152060A (zh) * 2020-02-27 2022-10-04 松下知识产权经营株式会社 非水电解质二次电池用正极活性物质和非水电解质二次电池
US11804600B2 (en) 2016-03-31 2023-10-31 Nichia Corporation Positive electrode active material for nonaqueous electrolyte secondary battery
JP2024159021A (ja) * 2023-04-28 2024-11-08 トヨタ自動車株式会社 正極活物質及びリチウムイオン二次電池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008147068A (ja) * 2006-12-12 2008-06-26 Ise Chemicals Corp 非水電解液二次電池用リチウム複合酸化物
JP2010536697A (ja) * 2007-08-21 2010-12-02 ハー．ツェー．スタルク ゲゼルシャフト ミット ベシュレンクテル ハフツング 粉末状化合物、その製造方法並びにリチウム二次電池におけるその使用
JP2011116580A (ja) * 2009-12-02 2011-06-16 Sumitomo Metal Mining Co Ltd ニッケルコバルトマンガン複合水酸化物粒子とその製造方法、非水系電解質二次電池用正極活物質とその製造方法、および非水系電解質二次電池

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2008319749B2 (en) * 2007-11-01 2012-10-18 Agc Seimi Chemical Co., Ltd. Granulated powder of transition metal compound for raw material for positive electrode active material of lithium secondary battery, and method for producing the same
JP6428105B2 (ja) * 2014-09-29 2018-11-28 住友金属鉱山株式会社 ニッケルコバルトマンガン化合物及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008147068A (ja) * 2006-12-12 2008-06-26 Ise Chemicals Corp 非水電解液二次電池用リチウム複合酸化物
JP2010536697A (ja) * 2007-08-21 2010-12-02 ハー．ツェー．スタルク ゲゼルシャフト ミット ベシュレンクテル ハフツング 粉末状化合物、その製造方法並びにリチウム二次電池におけるその使用
JP2011116580A (ja) * 2009-12-02 2011-06-16 Sumitomo Metal Mining Co Ltd ニッケルコバルトマンガン複合水酸化物粒子とその製造方法、非水系電解質二次電池用正極活物質とその製造方法、および非水系電解質二次電池

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015115547A1 (fr) * 2014-01-31 2015-08-06 住友金属鉱山株式会社 Particules d'hydroxyde de composite nickel-manganèse, son procédé de fabrication, matériau actif d'électrode positive pour batteries rechargeables à électrolyte non aqueux, procédé de production d'un matériau actif d'électrode positive pour batteries rechargeables à électrolyte non aqueux, et batterie rechargeable à électrolyte non aqueux
JPWO2015115547A1 (ja) * 2014-01-31 2017-03-23 住友金属鉱山株式会社 ニッケルマンガン複合水酸化物粒子とその製造方法、非水電解質二次電池用正極活物質とその製造方法、および非水電解質二次電池
US10236507B2 (en) 2014-01-31 2019-03-19 Sumitomo Metal Mining Co., Ltd. Nickel-manganese composite hydroxide particles, method for producing same, cathode active material for non-aqueous electrolyte secondary batteries, method for producing same, and non-aqueous electrolyte secondary battery
JP2017525090A (ja) * 2014-06-12 2017-08-31 ユミコア 充電式バッテリー用のリチウム遷移金属酸化物カソード材料の前駆体
JP2016095934A (ja) * 2014-11-12 2016-05-26 トヨタ自動車株式会社 二次電池
JP2016184528A (ja) * 2015-03-26 2016-10-20 日産自動車株式会社 非水電解質二次電池用正極およびこれを用いた非水電解質二次電池
US12218351B2 (en) 2016-03-31 2025-02-04 Honda Motor Co., Ltd. Positive electrode active material for nonaqueous electrolyte secondary battery
US11804600B2 (en) 2016-03-31 2023-10-31 Nichia Corporation Positive electrode active material for nonaqueous electrolyte secondary battery
JP2018147889A (ja) * 2016-03-31 2018-09-20 日亜化学工業株式会社 非水系電解質二次電池用正極活物質の製造方法
EP3225592A1 (fr) * 2016-03-31 2017-10-04 Honda Motor Co., Ltd. Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux
EP3594182A1 (fr) * 2016-03-31 2020-01-15 Honda Motor Co., Ltd. Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux
US11380892B2 (en) 2016-03-31 2022-07-05 Nichia Corporation Positive electrode active material for nonaqueous electrolyte secondary battery
JP2017188443A (ja) * 2016-03-31 2017-10-12 日亜化学工業株式会社 非水系電解質二次電池用正極活物質の製造方法
US10622629B2 (en) 2016-03-31 2020-04-14 Honda Motor Co., Ltd. Positive electrode active material for nonaqueous electrolyte secondary battery
US11165060B2 (en) 2016-05-24 2021-11-02 Sumitomo Chemical Company, Limited Cathode active material, its production process, and positive electrode for lithium ion secondary battery
WO2017204164A1 (fr) * 2016-05-24 2017-11-30 住友化学株式会社 Matériau actif d'électrode positive, son procédé de production, et électrode positive pour batteries rechargeables au lithium-ion
JPWO2017204164A1 (ja) * 2016-05-24 2019-03-22 住友化学株式会社 正極活物質、その製造方法およびリチウムイオン二次電池用正極
CN109155410A (zh) * 2016-05-24 2019-01-04 住友化学株式会社 正极活性物质、其制造方法和锂离子二次电池用正极
JP2018198132A (ja) * 2017-05-23 2018-12-13 本田技研工業株式会社 リチウムイオン二次電池用正極及びそれを用いるリチウムイオン二次電池
CN109244450A (zh) * 2018-10-24 2019-01-18 湖南海利锂电科技股份有限公司 一种用于混掺三元材料的高压实高容量型锰酸锂复合正极材料的制备方法
CN113474296A (zh) * 2019-02-22 2021-10-01 住友金属矿山株式会社 锂离子二次电池用正极活性物质、锂离子二次电池用正极活性物质的制造方法、锂离子二次电池
WO2020220662A1 (fr) * 2019-04-28 2020-11-05 宁德时代新能源科技股份有限公司 Matériau actif d'électrode positive, pôle d'électrode positive, batterie secondaire au lithium-ion et appareil
US12300816B2 (en) 2019-04-28 2025-05-13 Contemporary Amperex Technology (Hong Kong) Limited Positive electrode active material, positive electrode plate, lithium-ion secondary battery, and apparatus
US12176534B2 (en) 2019-04-28 2024-12-24 Contemporary Amperex Technology (Hong Kong) Limited Positive electrode active material, positive electrode plate, lithium-ion secondary battery, and apparatus
EP4148830A3 (fr) * 2019-04-28 2023-04-05 Contemporary Amperex Technology Co., Limited Matériau actif d'électrode positive, plaque d'électrode positive, batterie secondaire au lithium-ion et appareil
WO2021025101A1 (fr) 2019-08-06 2021-02-11 株式会社田中化学研究所 Particules d'hydroxyde composite de nickel, matériau actif d'électrode positive ayant des particules d'hydroxyde composite de nickel en tant que précurseurs, et procédé de production de matériau actif d'électrode positive
JPWO2021040033A1 (fr) * 2019-08-30 2021-03-04
US20220285676A1 (en) * 2019-08-30 2022-09-08 Sumitomo Metal Mining Co., Ltd. Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery
US12261293B2 (en) * 2019-08-30 2025-03-25 Sumitomo Metal Mining Co., Ltd. Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery
JP7677150B2 (ja) 2019-08-30 2025-05-15 住友金属鉱山株式会社 リチウムイオン二次電池用正極活物質およびリチウムイオン二次電池
US12334549B2 (en) 2019-08-30 2025-06-17 Sumitomo Metal Mining Co., Ltd. Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery
US12334550B2 (en) 2019-08-30 2025-06-17 Sumitomo Metal Mining Co., Ltd. Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery
CN115152060A (zh) * 2020-02-27 2022-10-04 松下知识产权经营株式会社 非水电解质二次电池用正极活性物质和非水电解质二次电池
JP7416734B2 (ja) 2021-02-05 2024-01-17 プライムプラネットエナジー＆ソリューションズ株式会社 非水電解質二次電池
JP2022120400A (ja) * 2021-02-05 2022-08-18 プライムプラネットエナジー＆ソリューションズ株式会社 非水電解質二次電池
US12431486B2 (en) 2021-02-05 2025-09-30 Prime Planet Energy & Solutions, Inc. Non-aqueous electrolyte secondary battery
JP2024159021A (ja) * 2023-04-28 2024-11-08 トヨタ自動車株式会社 正極活物質及びリチウムイオン二次電池

Also Published As

Publication number Publication date
JP6510402B2 (ja) 2019-05-08
JPWO2014175191A1 (ja) 2017-02-23

Similar Documents

Publication Publication Date Title
JP6510402B2 (ja) 複合化合物、リチウム含有複合酸化物、及びそれらの製造方法
JP6062947B2 (ja) リチウム二次電池用正極活物質の前駆体、正極活物質、その製造方法及びこれを含むリチウム二次電池
JP6471025B2 (ja) リチウム含有複合酸化物およびその製造方法
JP5428251B2 (ja) リチウム遷移金属系化合物粉体、それを用いたリチウム二次電池用正極及びリチウム二次電池
JP6487279B2 (ja) リチウム含有複合酸化物、正極活物質、リチウムイオン二次電池用正極およびリチウムイオン二次電池
JP6903260B2 (ja) リチウムイオン二次電池用負極及びリチウムイオン二次電池
WO2011125722A1 (fr) Matériau d'électrode positive pour batterie secondaire au lithium, procédé de production correspondant, électrode positive pour batterie secondaire au lithium et batterie secondaire au lithium
CN102714313A (zh) 锂二次电池正极材料用粉末及其制造方法、以及使用其的锂二次电池用正极及锂二次电池
JP2011108554A (ja) リチウム遷移金属系化合物粉体、その製造方法、及びそれを用いたリチウム二次電池用正極及びリチウム二次電池
JP2013065467A (ja) リチウムイオン二次電池
JP2008305777A (ja) リチウム遷移金属系化合物粉体、その製造方法、及びその焼成前躯体となる噴霧乾燥体、並びにそれを用いたリチウム二次電池用正極及びリチウム二次電池
US20070298324A1 (en) Process for producing lithium-containing composite oxide for positive electrode for lithium secondary battery
WO2013048071A2 (fr) Précurseur de matériau actif de cathode pour une pile secondaire au lithium, procédé de fabrication du précurseur, du matériau actif de cathode et pile secondaire au lithium comprenant le matériau actif de cathode
WO2009119104A1 (fr) Poudre de particules d’hydroxyde d’oxycobalt et procédé de fabrication de cette poudre, et également poudre de particules de cobaltate de lithium, procédé de fabrication de cette poudre, et batterie secondaire à électrolyte non aqueux les utilisant
JP2010534915A (ja) 非水電解質二次電池用多孔質網目構造電極
JP6495824B2 (ja) リチウム含有複合酸化物の製造方法、リチウムイオン二次電池用正極およびリチウムイオン二次電池
JP2012038680A (ja) リチウム二次電池用正極活物質材料及びその製造方法、並びにそれを用いたリチウム二次電池用正極及びリチウム二次電池
JP2014116162A (ja) 正極活物質
JP2006172753A (ja) リチウム二次電池正極材料用リチウムニッケルマンガン系複合酸化物粉体及びその製造方法、並びにそれを用いたリチウム二次電池用正極及びリチウム二次電池
JP4591716B2 (ja) リチウム二次電池正極材料用リチウム遷移金属系化合物粉体、その製造方法、噴霧乾燥体、および焼成前駆体、並びにそれを用いたリチウム二次電池用正極及びリチウム二次電池
WO2018123603A1 (fr) Électrode positive de batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
JP5232353B2 (ja) 非水電解質二次電池用電極組成物、これを用いた電極および電池
WO2018123671A1 (fr) Électrode positive de batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux
JP2014089848A (ja) 正極活物質およびその製造方法
JP2017200859A (ja) リチウム含有複合酸化物の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14789092

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015513733

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14789092

Country of ref document: EP

Kind code of ref document: A1