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WO2013100692A1 - Procédé de préparation de matériau actif de cathode pour batterie secondaire au lithium, et matériau actif de cathode - Google Patents

Procédé de préparation de matériau actif de cathode pour batterie secondaire au lithium, et matériau actif de cathode Download PDF

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Publication number
WO2013100692A1
WO2013100692A1 PCT/KR2012/011706 KR2012011706W WO2013100692A1 WO 2013100692 A1 WO2013100692 A1 WO 2013100692A1 KR 2012011706 W KR2012011706 W KR 2012011706W WO 2013100692 A1 WO2013100692 A1 WO 2013100692A1
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Prior art keywords
lithium
solvent
composite oxide
intercalating
deintercalating
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Korean (ko)
Inventor
최수안
이승원
권수연
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L&F MATERIAL CO Ltd
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L&F MATERIAL CO Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • 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

  • It relates to a method for producing a cathode active material for a lithium secondary battery and a cathode active material.
  • a battery generates power by using a material capable of electrochemical reactions at a positive electrode and a negative electrode.
  • a typical example of such a battery is a lithium secondary battery that generates electrical energy by a change in chemical potential when lithium ions are intercalated / deintercalated at a positive electrode and a negative electrode.
  • the lithium secondary battery is prepared by using a material capable of reversible intercalation / deintercalation of lithium ions as a positive electrode and a negative electrode active material, and filling an organic electrolyte or a polymer electrolyte between the positive electrode and the negative electrode.
  • a lithium composite metal compound is used as a cathode active material of a lithium secondary battery, and composite metal oxides such as LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , and LiMnO 2 have been studied.
  • Mn-based cathode active materials such as LiMn 2 O 4 and LiMnO 2 are easy to synthesize, are relatively inexpensive, have the best thermal stability compared to other active materials when overcharged, and have low environmental pollution and are attractive. Although it has a disadvantage, the capacity is small.
  • LiCoO 2 has a good electrical conductivity and a high battery voltage of about 3.7V, and also has excellent cycle life characteristics, stability, and discharge capacity, and thus, is a representative cathode active material commercially available and commercially available. However, since LiCoO 2 is expensive, it takes up more than 30% of the battery price, and thus, price competitiveness is inferior.
  • LiNiO 2 exhibits the highest discharge capacity of battery characteristics among the cathode active materials mentioned above, but has a disadvantage in that it is difficult to synthesize.
  • the high oxidation state of nickel causes a decrease in battery and electrode life, and there is a problem of severe self discharge and inferior reversibility.
  • it is difficult to commercialize the stability is not perfect.
  • LiNi 0.8 Co 0.2 is a partial substitution of Co for LiNiO 2 O 2 cathode material and to form a well layered structure required as the positive electrode material by the Co doped, where LiNi to kkoehagi structural stabilization to 0.8 Co 0.2 O 2 in the positive electrode material Al LiNi 0.8 Co 0.15 Al 0.05 O 2 (hereinafter referred to as NCA) material which is partially doped with is gradually being applied as a high capacity material.
  • NCA LiNi 0.8 Co 0.15 Al 0.05 O 2
  • Al element is widely used as a doping material to improve the structural stability of the positive electrode material, and is also widely used as an oxide coating material mainly for the purpose of improving the high rate characteristics and battery life. (KR 2002-0029218)
  • JP 1998-097857 a method for producing Al-containing nickel hydroxide is disclosed, but when Al is co-precipitated on a precursor, particle growth is not good and a high density precursor is difficult to obtain.
  • JP 2012-009458 discloses a technique for introducing Al by mixing and firing a lithium compound, a nickel compound, aluminum or an aluminum compound, but has difficulty in uniformly doping Al into an active material or controlling a desired doping thickness.
  • JP 2010-24083 discloses a nickel cobalt composite hydroxide coated with aluminum hydroxide, but Al is diffused into the active material under baking conditions (750 ° C. or more) to have a sufficient crystal structure as a cathode material by mixing with a lithium compound It has the disadvantage that doping thickness control is difficult.
  • preparing a coating solution by mixing a first solvent, a first Al feed material soluble in the first solvent and a second Al feed material insoluble in the first solvent; Injecting a lithium composite oxide capable of intercalating / deintercalating lithium ions into the coating solution, the first Al supply material on the surface of the lithium composite oxide capable of intercalating / deintercalating the lithium ions And stirring to coat the second Al feed material; And calcining a lithium composite oxide capable of intercalating / deintercalating lithium ions coated with the first Al supply material and the second Al supply material on the surface thereof. It provides a method for producing.
  • the first Al supply material on the surface of the lithium composite oxide capable of intercalating / deintercalating the lithium ions
  • stirring the second Al feed material to be coated wherein the second Al feed material is coated in an island form on a surface of the lithium composite oxide capable of intercalating / deintercalating the lithium ions.
  • the first Al feed material may be coated on a lithium composite oxide surface capable of intercalating / deintercalating the lithium ions in a film form.
  • Preparing a coating solution by mixing the first solvent, a first Al feed material soluble in the first solvent, and a second Al feed material insoluble in the first solvent, wherein the first solvent is soluble in the first solvent. Dissolving 1 Al feed material in said first solvent; And preparing a coating solution by mixing a second Al feed material which is insoluble in the first solvent in a solvent in which the first Al feed material is dissolved.
  • Preparing a coating solution by mixing the first solvent, a first Al feed material soluble in the first solvent, and a second Al feed material insoluble in the first solvent, wherein the first solvent is soluble in the first solvent. Dissolving 1 Al feed material in said first solvent; And preparing a coating solution by mixing a second Al supply material insoluble in the first solvent and a lithium supply material in a solvent in which the first Al supply material is dissolved.
  • the lithium feed material may be soluble in the first solvent.
  • the first solvent and the second solvent may be the same.
  • the first Al feed material soluble in the first solvent may be Al-alkoxide, Al-acetate, Al-nitrate, Al-sulfate, or a combination thereof.
  • the second Al feed material insoluble in the first solvent may be Al 2 O 3 , Al (OH) 3 , or a combination thereof, but is not limited thereto.
  • the lithium supply material may be any one of nitrate, carbonate, acetate, oxalate, oxide, hydroxide, and sulfate including lithium. May be selected or a combination thereof.
  • the ratio of the second Al feed material / first Al feed material may be 1.5 to 4 based on the Al element.
  • the method may further include evaporating the first solvent included in the coating solution.
  • the lithium composite oxide capable of intercalating / deintercalating the lithium ions may be nickel-cobalt oxide or nickel-manganese oxide.
  • the lithium composite oxide capable of intercalating / deintercalating the lithium ions may include Li a A 1 -b X b D 2 (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5); Li a A 1-b X b O 2-c T c (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); LiE 1-b X b O 2-c D c (0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); LiE 2-b X b 0 4-c T c (0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); Li a Ni 1-bc Co b X c D ⁇ (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, 0 ⁇ ⁇ 2); Li a Ni 1-bc Co b X c 0
  • A is selected from the group consisting of Ni, Co, Mn, and combinations thereof;
  • X is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements and combinations thereof;
  • D is selected from the group consisting of O, F, S, P, and combinations thereof;
  • E is selected from the group consisting of Co, Mn, Ni, and combinations thereof;
  • T is selected from the group consisting of F, S, P, and combinations thereof;
  • G is selected from the group consisting of Ni, Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V and combinations thereof;
  • G ⁇ is selected from the group consisting of Ni, Al, Cr, Fe, Mg, La, Ce, Sr, V and combinations thereof;
  • Q is selected from the group consisting of Ti, Mo, Mn, Ni, and combinations thereof;
  • Z is selected from the group consisting of Cr, V, Fe, Sc, Y, Ni, and combinations thereof;
  • J is
  • Preparing a coating solution by mixing the first solvent, a first Al supply material soluble in the first solvent, and a second Al supply material insoluble in the first solvent; the first solvent, the first solvent Preparing a coating solution by mixing a first Al supply material soluble in a solvent, a second Al supply material insoluble in the first solvent, and a lithium supply material.
  • the first Al feed material coated in a film form diffuses into the lithium composite oxide to form an Al doping layer
  • the second feed material coated in an island form on the surface of the lithium composite oxide forms a film on the surface of the lithium composite oxide. May be coated to form an Al coating layer.
  • lithium composite oxide core particles capable of intercalating / deintercalating lithium ions; An Al doped layer diffused inward from the surface portion of the core particles; And it provides a cathode active material for a lithium secondary battery comprising an Al coating layer formed on the surface of the core particles.
  • the lattice constant of the X-ray diffraction image (XRD) phase of the positive electrode active material may have a value of 2.864 to 2.868 ⁇ .
  • the Al coating layer may be a coating layer containing Li-Al.
  • the lithium composite oxide core particles capable of intercalating / deintercalating the lithium ions may be represented by the following Chemical Formula 1.
  • the cathode active material may be prepared by the manufacturing method according to the embodiment of the present invention described above.
  • cathode active material having high capacity and improved high rate and long life characteristics.
  • FIG. 1 is a schematic view of a lithium secondary battery.
  • lithium composite oxide core particles capable of intercalating / deintercalating lithium ions; An Al doped layer diffused inward from the surface portion of the core particles; And it provides a cathode active material for a lithium secondary battery comprising an Al coating layer formed on the surface of the core particles.
  • the cathode active material may be appropriately doped and / or coated with Al to improve the life characteristics of the battery using the same.
  • the Al doped layer may have a thickness of 0.5 to 3 ⁇ m.
  • the Al coating layer may have a thickness of 10 to 100nm.
  • the cathode active material may have a lattice constant of a value of 2.864 to 2.868 ⁇ due to an Al doped layer diffused from the surface portion of the core particle into the X-ray diffraction image (XRD).
  • XRD X-ray diffraction image
  • the Al coating layer may be a Li-Al composite compound based on the remaining lithium on the surface of the active material or a separately added Li source.
  • the lithium composite oxide core particles capable of intercalating / deintercalating the lithium ions may be represented by the following Chemical Formula 1, but are not limited thereto.
  • the lithium composite oxide core particles capable of intercalating / deintercalating the lithium ions may be represented by the following Chemical Formula 1-1, but are not limited thereto.
  • preparing a coating solution by mixing a first solvent, a first Al feed material soluble in the first solvent and a second Al feed material insoluble in the first solvent; Injecting a lithium composite oxide capable of intercalating / deintercalating lithium ions into the coating solution, the first Al supply material on the surface of the lithium composite oxide capable of intercalating / deintercalating the lithium ions And stirring to coat the second Al feed material; And calcining a lithium composite oxide capable of intercalating / deintercalating lithium ions coated with the first Al supply material and the second Al supply material on the surface thereof. It provides a method for producing.
  • the positive electrode active material may be appropriately doped and coated with an Al component by simultaneously using a first Al supply material soluble in the first solvent and a second Al supply material insoluble in the first solvent. This may improve the battery life characteristics.
  • a lithium composite oxide capable of intercalating / deintercalating lithium ions is introduced into the coating solution to the surface of the lithium composite oxide capable of intercalating / deintercalating the lithium ions.
  • the first Al feed material may be coated on a lithium composite oxide surface capable of intercalating / deintercalating the lithium ions in a film form.
  • the first Al feed material coated in a film form diffuses into the lithium composite oxide to form an Al doping layer
  • the second feed material coated in an island form on the surface of the lithium composite oxide forms a film on the surface of the lithium composite oxide. May be coated to form an Al coating layer.
  • the first Al supply material and the second Al supply material may react more effectively with the lithium composite oxide capable of intercalating / deintercalating the lithium ions.
  • a mixing method There is no limit.
  • Preparing a coating solution by mixing the first solvent, a first Al supply material soluble in the first solvent, and a second Al supply material insoluble in the first solvent; the first solvent, the first solvent Preparing a coating solution by mixing a first Al supply material soluble in a solvent, a second Al supply material insoluble in the first solvent, and a lithium supply material.
  • preparing a coating solution by mixing the first solvent, the first Al feed material soluble in the first solvent and the second Al feed material insoluble in the first solvent; Dissolving a first Al feed material soluble in the first solvent; And preparing a coating solution by mixing a second Al supply material insoluble in the first solvent and a lithium supply material in a solvent in which the first Al supply material is dissolved.
  • lithium which may be lost in the subsequent firing step may be replenished, and doping of Al may be promoted by lithium, thereby improving the lifespan characteristics of the battery.
  • the lithium feed material may be soluble in the first solvent.
  • the lithium supply material may be any one of nitrate, carbonate, acetate, oxalate, oxide, hydroxide, and sulfate including lithium. May be selected or a combination thereof, but is not limited thereto.
  • the first solvent is ethyl alcohol, methyl alcohol, normal propyl alcohol, n-propyl alcohol, i-propyl alcohol, normal butyl alcohol, sec It may be an alcohol solvent of butyl alcohol (sec-butyl alcohol) and tert-butyl alcohol (tert-butyl alcohol).
  • the second solvent may be an alcohol solvent, water, acetone, or the like.
  • the first solvent and the second solvent may be the same.
  • the first Al feed material soluble in the first solvent may be, but is not limited to, Al-alkoxide, Al-acetate, Al-nitrate, Al-sulfate, or a combination thereof.
  • the second Al feed material insoluble in the first solvent may be Al 2 O 3 , Al (OH) 3 , or a combination thereof, but is not limited thereto.
  • the ratio of the first Al feed material and the second Al feed material may be 1.5 to 4. In this case, doping and coating can take place effectively.
  • the ratio is less than 1.5, the amount of the soluble Al feed material for doping and coating is relatively increased, causing ignition due to the catalytic properties of the nano Al compound during firing.
  • the ratio exceeds 4, the amount of insoluble Al feedstock is increased so that doping may not be sufficient and an excess of Al compound remains on the surface.
  • the method may further include evaporating the first solvent included in the coating solution.
  • the lithium composite oxide capable of intercalating / deintercalating the lithium ions may be nickel-cobalt-based oxide or nickel-cobalt-manganese oxide and nickel-manganese oxide.
  • Li a A 1-b X b D 2 (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5); Li a A 1-b X b O 2-c T c (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); LiE 1-b X b O 2-c D c (0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); LiE 2-b X b 0 4-c T c (0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); Li a Ni 1-bc Co b X c D ⁇ (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, 0 ⁇ ⁇ 2); Li a Ni 1-bc Co b X c 0 2- ⁇ T ⁇ (0.90 ⁇ a ⁇ 1.8, 0 ⁇ b
  • A is selected from the group consisting of Ni, Co, Mn, and combinations thereof;
  • X is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements and combinations thereof;
  • D is selected from the group consisting of O, F, S, P, and combinations thereof;
  • E is selected from the group consisting of Co, Mn, Ni, and combinations thereof;
  • T is selected from the group consisting of F, S, P, and combinations thereof;
  • G is selected from the group consisting of Ni, Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V and combinations thereof;
  • G ⁇ is selected from the group consisting of Ni, Al, Cr, Fe, Mg, La, Ce, Sr, V and combinations thereof;
  • Q is selected from the group consisting of Ti, Mo, Mn, Ni, and combinations thereof;
  • Z is selected from the group consisting of Cr, V, Fe, Sc, Y, Ni, and combinations thereof;
  • J is
  • a lithium secondary battery including a positive electrode, a negative electrode and an electrolyte, the positive electrode includes a current collector and a positive electrode active material layer formed on the current collector, the positive electrode active material layer, It provides a lithium secondary battery comprising one cathode active material.
  • the positive electrode active material layer may include a binder and a conductive material.
  • the binder adheres positively to the positive electrode active material particles, and also serves to adhere the positive electrode active material to the current collector well, and examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and polyvinyl. Chloride, carboxylated polyvinylchloride, polyvinylfluoride, polymer comprising ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene- Butadiene rubber, acrylic styrene-butadiene rubber, epoxy resin, nylon and the like can be used, but is not limited thereto.
  • the conductive material is used to impart conductivity to the electrode, and any battery can be used as long as it is an electronic conductive material without causing chemical change in the battery.
  • any battery can be used as long as it is an electronic conductive material without causing chemical change in the battery.
  • Carbon-based materials such as black and carbon fibers;
  • Metal materials such as metal powder or metal fibers such as copper, nickel, aluminum and silver; Conductive polymers such as polyphenylene derivatives; Or a conductive material containing a mixture thereof.
  • the negative electrode includes a current collector and a negative electrode active material layer formed on the current collector, and the negative electrode active material layer includes a negative electrode active material.
  • the anode active material includes a material capable of reversibly intercalating / deintercalating lithium ions, a lithium metal, an alloy of lithium metal, a material capable of doping and undoping lithium, or a transition metal oxide.
  • any carbon-based negative electrode active material generally used in a lithium ion secondary battery may be used, and representative examples thereof include crystalline carbon. , Amorphous carbon or these can be used together.
  • the crystalline carbon include graphite such as amorphous, plate, flake, spherical or fibrous natural graphite or artificial graphite.
  • the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, calcined coke, or the like.
  • alloy of the lithium metal examples include lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn. Alloys of the metals selected may be used.
  • Examples of the material capable of doping and undoping lithium include Si, SiO x (0 ⁇ x ⁇ 2), Si-Y alloys (wherein Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, Is an element selected from the group consisting of rare earth elements and combinations thereof, not Si), Sn, SnO 2 , Sn-Y (Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth) An element selected from the group consisting of elements and combinations thereof, and not Sn; and at least one of these and SiO 2 may be mixed and used.
  • transition metal oxide examples include vanadium oxide, lithium vanadium oxide, and the like.
  • the negative electrode active material layer also includes a binder, and optionally may further include a conductive material.
  • the binder adheres the anode active material particles to each other well, and also serves to adhere the anode active material to the current collector well, and representative examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, and carboxylation.
  • Polyvinylchloride, polyvinylfluoride, polymers including ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylic ray Tied styrene-butadiene rubber, epoxy resin, nylon, and the like may be used, but is not limited thereto.
  • the conductive material is used to impart conductivity to the electrode, and any battery can be used as long as it is an electronic conductive material without causing chemical change in the battery.
  • any battery can be used as long as it is an electronic conductive material without causing chemical change in the battery.
  • Carbon-based materials such as black and carbon fibers;
  • Metal materials such as metal powder or metal fibers such as copper, nickel, aluminum and silver; Conductive polymers such as polyphenylene derivatives; Or a conductive material containing a mixture thereof.
  • the current collector may be selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and combinations thereof.
  • Al may be used as the current collector, but is not limited thereto.
  • the negative electrode and the positive electrode are prepared by mixing an active material, a conductive material and a binder in a solvent to prepare an active material composition, and applying the composition to a current collector. Since such an electrode manufacturing method is well known in the art, detailed description thereof will be omitted. N-methylpyrrolidone may be used as the solvent, but is not limited thereto.
  • the electrolyte contains a non-aqueous organic solvent and a lithium salt.
  • the non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the cell can move.
  • a carbonate, ester, ether, ketone, alcohol or aprotic solvent can be used as the non-aqueous organic solvent.
  • the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), and ethylene carbonate ( EC), propylene carbonate (PC), butylene carbonate (BC) and the like
  • the ester solvent is methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate , ⁇ -butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, and the like may be used.
  • Dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran may be used as the ether solvent, and cyclohexanone may be used as the ketone solvent.
  • ethyl alcohol, isopropyl alcohol, etc. may be used as the alcohol solvent, and the aprotic solvent may be R-CN (R is a straight-chain, branched, or cyclic hydrocarbon group having 2 to 20 carbon atoms.
  • Amides such as nitriles, dimethylformamide, and dioxolanes such as 1,3-dioxolane, and sulfolanes such as 1,3-dioxolane.
  • the non-aqueous organic solvent may be used alone or in combination of one or more, and the mixing ratio in the case of mixing one or more may be appropriately adjusted according to the desired battery performance, which is widely understood by those skilled in the art. Can be.
  • the carbonate solvent it is preferable to use a mixture of a cyclic carbonate and a chain carbonate.
  • the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of 1: 1 to 1: 9, so that the performance of the electrolyte may be excellent.
  • the non-aqueous organic solvent of the present invention may further include an aromatic hydrocarbon organic solvent in the carbonate solvent.
  • the carbonate solvent and the aromatic hydrocarbon organic solvent may be mixed in a volume ratio of 1: 1 to 30: 1.
  • an aromatic hydrocarbon compound of Formula 2 may be used as the aromatic hydrocarbon organic solvent.
  • R 1 to R 6 are each independently hydrogen, halogen, C1 to C10 alkyl group, haloalkyl group, or a combination thereof.
  • the aromatic hydrocarbon organic solvent is benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene , 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2, 4-trichlorobenzene, iodobenzene, 1,2-dioodobenzene, 1,3-dioodobenzene, 1,4-dioiobenzene, 1,2,3-triiodobenzene, 1,2,4 -Triiodobenzene, toluene, fluorotoluene, 1,2-difluorotoluene, 1,3-difluorotoluene
  • the non-aqueous electrolyte may further include vinylene carbonate or an ethylene carbonate-based compound of Formula 3 to improve battery life.
  • R 7 and R 8 are each independently hydrogen, a halogen group, a cyano group (CN), a nitro group (NO 2 ), or a C1 to C5 fluoroalkyl group, and at least one of R 7 and R 8 Is a halogen group, cyano group (CN), nitro group (NO 2 ) or C1 to C5 fluoroalkyl group.
  • ethylene carbonate-based compound examples include difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate or fluoroethylene carbonate. Can be. In the case of further using such life improving additives, the amount thereof can be properly adjusted.
  • the lithium salt is a substance that dissolves in an organic solvent, acts as a source of lithium ions in the battery to enable operation of the basic lithium secondary battery, and promotes movement of lithium ions between the positive electrode and the negative electrode.
  • Representative examples of such lithium salts are LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y +1 SO 2 ), where x and y are natural water, LiCl, LiI and LiB (C 2 O 4 ) 2 (lithium bis (oxalato) borate (LiBOB) Including one or more of the supporting electrolytic salt, the concentration of the lithium salt is preferably used within the range of 0.1 to 2.0 M. When the concentration of the lithium salt is included in the above range, the electrolyte has an appropriate conductivity and viscosity
  • a separator may exist between the positive electrode and the negative electrode.
  • the separator polyethylene, polypropylene, polyvinylidene fluoride or two or more multilayer films thereof may be used, and polyethylene / polypropylene two-layer separator, polyethylene / polypropylene / polyethylene three-layer separator, polypropylene / polyethylene / poly It goes without saying that a mixed multilayer film such as a propylene three-layer separator can be used.
  • the lithium secondary battery may be classified into a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery according to the type of separator and electrolyte used, and may be classified into a cylindrical shape, a square shape, a coin type, a pouch type, and the like. Depending on the size, it can be divided into bulk type and thin film type. Since the structure and manufacturing method of these batteries are well known in the art, detailed description thereof will be omitted.
  • the lithium secondary battery 1 schematically shows a typical structure of a lithium secondary battery of the present invention.
  • the lithium secondary battery 1 includes a positive electrode 3, a negative electrode 2, and an electrolyte solution impregnated in a separator 4 existing between the positive electrode 3 and the negative electrode 2.
  • the container 5 and the sealing member 6 which encloses the said battery container 5 are included.
  • LiNi 0.84 Co 0.16 O 2 as a lithium composite oxide core particle was insoluble based on Al element.
  • a lithium composite oxide capable of intercalating / deintercalating lithium ions was prepared in the same manner as in Example 1 except that the ratio of the Al feed material / soluble Al feed material was coated to be 1.5.
  • LiNi 0.84 Co 0.16 O 2 as a lithium composite oxide core particle was insoluble based on Al element.
  • a lithium composite oxide capable of intercalating / deintercalating lithium ions was prepared in the same manner as in Example 1 except that the ratio of the Al feed material / soluble Al feed material was coated to 4.
  • a lithium composite oxide capable of intercalating / deintercalating lithium ions was prepared in the same manner as in Example 2 except that Li actetate was not added.
  • a lithium composite oxide capable of intercalating / deintercalating lithium ions was prepared in the same manner as in Example 1 except that 100 g of LiNi 0.838 Co 0.16 Zr 0.002 O 2 was used as the lithium composite oxide core particle.
  • a lithium composite oxide capable of intercalating / deintercalating lithium ions was prepared in the same manner as in Example 1 except that 100 g of LiNi 0.838 Co 0.16 Ti 0.002 O 2 was used as the lithium composite oxide core particle.
  • a lithium composite oxide capable of intercalating / deintercalating lithium ions was prepared in the same manner as in Example 1, except that 100 g of LiNi 0.838 Co 0.16 Mg 0.002 O 2 was used as the lithium composite oxide core particle.
  • a lithium composite oxide capable of intercalating / deintercalating lithium ions was prepared in the same manner as in Example 1 except that 100 g of LiNi 0.70 Co 0.15 Mn 0.15 O 2 was used as the lithium composite oxide core particle.
  • a lithium composite oxide capable of intercalating / deintercalating lithium ions was prepared in the same manner as in Example 1 except that 100 g of LiNi 0.60 Co 0.20 Mn 0.20 O 2 was used as the lithium composite oxide core particle.
  • LiOH manufactured by the manufacturer: SQM
  • Ni 0.84 Co 0.16 (OH) 2 in a weight ratio of 1: 1.08 precursor: Li
  • the total baking time was 20 hours, and a fired body was produced.
  • the resulting fired body was slowly cooled and pulverized to prepare a positive electrode active material powder of the lithium metal composite oxide of the present invention.
  • the obtained active material is shown in Table 1 by measuring the C content and preparing a battery using the same, evaluating battery performance.
  • Li acetate 5 g was added to 152 g of the prepared coating solution, which was then stirred at a high speed to prepare a coating solution.
  • Lithium composite oxide core particles were coated in the same manner as in Example 1 except that only 100 g of LiNi 0.84 Co 0.16 O 2 was coated with a soluble Al feed material.
  • a lithium composite oxide capable of intercalating / deintercalating ions was prepared.
  • Example 1 Into the prepared coating solution 76g of Li acetate 5g and 1.8g of insoluble Al (OH) 3 , respectively, was added at a high speed to prepare a coating slurry.
  • the lithium composite oxide core particles were insoluble based on Al element for 100g of LiNi 0.84 Co 0.16 O 2.
  • a lithium composite oxide capable of intercalating / deintercalating lithium ions was prepared in the same manner as in Example 1 except that the ratio of the Al feed material / soluble Al feed material was coated to 1.0.
  • Li acetate and 3 g of insoluble Al (OH) 3 were added thereto, followed by high-speed stirring to prepare a coating slurry.
  • LiNi 0.84 Co 0.16 O 2 was used as insoluble Al based on Al element.
  • a lithium composite oxide capable of intercalating / deintercalating lithium ions was prepared in the same manner as in Example 1 except that the ratio of the feed material / soluble Al feed material was coated to 5.
  • LiOH manufactured by SQM
  • Ni 0.80 Co 0.15 Al 0.05 (OH) 2 Tiaka
  • the reaction time was raised in air for 6 hours, holding period.
  • the total calcining time was 20 hours.
  • the resulting fired body was slowly cooled and pulverized to prepare a positive electrode active material powder of the lithium metal composite oxide of the present invention.
  • the obtained active material is shown in Table 1 by measuring the C content and preparing a battery using the same, evaluating battery performance.
  • LiOH manufactured by SQM
  • the resulting fired body was slowly cooled and pulverized to prepare a positive electrode active material powder of the lithium metal composite oxide of the present invention.
  • the composition of the obtained active material is LiNi 0.80 Co 0.15 Al 0.05 O 2 by measuring the C content, and preparing a battery using the same, it is shown in Table 1 to evaluate the battery performance.
  • a coating solution was prepared using only a soluble Al feed material, and coated and calcined to have an Al content of 2000 ppm, thereby preparing a lithium composite oxide capable of intercalating / deintercalating lithium ions.
  • a positive electrode slurry was prepared by adding to pyrrolidone (NMP) 5.0 wt%. The positive electrode slurry was applied to an aluminum (Al) thin film, which is a positive electrode current collector having a thickness of 20 to 40 ⁇ m, vacuum dried, and roll pressed to prepare a positive electrode.
  • NMP pyrrolidone
  • Li-metal was used as the negative electrode.
  • a coin cell type half cell was manufactured by using a cathode and a Li-metal as the counter electrode and 1.15 M LiPF 6 EC: DMC (1: 1 vol%) as an electrolyte.
  • Table 1 shows data of lattice constants, initial formation, rate characteristics, capacity of 1 cycle, and capacity retention after 30 cycles of Examples 1 to 9 and Comparative Examples 1 to 7.
  • Examples 1 to 9 showed improved 1-cycle capacity and especially long life compared to Comparative Examples 1 to 6.
  • Examples 1 to 4 are slightly lower in efficiency compared to Comparative Examples 4 and 5, but it can be seen that the rate characteristics, 1 cycle capacity, and long life characteristics are significantly improved.
  • Comparative Example 1 was prepared from a Ni 0.84 Co 0.16 ( OH) 2 precursor having a composition of LiNi 0.84 Co 0.16 O 2 , and was not subjected to Al doping, which is an oxidizing element.
  • Comparative Example 2 was coated with only the soluble Al feed material, so that ignition occurred during firing, and thus application was impossible in the process.
  • Comparative Example 3 the ratio of the insoluble Al feed material / soluble Al feed material was coated to 1.0 based on the Al element, which is also coated with only the soluble Al feed material, so that ignition occurs during firing, and thus, the process cannot be applied.
  • Comparative Example 5 is an example of using a precursor doped with Al in a composition of LiNi 0.80 Co 0.15 OAl 0.05 O 2
  • the initial capacity and efficiency is high, but shows a low rate characteristics, 1 cycle capacity, and life characteristics compared to the embodiment.
  • Comparative Example 6 is an example obtained by mixing and baking a lithium raw material, Al (OH) 3, and Ni 0.86 Co 0.16 (OH) 2 , and the efficiency and 1cycle capacity are reduced compared to Comparative Example 5, and the 30-cycle lifespan characteristics are improved, but It shows a lower characteristic than the embodiment.
  • Comparative Example 7 the cathode material obtained in Comparative Example 6 was treated only with a soluble Al feed material, and it was found that the lifespan characteristics of the example were excellent although the improvement effect was obtained compared to Comparative Example 6.
  • the measurement equipment was an ultra-fine secondary ion mass spectrometer (Nano SIMS50, CAMECA) to perform Al line mapping from the Cs ion source to the bulk surface at the particle surface.

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KR20160093817A (ko) * 2015-01-30 2016-08-09 주식회사 엘 앤 에프 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지
KR102072221B1 (ko) * 2016-06-17 2020-03-02 주식회사 엘지화학 도펀트의 농도 구배가 있는 리튬 이차전지용 양극 활물질
KR102017421B1 (ko) * 2018-04-26 2019-09-02 서울과학기술대학교 산학협력단 원-포트(One-pot) 합성법을 통한 금속 산화물 코팅 및 금속 도핑된 양극 소재의 제조방법 및 이를 통해 제조된 양극 소재
KR20250093950A (ko) * 2023-12-18 2025-06-25 포스코홀딩스 주식회사 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지

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