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WO2015122690A1 - Cathode active material for lithium secondary battery, preparation method therefor, and lithium secondary batter containing same - Google Patents

Cathode active material for lithium secondary battery, preparation method therefor, and lithium secondary batter containing same Download PDF

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Publication number
WO2015122690A1
WO2015122690A1 PCT/KR2015/001388 KR2015001388W WO2015122690A1 WO 2015122690 A1 WO2015122690 A1 WO 2015122690A1 KR 2015001388 W KR2015001388 W KR 2015001388W WO 2015122690 A1 WO2015122690 A1 WO 2015122690A1
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Prior art keywords
formula
active material
lithium secondary
secondary battery
positive electrode
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PCT/KR2015/001388
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French (fr)
Korean (ko)
Inventor
이승원
권혁원
홍진곤
정봉준
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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
    • H01M4/36—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
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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 cathode active material for a lithium secondary battery, a method of manufacturing the same, and a lithium secondary battery including the same.
  • a battery generates electric power by using an electrochemical reaction material for the positive electrode and the negative electrode.
  • a typical example of such a battery is a lithium secondary battery that generates electrical energy by changing a chemical potential (chemi cal potential) when lithium silver is 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 silver 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 cathode active material of a lithium secondary battery is a lithium composite metal compound is used, it is.
  • Examples LiCo3 ⁇ 4, LiMn 2 0 4, LiNi0 2, LiMn0 2 such as a complex metal oxide have been studied in ".
  • Mn-based cathode active materials such as LiMn 2 O 4 and LiMn0 2 are easy to synthesize, are relatively inexpensive, have the best thermal stability compared to other active materials during overheating, and have low environmental pollution and are attractive materials. Although it has a disadvantage, the capacity is small.
  • LiCo0 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. Thus, LiCo0 2 is a representative cathode active material commercially available and commercially available. However, since LiCo0 2 is expensive, it takes up more than 30% of the battery price, which makes the price competitive. have.
  • LiNi0 2 exhibits the highest discharge capacity of battery characteristics among the cathode active materials mentioned above, but has a disadvantage of being 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.
  • a core comprising a compound represented by the following formula (1); And it provides a positive electrode active material for a lithium secondary battery comprising a coating layer located on the surface of the core and comprising a compound represented by the formula 2-1 and / or 2-2.
  • M 1 and M 2 are independently of each other, Zr, Ti, Ca, V, Zn, Mo,
  • Ni, Mn, or a combination thereof may be 0.90 ⁇ a ⁇ 1.10, 0 ⁇ b ⁇ 0.1, 0 ⁇ c ⁇ 0.1, 0 ⁇ d ⁇ 0.1, 0 ⁇ z ⁇ 0.1.
  • ⁇ 3 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, and may be 0 ⁇ x ⁇ 4.
  • M 4 F y -In Formula 2-2 M 4 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, and may be 0 ⁇ y ⁇ 4.
  • the weight ratio of MVM 2 in the cathode active material may be 0.8 to 1.2.
  • M 1 may be Ca.
  • M 2 may be Ti, Zr, or a combination thereof.
  • the molar dosing ratios of Mg, M 1, and M 2 may be 0.001 to 0.01 independently of each other.
  • the compound represented by Chemical Formula 2-1 may be CaF 2 or TiF 4 .
  • M 3 of Formula 2-1 may be derived from M 1 of Formula 1 , or M 2 .
  • M 4 of Chemical Formula 2-2 may be derived from Co, or Mg of Chemical Formula 1.
  • the weight ratio of Ca / Mg may be 0.3 to 0.8.
  • the core comprising a compound represented by the formula (3); And it provides a cathode active material for a lithium secondary battery comprising a coating layer located on the surface of the core and comprising a compound represented by the following formula 4-1 and / or 4-2.
  • A Ni a Co p Mn Y , M 1 and M 2 are independently of each other, Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, -0.05 ⁇ a ⁇ 0.1, 0 ⁇ b ⁇ 0.1, 0 ⁇ c ⁇ 0.1, 0 ⁇ d ⁇ 0.1, 0 ⁇ z ⁇ 0.1, 0.6 ⁇ a ⁇ 0.81, 0.10 ⁇ ⁇ 0.20 and 0.10 ⁇ 0.20,
  • M 3 is represented by Chemical Formula .
  • M 4 is derived from Ni, Co, Mn, or Mg of Formula 3, and 0 ⁇ y ⁇ 4, and the weight ratio of MVM 2 in the cathode active material is 0.8 to 1.2.
  • M 1 and M 2 are independently of each other, Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, 0.90 ⁇ a ⁇ 1.10, 0 ⁇ b ⁇ 0.1, 0 ⁇ c ⁇ 0.1, 0 ⁇ d ⁇ 0.1, 0 ⁇ z ⁇ 0.1.
  • M 3 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, and may be 0 ⁇ x ⁇ 4.
  • M 4 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, and may be 0 ⁇ y ⁇ 4.
  • the weight ratio of MVM 2 in the cathode active material may be 0.8 to 1.2.
  • the feed materials of Mg, M 1 and M 2 may independently be in the form of hydroxide, oxyhydroxide, nitrate, halide, carbonate, acetate, oxalate or citrate.
  • the fluorine feed material may be in the form of ammonium salt, lithium salt or metal salt.
  • the firing temperature may be 800 to 1,050 t.
  • a positive electrode active material having excellent battery characteristics and a lithium secondary battery including the same can be provided.
  • FIG. 1 is a schematic view of a lithium secondary battery.
  • Example 2 is an X-ray photoelectron spectroscopic analysis graph of the positive electrode active material of Example 1. [Specific contents to carry out invention]
  • the core comprising a compound represented by the formula (1); And it provides a cathode active material for a lithium secondary battery comprising a coating layer located on the surface of the core and comprising a compound represented by the following formulas 2-1 and / or 2-2 ⁇ [Formula 1]
  • M 1 and M 2 are each independently Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, and 0.90 ⁇ a ⁇ 1.10, 0 ⁇ b ⁇ 0.1, 0 ⁇ c ⁇ 0.1, 0 ⁇ d ⁇ 0.1, 0 ⁇ z ⁇ 0.1,
  • M 3 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, 0 ⁇ x ⁇ 4
  • M 4 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, 0 ⁇ y ⁇ 4,
  • the weight ratio of the positive electrode active material within the MVM 2 is 0.8 to 1.2.
  • the compound capable of reversible intercalation and deintercalation of lithium which is a core of the positive electrode active material according to the embodiment of the present invention, includes Mg and M 1 and M 2 are illustrated in FIG. 3 .
  • L and M 2 may be independently a metal which is Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof. .
  • the compound capable of reversible intercalation and deintercalation of lithium may be lithium cobalt complex oxide.
  • the general lithium cobalt composite oxide has severe capacity and life deterioration at high voltage.
  • improvement of the core part structure and surface modification of the surface part need improvement of this problem.
  • the thermal stability and the Mg to stabilize the structure must be included at the same time, the above problems can be solved by the doping of the M 1 and M 2 .
  • M 1 may be a Ca.
  • M 2 may be Ti, Zr, or a combination thereof.
  • the molar doping ratios of Mg, M 1, and M 2 may be 0.001 to 0.01 independently of each other.
  • the molar doping ratio of less than 0.001 may not show an effect due to doping, and the molar doping ratio of more than 0.01 may result in excessive decrease in initial capacity and decrease in efficiency characteristics.
  • the temperature for effective firing may be 800 to 1,050 ° C.
  • the temperature when the temperature is less than 800 ° C., a sudden decrease in battery characteristics at room temperature and high silver may appear.
  • firing at a temperature of more than 1,050 ° C. can drastically lower the capacity and capacity retention rate.
  • the Mg / M 1 and M 2 may be doped into the core while undergoing the firing process.
  • the doped elements vary depending on the ionic radius.
  • doping is uniform in the core, but Elements such as Ca, Ti, Zr, etc., which have a large radius, have a large ion radius in the bulk of the core, which causes some doping to the core part, but tends to exist on the surface.
  • the doping elements in the core reacts with fluorine on the surface to form a fluorinated metal compound You can see what's on the surface.
  • the tendency to exist on the surface can be used to improve the surface portion by placing the metal fluoride compound of Chemical Formula 2 on the surface.
  • the bleeding metal compound may serve to suppress wet reaction by reducing wetting with the electrolyte and may stabilize the surface.
  • the metal fluoride compound is produced by reaction of M 1 and / or M 2 and fluorine present on the surface.
  • the metal fluoride compound may be CaF 2 or TiF 4 .
  • M 3 of Formula 2-1 may be derived from M 1 of Formula 1 , or M 2 .
  • M 4 of Formula 2-2 may be derived from Co of Formula 1 or Mg.
  • the Ca / Mg increase ratio may be 0.3 to 0.8.
  • the Mg and Ca are the same Group 2 elements, and Mg is uniformly doped in the core due to the difference in ion radius, but Ca is partially doped, but the structural improvement and the surface modification of the core part are caused by the tendency to be located on the surface.
  • the difference in battery characteristics is caused by the ratio between each other.
  • the core comprising a compound represented by the formula (3);
  • a cathode active material for a lithium secondary battery comprising a coating layer on the surface of the core and including a compound represented by the following Chemical Formulas 4-1 and / or 4-2:
  • A Ni a CopMny, M 1 and M 2 are independently of each other, Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, -0.05 ⁇ a ⁇ 0.1 , 0 ⁇ b ⁇ 0. 1, 0 ⁇ c ⁇ 0.1, 0 ⁇ d ⁇ 0.1, 0 ⁇ z ⁇ 0.1, 0.6 ⁇ a ⁇ 0.81, 0.10 ⁇ ⁇ 0.20 and 0.10 ⁇ ⁇ 0.20,
  • M 3 is derived from Ml or M2 in Chemical Formula 3, and 0 ⁇ x ⁇ 4, [Formula 4-2]
  • M 4 is derived from Ni, Co, Mn, or Mg of Chemical Formula 3, wherein 0 ⁇ y ⁇ 4,
  • the weight ratio of MVM 2 in the cathode active material is 0.8 to 1.2.
  • composition is the same as the above-described embodiment of the present invention, a detailed description thereof will be omitted.
  • M 1 and M 2 are each independently Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, and 0.90 ⁇ a ⁇ 1.10, 0 ⁇ b ⁇ 0.1, 0 ⁇ c ⁇ 0.1, 0 ⁇ d ⁇ 0.1, 0 ⁇ z ⁇ 0.1,
  • ⁇ 3 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, 0 ⁇ x ⁇ 4,
  • M 4 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, 0 ⁇ y ⁇ 4,
  • the weight ratio of MVM 2 in the cathode active material is 0.8 to 1.2.
  • the feed materials of M g , M 1 and M 2 may be, independently of one another, in the form of hydroxides, oxyhydroxides, nitrates, halides, carbonates, acetates, oxalates or citrates.
  • the fluorine feed material may be in the form of ammonium salt, lithium salt or metal salt.
  • the temperature for effective firing for firing the prepared mixture to produce the cathode active material may be 800 ° C to 1050 ° C.
  • 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 positive electrode active material.
  • the positive electrode active material layer may include a binder and a conductive material.
  • the binder adheres the positive electrode active material particles to each other well, and also serves to adhere the positive electrode active material to the current collector well.
  • Polyvinylchloride carboxylated polyvinylchloride , Polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyridone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated 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 an 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 comprising a mixture of these.
  • 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. Or amorphous carbon or these may be used together.
  • the crystalline carbons include amorphous, plate-like, flake, spherical or fibrous natural graphites or lumps such as artificial alums.
  • amorphous carbons include soft carbon ( S0 ft carbon: low temperature calcined carbon). Or hard carbon, mesophase pitch carbide, calcined coke, and 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 alloy (Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, Rare earth element and an element selected from the group consisting of a combination thereof, not Si), Sn, Sn0 2 , Sn-Y (Y is an alkali metal, alkaline earth metal, group 13 element, An element selected from the group consisting of Group 14 elements, transition metals, rare earth elements, and combinations thereof, and not Sn), and at least one of them and Si0 2 may be used in combination.
  • transition metal oxides include vanadium oxide and lithium vanadium oxide.
  • the negative electrode active material layer also includes a binder, and may optionally further include a conductive material.
  • the binder adheres well to the negative electrode active material particles, and also adheres the negative electrode active material to the current collector.
  • the binder include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl salose, polyvinyl chloride, and carbon.
  • Carboxylated polyvinylchloride, polyvinylfluoride, polymers including 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 fiber;
  • 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 can be selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam (foam), copper foam, a polymer substrate coated with a conductive metal, and combinations thereof.
  • A1 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.
  • Such "electrode manufacturing method is detailed described herein because it is well known in the art and details thereof will be omitted.
  • the solvent to be used but may include an N- methyl pyrrolidone blood but is not limited to such.
  • 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-based, ester-based, ether-based, ketone-based, alcohol-based, or aprotic solvent may be used.
  • 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), etc.
  • the ester solvent may be methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate.
  • ⁇ -butyrolactone, decanolide, valerolactone, mevalonol actone, caprolactone, and the like may be used.
  • the ether solvent dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and the like may be used, and as the ketone solvent, cyclonucleanone may be used. have.
  • 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 the like, and sulfolane such as 1,3'dioxolane, and the like. .
  • the non-aqueous organic solvent may be used alone or in combination of one or more, and the mixing ratio in the case of using one or more in combination can 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 cyclic carbonate and a chain carbonate in combination.
  • annular When carbonate and chain carbonate are mixed and used in a volume ratio of 1: 1 to 1: 9, the performance of the electrolyte may be excellent.
  • the non-aqueous organic solvent according to the embodiment 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.
  • aromatic hydrocarbon organic solvent an aromatic hydrocarbon compound of the following Formula 5 may be used.
  • 3 ⁇ 4 to 3 ⁇ 4 are each independently hydrogen, halogen, C1 to C10 alkyl group, haloalkyl group, or a combination thereof.
  • the aromatic hydrocarbon-based organic solvent is banzen, fluorobenzene, 1,2 'difluorobenzene, 1,3' difluorobenzene, 1,4-difluorobenzene, 1,2,3-tripulobenzene , 1,2,4 ⁇ tripulobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2 , 4-trichlorobenzene, iodobenzene, 1,2, diiodobenzene, 1,3-diodiobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2, 4-triiodobenzene, toluene, fluoroluene, 1,2-difluoroluene, 1,3-difluoroluene, 1,4-diflu
  • the non-aqueous electrolyte may further include vinylene carbonate or an ethylene carbonate compound represented by Chemical Formula 6 to improve battery life.
  • R 7 and R 8 are each independently hydrogen, a halogen group, a cyano group (CN), a nitro group (N0 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 (N0 2 ) or C1 to C5 fluoroalkyl group.
  • ethylene carbonate compounds include difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate cyanoethylene carbonate, and fluoroethylene carbonate. have. 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, thereby enabling the operation of a basic lithium secondary battery, and promoting the 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 S0 3 , LiC10 4) LiA10 2) LiAlCl 4 , LiN (C x F 2x + 1 S0 2 ) (C y F 2y +1 S0 2 ), where x and y are natural numbers, LiCl, Li l and LiB (C 2 0 4 ) 2 (l ithium bis (oxalato) borate (LiBOB)
  • One or two or more selected from the group consisting of supporting salts may be used, and the concentration of the lithium salt may be used within the range of 0.1 to 2.0 M. If the concentration of the lithium salt is in the above range,
  • a separator may exist between the positive electrode and the negative electrode.
  • Such separators include polyethylene, polypropylene, polyvinylidene fluoride or two or more layers thereof .
  • Multilayer film can be used, Of course, a mixed multilayer film such as a polyethylene / polypropylene double-layer separator, a polyethylene / polypropylene / polyethylene three-layer separator, a polypropylene / polyethylene / polypropylene three-layer separator, and the like can be used.
  • Lithium secondary batteries may be classified into lithium ion batteries, lithium ion polymer batteries, and lithium polymer batteries according to the type of separator and electrolyte used, and may be classified into cylindrical, square, coin, and pouch types according to their type. 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.
  • Example 4 (: 0 3 0 4 MgC0 3 , CaF 2) and Ti0 2 based on the stoichiometric ratio of the mixture of Li 2 CO 3 to the contents shown in Table 1 below, and then dry mixed with the mixture, The mixture was heat-treated with locxrc for 10 hours to prepare a cathode active material.
  • Example 4
  • a positive electrode slurry was prepared by adding 5.0 wt% of N ⁇ methyl-2 pyrrolidone (NMP).
  • the positive electrode slurry was applied to a thin film of aluminum (A1), which is a positive electrode current collector having a thickness of 20 to 40 / im, and vacuum dried, followed by roll press to prepare an anode.
  • A1 aluminum
  • Li-metal was used as the negative electrode.
  • a coin cell type half cell was manufactured using 1.15M LiPF6EC: DMC (l: lvol%) as the electrolyte prepared by using a cathode and a Li-metal as a counter electrode.
  • Charging and discharging was carried out in the range of 4.5-3.0V and in the case of lifespan was conducted at 1.0C rate.
  • Table 2 below is 4.5V initial format ion, rate characteristic, lcyle, 30cycle, 50cycle capacity and life characteristic data of the above Examples and Comparative Examples.
  • Examples 1 to 3 containing the MF X compound on the surface have excellent battery characteristics compared to Comparative Examples 4 to 5.
  • Example 4 and Comparative Example 6 which are the positive electrode active material having a different composition, the above characteristic difference is confirmed.
  • Experimental Example 2 X-ray Photoelectron Spectroscopy (XPS) The XPS analysis of the cathode active material prepared in Example 1 was performed and the results are shown in FIG. 2. 2, the coating layer includes at least a part of LiF, and the coating layer is a metal fluoride compound (eg, TiF 4 , CaF 2 ) and a metal fluoride compound derived from the metal of the core portion bonded to the doped transition metal. (For example, CoF 2 ) can be confirmed to further include.
  • XPS X-ray Photoelectron Spectroscopy

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Abstract

The present invention relates to a cathode active material for a lithium secondary battery, a preparation method therefor, and a lithium secondary battery containing the same, and provides a cathode active material for a lithium secondary battery, comprising: a core comprising a compound represented by the following chemical formula 1; and a coating layer located on the surface of the core and comprising a compound represented by the following chemical formulas 2-1 and/or 2-2. [Chemical formula 1] LiaCo1-bMgbM1 cM2 dO2-zFz [Chemical formula 2-1] M3Fx [Chemical formula 2-2] M4Fy The definition with respect to chemical formulas 1, 2-1 and 2-2 is present in the specification.

Description

[명세서】  [Specification】

【발명의 명칭】  [Name of invention]

리튬 이차 전지용 양극 활물질， 이의 제조 방법 및 이를 포함하는 리튬 이차 전지' Cathode active material for lithium secondary battery, manufacturing method thereof and lithium secondary battery comprising same ''

【기술분야】 Technical Field

리튬 이차 전지용 양극 .활물질， 이의 제조 방법 및 이를 포함하는 리튬 이차 전지에 관한 것이다. [배경기술】  The present invention relates to a cathode active material for a lithium secondary battery, a method of manufacturing the same, and a lithium secondary battery including the same. Background Art

최근 휴대용 전자기기의 소형화 및 경량화 추세와 관련하여 이들 기기의 전원으로 사용되는 전지의 고성능화 및 대용량화에 대한 필요성이 높아지고 있다. 전지는 양극과 음극에 전기 화학 반웅이 가능한 물질을 사용함으로써 전력을 .발생시키는 것이다. 이러한 전지 중 대표적인 예로는 양극 및 음극에서 리튬 이은이 인터칼레이션 /디인터칼레이션될 때의 화학전위 (chemi cal potent ial )의 변화에 의하여 전기 에너지를 생성하는 리튬 이차 전지가 있다. 상기 리튬 이차 전지는 리튬 이은의 가역적인 인터칼레이션 /디인터칼레이션이 가능한 물질을 양극과 음극 활물질로 사용하고， 상기 양극과 음극 사이에 유기 전해액 또는 폴리머 전해액을 충전시켜 제조한다. 리튬 이차 전지의 양극 활물질로는 리튬 복합금속 화합물이 사용되고 있으며， 그 예로 LiCo¾ , LiMn204, LiNi02 , LiMn02 등의 복합금속 산화물들이 연구되고 '있다. Recently, with the trend toward miniaturization and light weight of portable electronic devices, the need for high performance and high capacity of batteries used as power sources for these devices is increasing. A battery generates electric power by using an electrochemical reaction material for the positive electrode and the negative electrode. A typical example of such a battery is a lithium secondary battery that generates electrical energy by changing a chemical potential (chemi cal potential) when lithium silver is 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 silver 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. As a cathode active material of a lithium secondary battery is a lithium composite metal compound is used, it is. Examples LiCo¾, LiMn 2 0 4, LiNi0 2, LiMn0 2 such as a complex metal oxide have been studied in ".

상기 양극 활물질 중 LiMn204, LiMn02 등의 Mn계 양극 활물질은 합성하기도 쉽고， 값이 비교적 싸며， 과층전시 다른 활물질에 비하여 열적 안정성이 가장 우수하고， 환경에 대한 오염이 낮아 매력이 있는 물질이기는 하나， 용량이 적다는 단점을 가지고 있다. Among the cathode active materials, Mn-based cathode active materials such as LiMn 2 O 4 and LiMn0 2 are easy to synthesize, are relatively inexpensive, have the best thermal stability compared to other active materials during overheating, and have low environmental pollution and are attractive materials. Although it has a disadvantage, the capacity is small.

LiCo02는 양호한 전기 전도도와 약 3.7V 정도의 높은 전지 전압을 가지며， 사이클 수명 특성， 안정성 또한 방전 용량 역시 우수하므로， 현재 상업화되어 시판되고 있는 대표적인 양극 활물질이다. 그러나 LiCo02는 가격이 비싸기 때문에 전지 가격의 30% 이상을 차지하므로 가격 경쟁력이 떨어지는 문제점이 있다. LiCo0 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. Thus, LiCo0 2 is a representative cathode active material commercially available and commercially available. However, since LiCo0 2 is expensive, it takes up more than 30% of the battery price, which makes the price competitive. have.

또한 LiNi02는 위에서 언급한 양극 활물질 중 가장 높은 방전 용량의 전지 특성을 나타내고 있으나， 합성하기 어려운 단점이 있다. 또한 니켈의 높은 산화상태는 전지 및 전극 수명 저하의 원인이 되며, 자기 방전이 심하고 가역성이 떨어지는 문제가 있다. 아울러, 안정성 확보가 완전하지 않아서 상용화에 어려움을 겪고 있다. In addition, LiNi0 2 exhibits the highest discharge capacity of battery characteristics among the cathode active materials mentioned above, but has a disadvantage of being difficult to synthesize. In addition, 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. In addition, it is difficult to commercialize the stability is not perfect.

【발명의 내용】 [Content of invention]

【해결하려는 과제】  [Problem to solve]

고율， 수명 특성이 우수한 리륨 이차 전지용 양극 활물질을 제공하며, 상기 양극 활물질을 포함하는 양극을 포함하는 리튬 이차 전지를 제공하는 것이다.  It is to provide a positive electrode active material for a lithium secondary battery excellent in high rate, life characteristics, and to provide a lithium secondary battery comprising a positive electrode containing the positive electrode active material.

【과제의 해결 수단】 [Measures of problem]

본 발명의 일 구현예에서는, 하기 화학식 1로 표시되는 화합물을 포함하는 코어; 및 상기 코어의 표면에 위치하고 하기 화학식 2-1 및 /또는 2-2로 표시되는 화합물을 포함하는 코팅층을 포함하는 리튬 이차 전지용 양극 활물질을 제공한다.  In one embodiment of the present invention, a core comprising a compound represented by the following formula (1); And it provides a positive electrode active material for a lithium secondary battery comprising a coating layer located on the surface of the core and comprising a compound represented by the formula 2-1 and / or 2-2.

[화학식 1]  [Formula 1]

LiaC0l— bMgbM^M2^— ZFZ Li a C 0l — b Mg b M ^ M 2 ^ — Z F Z

상기 화학식 1에서， M1 및 M2는 서로 독립적으로， Zr, Ti, Ca, V， Zn, Mo,In Formula 1, M 1 and M 2 are independently of each other, Zr, Ti, Ca, V, Zn, Mo,

Ni , Mn, 또는 이들의 조합이고， 0.90<a<1.10, 0<b<0.1, 0<c<0.1, 0<d<0.1, 0<z<0.1 일 수 있다. Ni, Mn, or a combination thereof, and may be 0.90 <a <1.10, 0 <b <0.1, 0 <c <0.1, 0 <d <0.1, 0 <z <0.1.

[화학식 2ᅳ 1]  [Formula 2-1]

M3FX M 3 X F

상기 화학식 2-1에서 ,Μ3는 Zr, Ti, Ca, V， Zn, Mo, Ni， Co, Mn, 또는 이들의 조합이고， 0<x≤4 일 수 있다. In Formula 2-1, Μ 3 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, and may be 0 <x≤4.

[화학식 2-2]  [Formula 2-2]

M4Fy - 상기 화학식 2-2에서， M4는 Zr, Ti, Ca, V， Zn, Mo, Ni， Co, Mn, 또는 이들의 조합이고, 0<y≤4 일 수 있다. 상기 양극 활물질 내 MVM2의 중량비는 0.8 내지 1.2 일 수 있다. M 4 F y -In Formula 2-2, M 4 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, and may be 0 <y ≦ 4. The weight ratio of MVM 2 in the cathode active material may be 0.8 to 1.2.

상기 M1은 Ca일 수 있다. M 1 may be Ca.

상기 M2은 Ti, Zr 또는 이들의 조합일 수 있다. M 2 may be Ti, Zr, or a combination thereof.

상기 Mg, M1 및 M2의 몰 도큉비율은, 서로 독립적으로 0.001 내지 0.01일 수 있다. The molar dosing ratios of Mg, M 1, and M 2 may be 0.001 to 0.01 independently of each other.

상기 화학식 2-1로 표시되는 화합물은 CaF2 또는 TiF4 일 수 있다. The compound represented by Chemical Formula 2-1 may be CaF 2 or TiF 4 .

상기 화학식 2-1의 M3은， 상기 화학식 1의 M1, 또는 M2로부터 유래될 수 있다. M 3 of Formula 2-1 may be derived from M 1 of Formula 1 , or M 2 .

상기 화학식 2-2의 M4은， 상기 화학식 1의 Co, 또는 Mg로부터 유래될 수 있다. M 4 of Chemical Formula 2-2 may be derived from Co, or Mg of Chemical Formula 1.

상기 M1은 Ca일 때 Ca/Mg의 중량비는 0.3 내지 0.8 일 수 있다. When M 1 is Ca, the weight ratio of Ca / Mg may be 0.3 to 0.8.

본 발명의 다른 일 구현예에서는， 하기 화학식 3로 표시되는 화합물을 포함하는 코어; 및 상기 코어의 표면에 위치하고 하기 화학식 4—1 및 /또는 4-2로 표시되는 화합물을 포함하는 코팅층을 포함하는 리튬 이차 전지용 양극 활물질을 제공한다.  In another embodiment of the present invention, the core comprising a compound represented by the formula (3); And it provides a cathode active material for a lithium secondary battery comprising a coating layer located on the surface of the core and comprising a compound represented by the following formula 4-1 and / or 4-2.

[화학식 3]  [Formula 3]

Li [LiaA(i-a-b)MgbM1 cM2 d ] 02-zF2 Li [Li a A (i- a - b) Mg b M 1 c M 2 d ] 0 2 - z F 2

상기 화학식 3에서, A = NiaCopMnY이고， M1 및 M2는 서로 독립적으로， Zr, Ti, Ca, V， Zn, Mo, Ni , Mn, 또는 이들의 조합이고， -0.05 < a < 0.1， 0<b<0.1, 0<c<0.1, 0<d<0.1, 0<z<0.1이고， 0.6 < a < 0.81, 0.10< β<0.20 및 0.10< γ≤0.20 이고, In Formula 3, A = Ni a Co p Mn Y , M 1 and M 2 are independently of each other, Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, -0.05 < a <0.1, 0 <b <0.1, 0 <c <0.1, 0 <d <0.1, 0 <z <0.1, 0.6 <a <0.81, 0.10 <β <0.20 and 0.10 <γ≤0.20,

[화학식 4-1]  [Formula 4-1]

M3FX M 3 F X

상기 화학식 4-1에서， M3는 상기 화학식 .3의 Ml, 또는 M2로부터 유래된 것이고， 0<x<4 이고， In Chemical Formula 4-1, M 3 is represented by Chemical Formula . Ml of 3 or M2, 0 <x <4,

[화학식 4-2]  [Formula 4-2]

M4Fy M 4 F y

상기 화학식 4ᅳ 2에서, M4는 상기 화학식 3의 Ni, Co, Mn 또는 Mg로부터 유래된 것이고， 0<y≤4 이고， 상기 양극 활물질 내 MVM2의 중량비는 0.8 내지 1.2이다. 본 발명의 다른 일 구현예에서는, 리튬 공급 물질， 전이 금속 전구체， Mg 공급 물질, 공급 물질， M2 공급 물질， 및 불소 공급 물질을 건식 흔합하는 단계; 상기 흔합물을 소성하는 단계; 및 하기 화학식 1로 표시되는 화합물을 포함하는 코어; 및 상기 코어의 표면에 위치하고 하기 화학식 2—1 및 /또는 2ᅳ 2로 표시되는 화합물을 포함하는 코팅층；을 포함하는 리튬 이차 전지용 양극 활물질을 수득하는 단계;를 포함하는 리륨 이차 전지용 양극 활물질의 제조 방법을 제공한다. In Formula 4-4, M 4 is derived from Ni, Co, Mn, or Mg of Formula 3, and 0 <y ≦ 4, and the weight ratio of MVM 2 in the cathode active material is 0.8 to 1.2. In another embodiment of the invention, dry mixing a lithium feed material, transition metal precursor, Mg feed material, feed material, M 2 feed material, and fluorine feed material; Firing the mixture; And a core comprising a compound represented by Formula 1 below; Preparing a positive electrode active material for a lithium secondary battery comprising a; coating layer comprising a compound represented on the surface of the core and represented by the formula 2-1 and / or 2 '2; Provide a method.

[화학식 1] [Formula 1]

Figure imgf000006_0001
Figure imgf000006_0001

상기 화학식 1에서， M1 및 M2는 서로 독립적으로, Zr, Ti, Ca, V， Zn, Mo, Ni , Mn, 또는 이들의 조합이고, 0.90<a<1.10, 0<b<0.1 , 0<c<0.1, 0<d<0.1, 0<z<0.1 일 수 있다. In Formula 1, M 1 and M 2 are independently of each other, Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, 0.90 <a <1.10, 0 <b <0.1, 0 <c <0.1, 0 <d <0.1, 0 <z <0.1.

[화학식 2ᅳ 1]  [Formula 2-1]

M3FX M 3 F X

상기 화학식 2ᅳ 1에서， M3는 Zr, Ti, Ca, V, Zn, Mo, Ni , Co, Mn, 또는 이들의 조합이고， 0<x≤4 일 수 있다. In Formula 2-1, M 3 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, and may be 0 <x≤4.

[화학식 2-2]  [Formula 2-2]

M4Fy M 4 F y

상기 화학식 2-2에서， M4는 Zr, Ti, Ca, V， Zn, Mo, Ni， Co, Mn, 또는 이들의 조합이고， 0<y≤4 일 수 있다. In Formula 2-2, M 4 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, and may be 0 <y ≦ 4.

상기 양극 활물질 내 MVM2의 중량비는 0.8 내지 1.2일 수 있다. The weight ratio of MVM 2 in the cathode active material may be 0.8 to 1.2.

상기 Mg, M1 및 M2의 공급 물질은， 서로 독립적으로 수산화물, 옥시수산화물， 질산염， 할로겐화물， 탄산염， 초산염， 옥살산염 또는 시트르산염 형태일 수 있다. The feed materials of Mg, M 1 and M 2 may independently be in the form of hydroxide, oxyhydroxide, nitrate, halide, carbonate, acetate, oxalate or citrate.

상기 불소 공급 물질은 암모늄염， 리튬염 또는 금속염 형태일 수 있다. 상기 흔합물을 소성하는 단계;에서， 소성 온도는 800 내지 1，050 t일 수 있다.  The fluorine feed material may be in the form of ammonium salt, lithium salt or metal salt. In the step of firing the mixture; the firing temperature may be 800 to 1,050 t.

본 발명의 또 다른 일 구현예에서는 전술한 본 발명의 일 구현예에 따른 리튬 이차 전지용 양극 활물질을 포함하는 양극;음극 활물질을 포함하는 음극; 및 전해질；을 포함하는 리튬 이차 전지를 제공한다. 【발명의 효과] In still another embodiment of the present invention, a positive electrode including a positive electrode active material for a lithium secondary battery according to an embodiment of the present invention described above; a negative electrode including a negative electrode active material; And it provides an lithium secondary battery comprising an electrolyte. 【Effects of the Invention]

우수한 전지 특성을 갖는 양극 활물질 및 이를 포함하는 리륨 이차 전지를 제공할 수 있다.  A positive electrode active material having excellent battery characteristics and a lithium secondary battery including the same can be provided.

【도면의 간단한 설명】 [Brief Description of Drawings]

도 1은 리튬 이차 전지의 개략도이다.  1 is a schematic view of a lithium secondary battery.

도 2는 실시예 1의 양극 활물질에 대한 X선 광전자 분광 분석 그래프이다. 【발명을 실시하기 위한 구체적인 내용】  2 is an X-ray photoelectron spectroscopic analysis graph of the positive electrode active material of Example 1. [Specific contents to carry out invention]

이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만， 이는 예시로서 제시되는 것으로， 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구범위의 범주에 의해 정의될 뿐이다. 본 발명의 일 구현예에서는， 하기 화학식 1로 표시되는 화합물을 포함하는 코어 ; 및 상기 코어의 표면에 위치하고 하기 화학식 2-1 및 /또는 2-2로 표시되는 화합물을 포함하는 코팅층을 포함하는 리튬 이차 전지용 양극 활물질을 제공한다ᅳ [화학식 1]  Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later. In one embodiment of the present invention, the core comprising a compound represented by the formula (1); And it provides a cathode active material for a lithium secondary battery comprising a coating layer located on the surface of the core and comprising a compound represented by the following formulas 2-1 and / or 2-2 ᅳ [Formula 1]

LiaCoi-bMgbM1 cM2 d02-2Fz Li a Coi- b Mg b M 1 c M 2 d 0 2 - 2 F z

상기 화학식 1에서,  In Chemical Formula 1,

M1 및 M2는 서로 독립적으로， Zr, Ti, Ca, V, Zn, Mo, Ni , Mn, 또는 이들의 조합이고， 0.90<a<1.10, 0<b<0.1 , 0<c<0.1 , 0<d<0.1 , 0<z<0.1 이고， M 1 and M 2 are each independently Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, and 0.90 <a <1.10, 0 <b <0.1, 0 <c <0.1, 0 <d <0.1, 0 <z <0.1,

[화학식 2-1]  [Formula 2-1]

M3FX M 3 F X

상기 화학식 2—1에서,  In Chemical Formula 2-1,

M3는 Zr, Ti, Ca, V， Zn, Mo, Ni , Co, Mn, 또는 이들의 조합이고， 0<x≤4 이고 ,· M 3 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, 0 <x≤4

[화학식 2-2]  [Formula 2-2]

M4Fy 4 M y F

상기 화학식 2-2에서， M4는 Zr, Ti, Ca, V， Zn, Mo, Ni , Co, Mn, 또는 이들의 조합이고， 0<y<4 이고， In Chemical Formula 2-2, M 4 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, 0 <y <4,

상기 양극 활물질 내 MVM2의 중량비는 0.8 내지 1.2이다. The weight ratio of the positive electrode active material within the MVM 2 is 0.8 to 1.2.

상기 본 발명의 일 구현예에 따른 양극 활물질의 코어인 리튬의 가역적인 인터칼레이션 및 디인터칼레이션이 가능한 화합물은 Mg을 반드시 포함하며 M1 및 M2가 도3 §된 것이되， 상기 ML 및 M2는, 서로 독립적으로 Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, 또는 이들의 조합인 금속일 수 있다. . The compound capable of reversible intercalation and deintercalation of lithium, which is a core of the positive electrode active material according to the embodiment of the present invention, includes Mg and M 1 and M 2 are illustrated in FIG. 3 . L and M 2 may be independently a metal which is Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof. .

상기 리튬의 가역적인 인터칼레이션 및 디인터칼레이션이 가능한 화합물은 리튬 코발트 복합 산화물일 수 있다.  The compound capable of reversible intercalation and deintercalation of lithium may be lithium cobalt complex oxide.

상기 일반적인 리튬 코발트 복합 산화물은 고전압에서 용량 및 수명 열화가 심하다. 이 문제점을 개선하기 위하여 코어부 구조 개선 및 표면부의 표면 개질로 이 문제점의 개선이 필요하다. 코어부의 구조 개선을 위하여 열적 안정성 및 구조를 안정하게 하는 Mg을 반드시 포함함과 동시에， 상기 M1 및 M2의 도핑으로 전술한 문제점을 해결 할 수 있다. The general lithium cobalt composite oxide has severe capacity and life deterioration at high voltage. In order to remedy this problem, improvement of the core part structure and surface modification of the surface part need improvement of this problem. In order to improve the structure of the core part, the thermal stability and the Mg to stabilize the structure must be included at the same time, the above problems can be solved by the doping of the M 1 and M 2 .

상기 M1은 Ca 일 수 있다. Wherein M 1 may be a Ca.

상기 M2은 Ti, Zr 또는 이의 조합일 수 있다. . M 2 may be Ti, Zr, or a combination thereof. .

상기 Mg, M1 및 M2의 몰 도핑비율은， 서로 독립적으로 0.001 내지 0.01 일 수 있다. The molar doping ratios of Mg, M 1, and M 2 may be 0.001 to 0.01 independently of each other.

상기 0.001 미만의 몰 도큉비에서는 도핑에 따른 효과가 나타나지 않을 수 있으며， 0.01 초과의 몰 도핑비에서는 초기 용량의 과도한 감소와 효율 특성의 감소가 나타날 수 있다.  The molar doping ratio of less than 0.001 may not show an effect due to doping, and the molar doping ratio of more than 0.01 may result in excessive decrease in initial capacity and decrease in efficiency characteristics.

상기 Mg, M1 및 M2의 도핑을 위해， 전구체와 함께 도핑 원료 물질을 함께 소성할 경우, 이 때 효과적인 소성을 위한 온도는 800 내지 1,050°C 일 수 있다. 상기 소성 온도 범위에서， 800°C 미만인 경우에는 상온， 및 고은에서의 전지 특성의 급격한 저하가 나타날 수 있다. 또한， 1,050°C 초과의 온도에서 소성할 경우에도 용량 및 용량 유지율의 급격한 저하가 일어날 수 있다. For the doping of the Mg, M 1 and M 2, when the doping raw material is fired together with the precursor, the temperature for effective firing may be 800 to 1,050 ° C. In the firing temperature range, when the temperature is less than 800 ° C., a sudden decrease in battery characteristics at room temperature and high silver may appear. In addition, even when firing at a temperature of more than 1,050 ° C. can drastically lower the capacity and capacity retention rate.

상기 소성 과정을 거치면서 상기 Mg/ M1 및 M2는 상기 코어에 도핑될 수 있다. 그러나 상기 도핑되는 원소들은 이온 반경에 따라 코어에 도¾되는 정도가 달라진다. The Mg / M 1 and M 2 may be doped into the core while undergoing the firing process. However, the doped elements vary depending on the ionic radius.

이온 반경이 작은 Mg의 경우에는 코어에 도핑이 균일하게 되지만 이온 반경이 큰 Ca , Ti , Zr 등과 같은 원소들은 코어의 벌크 내에서 이온 반경이 커 밀어내는 현상이 발생하여 코어부에 일부 도핑되나 표면에 존재하는 경향이 있다. 이후 실시예에서 보다 자세히 설명하겠지만， 본 발명의 실시예에 따른 도 2의 X선 광전자 분광 분석 (XPS)의 그래프에서 알 수 있듯이， 코어 내 도핑 원소들이 표면에서 불소와 반응하여 불화 금속 화합물를 형성하여 표면에서 존재하는 것을 확인 할 수 있다. For Mg with small ion radius, doping is uniform in the core, but Elements such as Ca, Ti, Zr, etc., which have a large radius, have a large ion radius in the bulk of the core, which causes some doping to the core part, but tends to exist on the surface. As will be described later in more detail, as can be seen in the graph of X-ray photoelectron spectroscopy (XPS) of Figure 2 according to an embodiment of the present invention, the doping elements in the core reacts with fluorine on the surface to form a fluorinated metal compound You can see what's on the surface.

이러한 불화 금속 화합물을 확인해보면， Ca , Ti 등의 원소들과 결합한 화합물은 확인할 수 있으나, Mg는 표면에서 확인 할 수 없다.  When confirming such a metal fluoride compound, compounds combined with elements such as Ca and Ti can be identified, but Mg cannot be identified from the surface.

이러한 표면에 존재하는 경향을 웅용하여 표면에 상기 화학식 2의 불화 금속 화합물을 표면에 위치하게 하여 표면부를 개선할 수 있다. 블화 금속 화합물은 전해액과의 젖음성 (wet t ing)을 떨어뜨려 부반웅을 억제하는 역할을 수행하여 표면 안정화를 시킬 수 있다.  The tendency to exist on the surface can be used to improve the surface portion by placing the metal fluoride compound of Chemical Formula 2 on the surface. The bleeding metal compound may serve to suppress wet reaction by reducing wetting with the electrolyte and may stabilize the surface.

상기 불화 금속 화합물은 표면에 존재하는 M1 및 /또는 M2와 불소의 반웅으로 생성된다. The metal fluoride compound is produced by reaction of M 1 and / or M 2 and fluorine present on the surface.

상기 불화 금속 화합물은 CaF2 또는 TiF4 일 수 있다. The metal fluoride compound may be CaF 2 or TiF 4 .

상기 화학식 2-1의 M3은， 상기 화학식 1의 M1 , 또는 M2로부터 유래될 수 있다. M 3 of Formula 2-1 may be derived from M 1 of Formula 1 , or M 2 .

상기 화학식 2-2의 M4은， 상기 화학식 1의 Co , 또는 Mg로부터 유래될 수 있다. M 4 of Formula 2-2 may be derived from Co of Formula 1 or Mg.

상기 M1이 Ca 일 때 Ca/Mg 증량비는 0 .3 내지 0.8 일 수 있다. When M 1 is Ca, the Ca / Mg increase ratio may be 0.3 to 0.8.

상기 Mg과 Ca는 같은 2족 원소로서 이온반경의 차이에 의해 Mg는 코어에 도핑이 균일하게 되나 Ca는 일부는 도핑이 되나 표면에 위치하는 경향에 의해서 서로 간의 코어부의 구조개선과 표면부의 표면 개질에 있어서 서로 간의 비율에 의하여 전지 특성에 차이가 발생하게 된다. 본 발명의 다른 일 구현예에서는, 하기 화학식 3로 표시되는 화합물을 포함하는 코어； 및  The Mg and Ca are the same Group 2 elements, and Mg is uniformly doped in the core due to the difference in ion radius, but Ca is partially doped, but the structural improvement and the surface modification of the core part are caused by the tendency to be located on the surface. The difference in battery characteristics is caused by the ratio between each other. In another embodiment of the present invention, the core comprising a compound represented by the formula (3); And

상기 코어의 표면에 위치하고 하기 화학식 4-1 및 /또는 4-2로 표시되는 화합물을 포함하는 코팅층을 포함하는 리튬 이차 전지용 양극 활물질 :  A cathode active material for a lithium secondary battery comprising a coating layer on the surface of the core and including a compound represented by the following Chemical Formulas 4-1 and / or 4-2:

[화학식 3] Li[LiaA(i-a-b)MgbM1 cM-d]02-zFz [Formula 3] Li [Li a A (i- a - b ) Mg b M 1 c M- d ] 0 2 -zF z

. 상기 화학식 3에서， A = Ni aCopMny이고， M1 및 M2는 서로 독립적으로， Zr , Ti , Ca , V, Zn, Mo , Ni， Mn, 또는 이들의 조합이고, -0.05 < a < 0.1， 0<b<0. 1 , 0<c<0.1 , 0<d<0.1 , 0<z<0.1이고， 0.6 < a < 0.81， 0.10< β<0.20 및 0.10< γ<0.20 이고， . In Formula 3, A = Ni a CopMny, M 1 and M 2 are independently of each other, Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, -0.05 <a <0.1 , 0 <b <0. 1, 0 <c <0.1, 0 <d <0.1, 0 <z <0.1, 0.6 <a <0.81, 0.10 <β <0.20 and 0.10 <γ <0.20,

[화학식 4-1]  [Formula 4-1]

M3FX M 3 F X

상기 화학식 4-1에서，  In Chemical Formula 4-1,

M3는 상기 화학식 3의 Ml , 또는 M2로부터 유래된 것이고， 0<x≤4 이고， [화학식 4-2] M 3 is derived from Ml or M2 in Chemical Formula 3, and 0 <x ≦ 4, [Formula 4-2]

M4Fy M 4 F y

상기 화학식 4-2에서，  In Chemical Formula 4-2,

M4는 상기 화학식 3의 Ni , Co , Mn 또는 Mg로부터 유래된 것이고， 0<y≤4 이고， M 4 is derived from Ni, Co, Mn, or Mg of Chemical Formula 3, wherein 0 <y≤4,

상기 양극 활물질 내 MVM2의 중량비는 0.8 내지 1.2이다. The weight ratio of MVM 2 in the cathode active material is 0.8 to 1.2.

상기의 조성에서도 전술한 본 발명의 일 구현예와 동일하기 때문에 구체적인 설명은 생략하도록 한다.  Since the composition is the same as the above-described embodiment of the present invention, a detailed description thereof will be omitted.

본 발명의 다른 일 구현예에서는， 리튬 공급 물질， 전이 금속 전구체， Mg 공급 물질， M1 공급 물질, M2 공급 물질 및 불소 공급 물질을 건식 흔합하는 단계; 상기 흔합물을 소성하는 단계; 및 하기 화학식 1로 표시되는 화합물을 포함하는 코어; 및 상기 코어의 표면에 위치하고 하기 화학식 2-1 및 /또는 2 2로 표시되는 화합물을 포함하는 코팅층；을 포함하는 리튬 아차 전지용 양극 활물질을 수득하는 단계;를 포함하는 리튬 이차 전지용 양극 활물질의 제조 방법을 제공한다. In another embodiment of the present invention, dry mixing a lithium feed material, transition metal precursor, Mg feed material, M 1 feed material, M 2 feed material and fluorine feed material; Firing the mixture; And a core comprising a compound represented by Formula 1 below; And obtaining a cathode active material for a lithium secondary battery, including a coating layer disposed on a surface of the core and including a compound represented by the following Chemical Formulas 2-1 and / or 2 2; To provide.

[화학식 1]  [Formula 1]

LiaCoi-bMgbM1 cM2 d02-zFz Li a Coi- b Mg b M 1 c M 2 d 0 2 - z F z

상기 화학식 1에서,  In Chemical Formula 1,

M1 및 M2는 서로 독립적으로， Zr , Ti , Ca , V, Zn, Mo, Ni , Mn, 또는 이들의 조합이고, 0.90<a<1.10 , 0<b<0.1 , 0<c<0.1 , 0<d<0.1 , 0<z<0.1 이고， M 1 and M 2 are each independently Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, and 0.90 <a <1.10, 0 <b <0.1, 0 <c <0.1, 0 <d <0.1, 0 <z <0.1,

[화학식 2-1] 상기 화학식 2-1에서， [Formula 2-1] In Chemical Formula 2-1,

Μ3는 Zr , Ti , Ca , V， Zn, Mo , Ni , Co , Mn , 또는 이들의 조합이고， 0<x≤4 이고， Μ 3 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, 0 <x≤4,

[화학식 2-2]  [Formula 2-2]

M4Fy M 4 F y

상기 화학식 2ᅳ 2에서,  In Chemical Formula 2 ′ 2,

M4는 Zr , Ti , Ca , V， Zn, Mo , Ni， Co , Mn , 또는 이들의 조합이고， 0<y <4 이고， M 4 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, 0 <y <4,

상기 양극 활물질 내 MVM2의 중량비는 0.8 내지 1.2이다. The weight ratio of MVM 2 in the cathode active material is 0.8 to 1.2.

상기 Mg , M1 및 M2의 공급 물질은 서로 독립적으로, 수산화물, 옥시수산화물， 질산염, 할로겐화물， 탄산염， 초산염， 옥살산염 또는 시트르산염 형태일 수 있다. The feed materials of M g , M 1 and M 2 may be, independently of one another, in the form of hydroxides, oxyhydroxides, nitrates, halides, carbonates, acetates, oxalates or citrates.

상기 불소 공급 물질은 암모늄염， 리튬염 또는 금속염 형태일 수 있다. 상기 제조된 흔합물을 소성하여 상기 양극 활물질을 제조하기 위한 효과적인 소성을 위한 온도는 800 °C 내지 1050 °C 일 수 있다. The fluorine feed material may be in the form of ammonium salt, lithium salt or metal salt. The temperature for effective firing for firing the prepared mixture to produce the cathode active material may be 800 ° C to 1050 ° C.

제조된 양극 활물질에 대한 설명은 전술한 본 발명의 일 구현예와 동일하기 때문에 구체적인 설명은 생략하도록 한다. 본 발명의 다른 일 구현예에서는, 양극， 음극 및 전해질을 포함하는 리튬 이차 전지며， 상기 양극은 전류 집전체 및 상기 전류 집전체 상에 형성된 양극 활물질층을 포함하며， 상기 양극 활물질층은， 전술한 양극 활물질을 포함하는 것인 리튬 이차 전지를 제공한다.  Description of the prepared cathode active material is the same as the embodiment of the present invention described above, so a detailed description thereof will be omitted. In another embodiment of the present invention, 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 positive electrode active material.

상기 양극 활물질과 관련된 설명은 전술한 본 발명의 일 구현예와 동일하기 때문쎄 생략하도록 한다.  Descriptions related to the cathode active material are omitted because they are the same as the above-described embodiments of the present invention.

상기 양극 활물질층은 바인더 및 도전재를 포함할 수 있다.  The positive electrode active material layer may include a binder and a conductive material.

상기 바인더는 양극 활물질 입자들을 서로 잘 부착시키고， 또한 양극 활물질을 전류 집전체에 잘 부착시키는 역할을 하며， 그 대표적인 예로는 폴리비닐알콜， 카르복시메틸샐를로즈 , 히드록시프로필샐를로즈， 디아세틸셀를로즈， 폴리비닐클로라이드， 카르복실화된 폴리비닐클로라이드， 폴리비닐플루오라이드， 에틸렌 옥사이드를 포함하는 폴리머， 폴리비닐피를리돈， 폴리우레탄， 폴리테트라플루오로에틸렌， 폴리비닐리덴 플루오라이드， 폴리에틸렌， 폴리프로필렌, 스티렌-부타디엔 러버， 아크릴레이티드 스티렌ᅳ부타디엔 .러버， 에폭시 수지, 나일론 등을 사용할 수 있으나， 이에 한정되는 것은 아니다. The binder adheres the positive electrode active material particles to each other well, and also serves to adhere the positive electrode active material to the current collector well. ， Polyvinylchloride ， carboxylated polyvinylchloride ， Polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyridone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene. Rubber, epoxy resin, nylon and the like can be used, but is not limited thereto.

상기 도전재는 전극에 도전성을 부여하기 위해 사용되는 것으로서, 구성되는 전지에 있어서， 화학변화를 야기하지 않고 전자 전도성 재료이면 어떠한 것도 사용가능하며， 그 예로 천연 흑연, 인조 혹연， 카본 블랙, 아세틸렌 블랙, 케첸블랙, 탄소섬유 등의 탄소계 물질; 구리， 니켈， 알루미늄, 은 등의 금속 분말 또는 금속 섬유 등의 금속계 물질 ; 폴리페닐렌 유도체 등의 도전성 폴리머 ; 또는.이들의 흔합물을 포함하는 도전성 재료를 사용할 수 있다.  The conductive material is used to impart conductivity to an electrode, and any battery can be used as long as it is an electronic conductive material without causing chemical change in the battery. For example, natural graphite, artificial alum, carbon black, acetylene black, and ketjen. 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 comprising a mixture of these.

상기 음극은 집전체 및 상기 집전체 위에 형성된 음극 활물질층을 포함하며， 상기 음극 활물질층은 음극 활물질을 포함한다.  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.

상기 음극 활물질로는 리튬 이온을 가역적으로 인터칼레이션 /디인터칼레이션할 수 있는 물질， 리튬 금속, 리튬 금속의 합금， 리튬을 도프 및 탈도프할 수 있는 물질， 또는 전이 금속 산화물을 포함한다.  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.

상기 리튬 이온을 가역적으로 인터칼레이션 /디인터칼레이션할 수 있는 물질로는 탄소 물질로서， 리튬 이온 이차 전지에서 일반적으로 사용되는 탄소계 음극 활물질은 어떠한 것도 사용할 수 있으며， 그 대표적인 예로는 결정질 탄소， 비정질 탄소 또는 이들을 함께 사용할 수 있다. 상기 결정질 탄소의 예로는 무정형， 판상， 린편상 (flake), 구형 또는 섬유형의 천연 흑연 또는 인조 혹연과 같은 혹연을 들 수 있고， 상기 비정질 탄소의 예로는 소프트 카본 (S0ft carbon: 저온 소성 탄소) 또는 하드 카본 (hard carbon) , 메조페이스 피치 탄화물， 소성된 코크스 등을 들 수 있다. As a material capable of reversibly intercalating / deintercalating the lithium ions, 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. Or amorphous carbon or these may be used together. Examples of the crystalline carbons include amorphous, plate-like, flake, spherical or fibrous natural graphites or lumps such as artificial alums. Examples of amorphous carbons include soft carbon ( S0 ft carbon: low temperature calcined carbon). Or hard carbon, mesophase pitch carbide, calcined coke, and the like.

상기 리튬 금속의 합금으로는 리튬과 Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al 및 Sn으로 이루어진 군에서 선택되는 금속의 합금이 사용될 수 있다.  Examples of the alloy of the lithium metal 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.

상기 리튬을 도프 및 탈도프할 수 있는 물질로는 Si, SiOx(0 < x < 2)， Si-Y 합금 (상기 Y는 알칼리 금속， 알칼리 토금속， 13족 원소， 14족 원소， 전이금속， 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며， Si은 아님)， Sn, Sn02, Sn-Y (상기 Y는 알칼리 금속, 알칼리 토금속， 13족 원소, 14족 원소， 전이금속， 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Sn은 아님) 등을 들 수 있고， 또한 이들 중 적어도 하나와 Si02를 흔합하여 사용할 수도 있다. 상기 원소 Y로는 Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf , Rf, V， Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt , Cu, Ag, Au, Zn, Cd, B, Al , Ga, Sn, In, Ti， Ge, P, As, Sb, Bi, S, Se, Te, Po, 및 이들의 조합으로 이루어진 군에서 선택될 수 있다. 상기 전이 금속 산화물로는 바나듬 산화물， 리튬 바나듐 산화물 등을 들 수 있다. Examples of the material capable of doping and undoping lithium include Si, SiO x (0 <x <2), Si-Y alloy (Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, Rare earth element and an element selected from the group consisting of a combination thereof, not Si), Sn, Sn0 2 , Sn-Y (Y is an alkali metal, alkaline earth metal, group 13 element, An element selected from the group consisting of Group 14 elements, transition metals, rare earth elements, and combinations thereof, and not Sn), and at least one of them and Si0 2 may be used in combination. As the element Y, Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof. Examples of the transition metal oxides include vanadium oxide and lithium vanadium oxide.

상기 음극 활물질 층은 또한 바인더를 포함하며， 선택적으로 도전재를 더욱 포함할 수도 있다.  The negative electrode active material layer also includes a binder, and may optionally further include a conductive material.

상기 바인더는 음극 활물질 입자들을 서로 잘 부착시키고, 또한 음극 활물질을 전류 집전체에 잘 부착시키는 역할을 하며， 그 대표적인 예로 폴리비닐알콜， 카르복시메틸셀를로즈， 히드록시프로필샐를로즈， 폴리비닐클로라이드， 카르복실화된 폴리비닐클로라이드， 폴리비닐플루오라이드, 에틸렌 옥사이드를 포함하는 폴리머， 폴리비닐피롤리돈, 폴리우레탄, 폴리테트라플루오로에틸렌， 폴리비닐리덴 플루오라이드， 폴리에틸렌， 폴리프로필렌, 스티렌-부타디엔 러버， 아크릴레이티드 스티렌-부타디엔 러버， 에폭시 수지, 나일론등을 사용할 수 있으나， 이에 한정되는 것은 아니다.  The binder adheres well to the negative electrode active material particles, and also adheres the negative electrode active material to the current collector. Examples of the binder include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl salose, polyvinyl chloride, and carbon. Carboxylated polyvinylchloride, polyvinylfluoride, polymers including 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.

상기 도전재는 전극에 도전성을 부여하기 위해 사용되는 것으로서， 구성되는 전지에 있어서， 화학변화를 야기하지 않고 전자 전도성 재료이면 어떠한 것도 사용가능하며， 그 예로 천연 흑연， 인조 혹연， 카본 블랙, 아세틸렌 블랙, 케첸블랙， 탄소섬유 등의 탄소계 물질; 구리， 니켈， 알루미늄， 은 등의 금속 분말 또는 금속 섬유 등의 금속계 물질; 폴리페닐렌 유도체 등의 도전성 폴리머; 또는 이들의 혼합물을 포함하는 도전성 재료를 사용할 수 있다.  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. For example, natural graphite, artificial alum, carbon black, acetylene black, and ketjen. Carbon-based materials such as black and carbon fiber; 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.

상기 집전체로는 구리 박, 니켈 박, 스테인레스강 박, 티타늄 박， 니켈 발포체 (foam), 구리 발포체, 전도성 금속이 코팅된 폴리머 기재， 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다.  The current collector can be selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam (foam), copper foam, a polymer substrate coated with a conductive metal, and combinations thereof.

상기 전류 집전체로는 A1을 사용할 수 있으나 이에 한정되는 것은 아니다. 상기 음극과 양극은 활물질， 도전재 및 결착제를 용매 중에서 흔합하여 활물질 조성물을 제조하고， 이 조성물을 전류 집전체에 도포하여 제조한다. 이와 같은"전극 제조 방법은 당해 분야에 널리 알려진 내용이므로 본 명세서에서 상세한 설명은 생략하기로 한다. 상기 용매로는 N-메틸피를리돈 등을 사용할 수 있으나 이에 한정되는 것은 아니다. A1 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. Such "electrode manufacturing method is detailed described herein because it is well known in the art and details thereof will be omitted. The solvent to be used, but may include an N- methyl pyrrolidone blood but is not limited to such.

상기 전해질은 비수성 유기 용매와 리튬염을 포함한다.  The electrolyte contains a non-aqueous organic solvent and a lithium salt.

상기 비수성 유기 용매는 전지의 전기화학적 반웅에 관여하는 이온들이 이동할 수 있는 매질 역할을 한다.  The non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the cell can move.

. 상기 비수성 유기용매로는 카보네이트계， 에스테르계， 에테르계, 케톤계， 알코을계， 또는 비양성자성 용매를 사용할 수 있다 . 상기 카보네이트계 용매로는 디메틸 카보네이트 (DMC) , 디에틸 카보네이트 (DEC) , 디프로필 카보네이트 (DPC) , 메틸프로필 카보네이트 (MPC) , 에틸프로필 카보네이트 (EPC) , 메틸에틸 카보네이트 (MEC) , 에틸렌 카보네이트 (EC) , 프로필렌 카보네이트 (PC) , 부틸렌 카보네이트 (BC) 등이 사용될 수 있으며， 상기 에스테르계 용매로는 메틸 아세테이트， 에틸 아세테이트， n-프로필 아세테이트， 디메틸아세테이트， 메틸프로피오네이트， 에틸프로피오네이트， γ-부티로락톤， 데카놀라이드 (decano l ide) , 발레로락톤, 메발로노락톤 (mevalonol actone)， 카프로락톤 (capro l actone) , 등이 사용될 수 있다. 상기 에테르계 용매로는 디부틸 에테르， 테트라글라임， 디글라임， 디메톡시에탄, 2-메틸테트라히드로퓨란， 테트라히드로퓨란 등이 사용될 수 있으며, 상기 케톤계 용매로는 시클로핵사논 등이 사용될 수 있다. 또한 상기 알코올계 용매로는 에틸알코올， 이소프로필 알코을 등이 사용될 수 있으며， 상기 비양성자성 용매로는 R-CN(R은 탄소수 2 내지 20의 직쇄상， 분지상, 또는 환 구조의 탄화수소기이며， 이증결합 방향 환 또는 에테르 결합을 포함할 수 있다) 등의 니트릴류 디메틸포름아미드 등의 아미드류, 1 , 3ᅳ디옥솔란 등의 디옥솔란류 설포란 ( sul fol ane)류 등이 사용될 수 있다. . As the non-aqueous organic solvent, a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, or aprotic solvent may be used. Examples of 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), etc. may be used, and the ester solvent may be methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, ethyl propionate. Γ -butyrolactone, decanolide, valerolactone, mevalonol actone, caprolactone, and the like may be used. As the ether solvent, dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and the like may be used, and as the ketone solvent, cyclonucleanone may be used. have. In addition, 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 the like, and sulfolane such as 1,3'dioxolane, and the like. .

상기 비수성 유기 용매는 단독으로 또는 하나 이상 흔합하여 사용할 수 있으며 , 하나 이상 흔합하여 사용하는 경우의 흔합 비율은 목적하는 전지 성능에 따라 적절하게 조절할 수 있고， 이는 당해 분야에 종사하는 사람들에게는 널리 이해될 수 있다.  The non-aqueous organic solvent may be used alone or in combination of one or more, and the mixing ratio in the case of using one or more in combination can be appropriately adjusted according to the desired battery performance, which is widely understood by those skilled in the art. Can be.

또한， 상기 카보네이트계 용매의 경우 환형 (cycl ic) 카보네이트와 사슬형 (chain) 카보네이트를 흔합하여 사용하는 것이 좋다. 이 경우 환형 카보네이트와 사슬형 카보네이트는 1:1 내지 1:9의 부피비로 흔합하여 사용하는 것이 전해액의 성능이 우수하게 나타날 수 있다. In the case of the carbonate solvent, it is preferable to use a cyclic carbonate and a chain carbonate in combination. In this case annular When carbonate and chain carbonate are mixed and used in a volume ratio of 1: 1 to 1: 9, the performance of the electrolyte may be excellent.

본 발명의— 일 구현예에 따른 비수성 유기용매는 상기 카보네이트계 용매에 방향족 탄화수소계 유기용매를 더 포함할 수도 있다. 이때 상기 카보네이트계 용매와 방향족 탄화수소계 유기용매는 1:1 내지 30:1의 부피비로 흔합될 수 있다.  The non-aqueous organic solvent according to the embodiment of the present invention may further include an aromatic hydrocarbon organic solvent in the carbonate solvent. At this time, the carbonate solvent and the aromatic hydrocarbon organic solvent may be mixed in a volume ratio of 1: 1 to 30: 1.

상기 방향족 탄화수소계 유기용매로는 하기 화학식 5의 방향족 탄화수소계 화합물이 사용될 수 있다.  As the aromatic hydrocarbon organic solvent, an aromatic hydrocarbon compound of the following Formula 5 may be used.

Figure imgf000015_0001
Figure imgf000015_0001

(상기 화학식 5에서， ¾ 내지 ¾는 각각 독립적으로 수소， 할로겐， C1 내지 C10 알킬기， 할로알킬기 또는 이들의 조합이다.) (In Formula 5, ¾ to ¾ are each independently hydrogen, halogen, C1 to C10 alkyl group, haloalkyl group, or a combination thereof.)

상기 방향족 탄화수소계 유기용매는 밴젠， 플루오로벤젠, 1,2ᅳ 디플루오로벤젠， 1,3ᅳ디플루오로벤젠， 1,4-디플루오로벤젠， 1,2，3- 트리풀루오로벤젠， 1,2，4ᅳ트리풀루오로벤젠， 클로로벤젠， 1,2-디클로로벤젠, 1，3ᅳ디클로로벤젠, 1，4-디클로로벤젠, 1,2,3-트리클로로벤젠， 1，2，4- 트리클로로벤젠, 아이오도벤젠， 1，2ᅳ디아이오도벤젠, 1,3-디아이오도벤젠， 1，4- 디아이오도벤젠， 1，2，3-트리아이오도벤젠， 1,2,4-트리아이오도벤젠， 를루엔, 플루오로를루엔， 1,2—디플루오로를루엔， 1，3-디플루오로를루엔， 1,4- 디플루오로를루엔, 1,2,3-트리플루오로를루엔， 1,2,4-트리폴루오로를루엔, 클로로를루엔， 1,2-디클로로를루엔， 1，3_디클로로를루엔, 1，4ᅳ디클로로를루엔， 1，2,3ᅳ트리클로로를루엔， 1，2，4ᅳ트리클로로를루엔, 아이오도를루엔， 1，2ᅳ 디아이오도를루엔， 1,3-디아이오도를루엔, 1,4-디아이오도를루엔， 1，2，3ᅳ 트리아이오도를루엔， 1，2，4-트리아이오도를루엔， 자일렌， 및 이들의 조합으로 이루어진 군에서 선택되는 것이다.  The aromatic hydrocarbon-based organic solvent is banzen, fluorobenzene, 1,2 'difluorobenzene, 1,3' difluorobenzene, 1,4-difluorobenzene, 1,2,3-tripulobenzene , 1,2,4 ᅳ tripulobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2 , 4-trichlorobenzene, iodobenzene, 1,2, diiodobenzene, 1,3-diodiobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2, 4-triiodobenzene, toluene, fluoroluene, 1,2-difluoroluene, 1,3-difluoroluene, 1,4-difluoroluene, 1,2,3 -Trifluoroluene, 1,2,4-trifluoroluene, chloroluene, 1,2-dichloroluene, 1,3_dichloroluene, 1,4 ᅳ dichloroluene, 1, 2,3 ᅳ trichloroluene ， 1,2，4 ᅳ trichloroluene, io Toluene, 1,2 ᅳ Diiodoluene, 1,3-Diiodoluene, 1,4-Diiodoluen, 1,2,3 ᅳ Triiodoruen, 1,2,4-Triio Toluene, xylene, and combinations thereof.

상기 비수성 전해질은 전지 수명을 향상시키기 위하여 비닐렌 카보네이트 또는 하기 화학식 6의 에틸렌 카보네이트계 화합물을 더욱 포함할 수도 있다. [화학식 6] The non-aqueous electrolyte may further include vinylene carbonate or an ethylene carbonate compound represented by Chemical Formula 6 to improve battery life. [Formula 6]

Figure imgf000016_0001
Figure imgf000016_0001

(상기 화학식 6에서， R7 및 R8는 각각 독립적으로 수소， 할로겐기， 시아노기 (CN) , 니트로기 (N02) 또는 C1 내지 C5 플루오로알킬기이고， 상기 R7과 R8중 적어도 하나는 할로겐기， 시아노기 (CN) , 니트로기 (N02) 또는 C1 내지 C5의 플루오로알킬기이다. ) In Formula 6, R 7 and R 8 are each independently hydrogen, a halogen group, a cyano group (CN), a nitro group (N0 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 (N0 2 ) or C1 to C5 fluoroalkyl group.)

상기 에틸렌 카보네이트계 화합물의 대표적인 예로는 디플루오로 에틸렌카보네이트， 클로로에틸렌 카보네이트， 디클로로에틸렌 카보네이트， 브로모에틸렌 카보네이트， 디브로모에틸렌 카보네이트, 니트로에틸렌 카보네이트 시아노에틸렌 카보네이트 또는 플루오로에틸렌 카보네이트 등을 들 수 있다. 이러한 수명 향상 첨가제를 더욱 사용하는 경우 그 사용량은 적절하게 조절할 수 있다.  Representative examples of the ethylene carbonate compounds include difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate cyanoethylene carbonate, and fluoroethylene carbonate. have. In the case of further using such life improving additives, the amount thereof can be properly adjusted.

상기 리튬염은 유기 용매에 용해되어， 전지 내에서 리튬 이온의 공급원으로 작용하여 기본적인 리튬 이차 전지의 작동을 가능하게 하고， 양극과 음극 사이의 리튬 이온의 이동을 촉진하는 역할을 하는 물질이다. 이러한 리튬염의 대표적인 예로는 LiPF6 , LiBF4 ) LiSbF6, LiAsF6, LiC4F9S03 , LiC104 ) LiA102 ) LiAlCl4, LiN(CxF2x+1S02) (CyF2y+1S02) (여기서， x 및 y는 자연수임)， LiCl , Li l 및 LiB(C204)2(리륨 비스옥살레이토 보레이트 ( l ithium bi s(oxalato) borate ; LiBOB)로 이루어진 군에서 선택되는 하나 또는 둘 이상을 지지 (support ing) 전해염으로 포함한다. 리튬염의 농도는 0. 1 내지 2.0M 범위 내에서 사용하는 것이 좋다. 리튬염의 농도가 상기 범위에 포함되면， 전해질이 적절한 전도도 및 점도를 가지므로 우수한 전해질 성능을 나타낼 수 있고, 리튬 이온이 효과적으로 이동할 수 있다. The lithium salt is a substance that dissolves in an organic solvent, acts as a source of lithium ions in the battery, thereby enabling the operation of a basic lithium secondary battery, and promoting the 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 S0 3 , LiC10 4) LiA10 2) LiAlCl 4 , LiN (C x F 2x + 1 S0 2 ) (C y F 2y +1 S0 2 ), where x and y are natural numbers, LiCl, Li l and LiB (C 2 0 4 ) 2 (l ithium bis (oxalato) borate (LiBOB) One or two or more selected from the group consisting of supporting salts may be used, and the concentration of the lithium salt may be used within the range of 0.1 to 2.0 M. If the concentration of the lithium salt is in the above range, the electrolyte is appropriate. Since it has conductivity and viscosity, it can exhibit excellent electrolyte performance and can efficiently move lithium ions.

리튬 이차 전지의 종류에 따라 양극과 음극 사이에 세퍼레이터가 존재할 수 도 있다. 이러한 세퍼레이터로는 폴리에틸렌， 폴리프로필렌, 폴리비닐리덴 플루오라이드 또는 이들의 2층 이상의 . 다층막이 사용될 수 있으며， 폴리에틸렌 /폴리프로필렌 2충 세퍼레이터， 폴리에틸렌 /폴리프로필렌 /폴리에틸렌 3층 세퍼레이터， 폴리프로필렌 /폴리에틸렌 /폴리프로필렌 3층 세퍼레이터 등과 같은 흔합 다층막이 사용될 수 있음은 물론이다. Depending on the type of lithium secondary battery, a separator may exist between the positive electrode and the negative electrode. Such separators include polyethylene, polypropylene, polyvinylidene fluoride or two or more layers thereof . Multilayer film can be used, Of course, a mixed multilayer film such as a polyethylene / polypropylene double-layer separator, a polyethylene / polypropylene / polyethylene three-layer separator, a polypropylene / polyethylene / polypropylene three-layer separator, and the like can be used.

리튬 이차 전지는 사용하는 세퍼레이터와 전해질의 종류에 따라 리튬 이온 전지， 리튬 이온 폴리머 전지 및 리튬 폴리머 전지로 분류될 수 있고, 형태에 따라 원통형， 각형， 코인형， 파우치형 등으로 분류될 수 있으며， 사이즈에 따라 벌크 타입과 박막 타입으로 나눌 수 있다. 이들 전지의 구조와 제조방법은 이 분야에 널리 알려져 있으므로 상세한 설명은 생략한다.  Lithium secondary batteries may be classified into lithium ion batteries, lithium ion polymer batteries, and lithium polymer batteries according to the type of separator and electrolyte used, and may be classified into cylindrical, square, coin, and pouch types according to their type. 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.

도 1에 본 발명의 리튬 이차 전지의 대표적인 구조를 개략적으로 나타내었다. 도 1에 나타낸 것과 같이 상기 리튬 이차 전지 ( 1)는 양극 (3)， 음극 (2) 및 상기 양극 (3)과 음극 (2) 사이에 존재하는 세퍼레이터 (4)에 함침된 전해액을 포함하는 전지 용기 (5)와, 상기 전지 용기 (5)를 봉입하는 봉입 부재 (6 )를 포함한다. 이하 본 발명의 실시예 및 비교예를 기재한다. 그러나 하기의 실시예는 본 발명의 일 실시예 일뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다. 실시예  1 schematically shows a typical structure of a lithium secondary battery of the present invention. As shown in FIG. 1, 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. Hereinafter, examples and comparative examples of the present invention are described. However, the following examples are only examples of the present invention and the present invention is not limited to the following examples. Example

실시예 1 내지 3, 비교예 1 및 비교예 2  Examples 1 to 3, Comparative Example 1 and Comparative Example 2

(：0304와 Li2C03의 화학양론적 비율의 흔합물에 활물질 기준으로 MgC03 , CaF2 ) 및 Ti02가 하기 표 1에 나타낸 함량이 되게 흔합물과 건식 흔합한 후， 흔합물을 locxrc로 10 시간 동안 열처리하여 양극 활물질을 제조하였다ᅵ. 실시예 4 (： 0 3 0 4 MgC0 3 , CaF 2) and Ti0 2 based on the stoichiometric ratio of the mixture of Li 2 CO 3 to the contents shown in Table 1 below, and then dry mixed with the mixture, The mixture was heat-treated with locxrc for 10 hours to prepare a cathode active material. Example 4

Ni0.60Co0.20Mn0.20(0H)2와 Li2C03의 화학양론적 비율의 흔합물에 활물질 기준으로 MgC03 , CaF2 , 및 Ti¾가 하기 표 1에 나타낸 함량이 되게 흔합물과 건식 흔합한 후, 흔합물을 850°C로 10 시간 동안 열처리하여 양극 활물질을 제조하였다. 비교예 3 MgC03 , 및 Ti02를 표 1에 나타낸 함량이 되게 투입한 흔합물에 LiF를 추가하여 건식 흔합한 후， 상기 실시예 1과 같이 양극 활물질을 제조하였다. 비교예 4 Ni 0 . 60 Co 0 . 20 Mn 0 . 20 (0H) 2 and Li 2 CO 3 in the mixture of the stoichiometric ratio of MgC0 3 , CaF 2 , and Ti¾ on the basis of the active material to the content shown in Table 1 after the dry mix with the mixture, and then the mixture Heat treatment at 850 ° C. for 10 hours to prepare a positive electrode active material. Comparative Example 3 After dry mixing by adding LiF to the mixture in which MgC0 3 and Ti0 2 were added to the contents shown in Table 1, a cathode active material was prepared as in Example 1. Comparative Example 4

MgC03 , CaC03 , 및 Ti02를 하기 표 1에 나타낸 함량이 되게 흔합물과 건식 흔합한 후, 상기 실시예 1과 같이 양극 활물질을 제조하였다. 비교예 5 The MgC0 3, CaC0 3, and Ti0 2 to the compound and then the combined common dry shake be the amount shown in Table 1, the positive electrode active material as in Example 1 was prepared. Comparative Example 5

Co304와 Li2C03의 화학양론적 비율의 흔합물을 건식 흔합한 후, 흔합물을 1000°C로 10 시간 동안 열처리하여 양극 활물질을 제조하였다. 비교예 6 After dry mixing the mixture of the stoichiometric ratio of Co 3 0 4 and Li 2 CO 3 , the mixture was heat-treated at 1000 ° C. for 10 hours to prepare a cathode active material. Comparative Example 6

Nio.60Coo.20Mn0.2o(OH)2와 Li2C03의 화학양론적 비율의 흔합물을 건식 흔합한 후， 흔합물을 850°C로 10 시간 동안 열처리하여 양극 활물질을 제조하였다ᅳ Nio. 60 Coo. 20 Mn 0 . After dry mixing a mixture of 2 o (OH) 2 and Li 2 CO 3 in a stoichiometric ratio, a cathode active material was prepared by heat-treating the mixture at 850 ° C. for 10 hours.

[표 1] TABLE 1

Figure imgf000018_0001
코인샐의 제조
Figure imgf000018_0001
Production of Coin Sal

상기 실시예 및 비교예에서 제조된 양극 활물질 95 중량 %， 도전제로 카본 블랙 (carbon bl ack) 2.5 중량 %， 및 결합제로 PVDF 2.5중량¾> 를 용제 (솔벤트)인 Nᅳ메틸 -2 피롤리돈 (NMP) 5.0 중량 %에 첨가하여 양극 슬러리를 제조하였다. 95% by weight of the positive electrode active material prepared in Examples and Comparative Examples, 2.5% by weight of carbon black (carbon bl ack) as a conductive agent, and 2.5% by weight of PVDF as a binder (solvent) A positive electrode slurry was prepared by adding 5.0 wt% of N ᅳ methyl-2 pyrrolidone (NMP).

상기 양극 슬러리를 두께 20 내지 40/im의 양극 집전체인 알루미늄 (A1 ) 박막에 도포 및 진공 건조하고 를 프레스 (rol l press)를 실시하여 앙극을 제조하였다.  The positive electrode slurry was applied to a thin film of aluminum (A1), which is a positive electrode current collector having a thickness of 20 to 40 / im, and vacuum dried, followed by roll press to prepare an anode.

음극으로는 Li-금속을 이용하였다.  Li-metal was used as the negative electrode.

이와 같이 제조된 양극과 Li-금속을 대극으로ᅳ 전해액으로는 1.15M LiPF6EC:DMC(l : lvol%)을 사용하여 코인 셀 타입의 반쪽 전지를 제조하였다.  A coin cell type half cell was manufactured using 1.15M LiPF6EC: DMC (l: lvol%) as the electrolyte prepared by using a cathode and a Li-metal as a counter electrode.

충방전은 4.5-3.0V 범위에서 실시하였으며 수명의 경우 1.0C 율로 실시하였다 실험예  Charging and discharging was carried out in the range of 4.5-3.0V and in the case of lifespan was conducted at 1.0C rate.

실험예 1 : 전지 특성 평가  Experimental Example 1 Battery Characteristic Evaluation

하기 표 2는 상기의 실시예 및 비교예의 4.5V 초기 Format ion, 율특성， lcyle , 30cycle , 50cycle 용량 및 수명특성 데이터이다.  Table 2 below is 4.5V initial format ion, rate characteristic, lcyle, 30cycle, 50cycle capacity and life characteristic data of the above Examples and Comparative Examples.

[표 2]  TABLE 2

Figure imgf000019_0001
상기 표 2에서 Mg, Ml (예를 들어， Ca) 및 M2(예를 들어， Ti )로 도핑되고, 표면에 MFX 화합물을 포함하는 실시예 1내지 3 은 비교예 4 내지 5에 비하여 뛰어난 전지 특성이 확인 된다.
Figure imgf000019_0001
In Table 2, doped with Mg, Ml (for example Ca) and M2 (for example Ti), Examples 1 to 3 containing the MF X compound on the surface have excellent battery characteristics compared to Comparative Examples 4 to 5.

또한， 실시예 1 내지 3은 비교예 3과 비교시 Ml인 Ca의 유무 차이에 의하여 전지특성에서 차이가 확인 된다. 또한 비교예 4와 비교시 불화금속 화합물을 포함하지 않음에 따라 수명특성에서 특성 저하가 확인 된다.  In addition, in Examples 1 to 3, the difference in battery characteristics is confirmed by the presence or absence of Ca, which is Ml, in comparison with Comparative Example 3. In addition, as compared with Comparative Example 4, it does not include the metal fluoride compound, it is confirmed that the characteristic degradation in the life characteristics.

Mg , Ml 및 M2로 도핑되고， 표면에 MFx 화합물을 포함하는 실시예 1 내지 3 및 비교예 1 내지 2를 볼 때 Ca/Mg의 함량비 (중량비 )에 따라 전지 특성 차이가 나는 것을 확인 할 수 있다.  When the doping with Mg, Ml and M2, and Examples 1 to 3 and Comparative Examples 1 to 2 containing the MFx compound on the surface it can be seen that the battery characteristics difference depending on the content ratio (weight ratio) of Ca / Mg have.

또한 조성이 다른 양극 활물질인 실시예 4와 비교예 6에서도 상기의 특성 차이가 확인 된다. 실험예 2: X선 광전자 분광 분석 (X-ray Photoelectron Spectroscopy; XPS) 상기 실시예 1에서 제조한 양극 활물질에 대하여 XPS 분석하여 그 결과를 도 2에 나타내었다. 도 2로부터 코팅층은 적어도 일부에 LiF를 포함하며， 또한 상기 코팅층은 상기 도핑되는 전이금속과 결합하는 불화 금속 화합물 (예를 들어， TiF4 , CaF2) 및 상기 코어부의 금속에서 유래하는 불화 금속 화합물 (예를 들어， CoF2)을 더 포함하는 것을 확인할 수 있다. 본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 쎄조될 수 있으며， 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. In addition, in Example 4 and Comparative Example 6 which are the positive electrode active material having a different composition, the above characteristic difference is confirmed. Experimental Example 2 X-ray Photoelectron Spectroscopy (XPS) The XPS analysis of the cathode active material prepared in Example 1 was performed and the results are shown in FIG. 2. 2, the coating layer includes at least a part of LiF, and the coating layer is a metal fluoride compound (eg, TiF 4 , CaF 2 ) and a metal fluoride compound derived from the metal of the core portion bonded to the doped transition metal. (For example, CoF 2 ) can be confirmed to further include. The present invention is not limited to the above embodiments, but can be prepared in a variety of different forms, and those skilled in the art to which the present invention pertains without changing the technical spirit or essential features of the present invention It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims

【특허청구범위】 【청구항 1】 하기 화학식 1로 표시되는 화합물을 포함하는 코어 ; 및 상기 코어의 표면에 위치하고 하기 화학식 2-1 및 /또는 2— 2로 표시되는 화합물을 포함하는 코팅층을 포함하는 리튬 이차 전지용 양극 활물질: [Patent Claims] [Claim 1] A core containing a compound represented by the following formula (1); And a positive active material for a lithium secondary battery comprising a coating layer located on the surface of the core and containing a compound represented by the following formulas 2-1 and/or 2-2: [화학식 1] [Formula 1]
Figure imgf000021_0001
Figure imgf000021_0001
 상기 화학식 1에서， In Formula 1, M1 및 M2는 서로 독립적으로， Zr, Ti, Ca, V， Zn, Mo, Ni， Mn, 또는 이들의 조합이고， 0.90<a<1.10, 0<b<0..1 , 0<c<0.1, 0<d<0.1, 0<z<0.1 이고， M 1 and M 2 are independently of each other, Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, 0.90<a<1.10, 0<b<0..1, 0<c <0.1, 0<d<0.1, 0<z<0.1, [화학식 2ᅳ 1] [Formula 2ᅳ 1] M3FX M 3 F 상기 화학식 2-1에서， In Formula 2-1, M3는 Zr, Ti, Ca, V, Zn, Mo, Ni , Co, Mn, 또는 이들의 조합이고， 0<x≤4 이고， M 3 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, and 0<x≤4, [화학식 2-2] 상기 화학식 2-2에서, [Formula 2-2] In Formula 2-2, M4는 Zr, Ti, Ca, V， Zn, Mo, Ni , Co, Mn, 또는 이들의 조합이고, 0<y<4 이고， M 4 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, and 0<y<4, 상기 양극 활물질 내 MVM2의 중량비는 0.8 내지 1.2이다. The weight ratio of MVM 2 in the positive electrode active material is 0.8 to 1.2. 【청구항 2】 【Claim 2】 제 1항에 있어서， In clause 1, 상기 M1은 Ca인 것인 리튬 이차 전지용 양극 활물질. Wherein M 1 is Ca, a positive electrode active material for a lithium secondary battery. 【청구항 3】 【Claim 3】 제 1항에 있어서, According to clause 1, 상기 M2은 Ti, Zr 또는 이들의 조합인 것인 리튬 이차 전지용 양극 활물질. The positive active material for a lithium secondary battery wherein M 2 is Ti, Zr, or a combination thereof. 【청구항 4】 【Claim 4】 계 1항에 있어서, In clause 1, 상기 Mg., M1 및 M2의 몰 도핑비율은， 서로 독립적으로 0 .001 내지 0.이인 것인 리튬 이차 전지용 양극 활물질. The molar doping ratio of Mg., M 1 and M 2 is independently 0.001 to 0. A positive electrode active material for a lithium secondary battery. 【청구항 5】 【Claim 5】 제 1항에 있어서, According to clause 1, 상기 화학식 2-1로 표시되는 화합물은 CaF2 또는 Ti F4 인 것인 리튬 이차 전지용 양극 활물질. The compound represented by Formula 2-1 is CaF 2 or Ti F 4 as a positive electrode active material for a lithium secondary battery. 【청구항 6】 【Claim 6】 계 1항에 있어서， In paragraph 1, 상기 화학식 2-1의 M3은， 상기 화학식 1의 M1 , 또는 M2로부터 유래된 것인 리튬 이차 전지용 양극 활물질. M 3 of Formula 2-1 is a positive electrode active material for a lithium secondary battery derived from M 1 or M 2 of Formula 1. 【청구항 7】 【Claim 7】 제 1항에 있어서， In clause 1, 상기 화학식 2-2의 M4은， 상기 화학식 1의 Co , 또는 Mg로부터 유래된 것인 리튬 이차 전지용 양극 활물질. M 4 of Formula 2-2 is a positive electrode active material for a lithium secondary battery derived from Co or Mg of Formula 1. 【청구항 8】 【Claim 8】 제 1항에 있어서， . In paragraph 1, . 상기 M1은 Ca일 때 Ca/Mg의 중량비는 0 .3 내지 0 . 8 인 것인 리튬 이차 전지용 양극 활물질. When M 1 is Ca, the weight ratio of Ca/Mg is 0.3 to 0. 8 A positive electrode active material for a lithium secondary battery. 【청구항 9】 【Claim 9】 하기 화학식 3로 표시되는 화합물을 포함하는 코어 ; 및 A core containing a compound represented by the following formula (3); and 상기 코어의 표면에 위치하고 하기 화학식 4-1 및 /또는 4— 2로 표시되는 화합물을 포함하는 코팅층을 포함하는 리튬 이차 전지용 양극 활물질 : A positive active material for a lithium secondary battery located on the surface of the core and comprising a coating layer containing a compound represented by the following formulas 4-1 and/or 4-2: [화학식 3] Li[LiaA(1-a-b)MgbM1 cM'd]02-zFz [Formula 3] Li[Li a A( 1 - a - b) Mg b M 1 c M' d ]02-zF z 상기 화학식 3에서, A = NiaCopMnY이고， M1 및 M2는 서로 독립적으로， Zr, Ti, Ca, V, Zn, Mo, Ni , Mn, 또는 이들의 조합이고， —0.05 < a 0.1, 0<b<0.1, 0<c<0.1, 0<d<0.1, 0<z<0.1이고， 0.6 ≤ a < 0.81， 0.10 β<0.20 및 0.10< γ≤0.20 이고， In Formula 3, A = Ni a Co p Mn Y , and M 1 and M 2 are independently of each other, Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, —0.05 < a 0.1, 0<b<0.1, 0<c<0.1, 0<d<0.1, 0<z<0.1, 0.6 ≤ a < 0.81, 0.10 β<0.20 and 0.10< γ≤0.20, [화학식 4-1] [Formula 4-1] M3FX M 3 F 상기 화학식 4-1에서， In Formula 4-1, M3는 상기 화학식 3의 Ml, 또는 M2로부터 유래된 것이고， 0<x≤4 이고， [화학식 4ᅳ 2] M 3 is derived from Ml or M2 of Formula 3, 0<x≤4, [Formula 4ᅳ 2] M4Fy M 4 F y 상기 화학식 4ᅳ 2에서， In Formula 4-2, M4는 상기 화학식 3의 Ni, Co, Mn 또는 Mg로부터 유래된 것이고, 0<y≤4 이고， M 4 is derived from Ni, Co, Mn or Mg of Formula 3, and 0<y≤4, 상기 양극 활물질 내 MVM2의 중량비는 0.8 내지 1.2·이다. The weight ratio of MVM 2 in the positive electrode active material is 0.8 to 1.2 · . 【청구항 10】 【Claim 10】 리튬 공급 물질， 전이 금속 전구체， Mg 공급 물질， M1 공급 물질， M2 공급 물질， 및 불소 공급 물질을 건식 흔합하는 단계 ; Dry mixing the lithium supply material, transition metal precursor, Mg supply material, M 1 supply material, M 2 supply material, and fluorine supply material; 상기 흔합물을 소성하는 단계 ; 및 Calcining the mixture; and 하기 화학식 1로 표시되는 화합물을 포함하는 코어; 및 상기 코어의 표면에 위치하고 하기 화학식 2-1 및 /또는 2-2로 표시되는 화합물을 포함하는 코팅층；을 포함하는 리튬 이차 전지용 양극 활물질을 수득하는 단계; A core containing a compound represented by Formula 1 below; and a coating layer located on the surface of the core and containing a compound represented by the following formula 2-1 and/or 2-2; Obtaining a positive electrode active material for a lithium secondary battery comprising: 를 포함하는 리튬 이차 전지용 양극 활물질의 제조 방법: Method for producing a positive electrode active material for a lithium secondary battery comprising: [화학식 1] [Formula 1]
Figure imgf000023_0001
Figure imgf000023_0001
 상기 화학식 1에서， In Formula 1, M1 및 M2는 서로 독립적으로， Zr, Ti, Ca, V， Zn, Mo, Ni , Mn, 또는 이들의 조합이고， 0.90<a<1.10, 0<b<0.1 , 0<c<0.1 , 0<d<0.1 , 0<z<0.1 이고， M 1 and M 2 are independently of each other, Zr, Ti, Ca, V, Zn, Mo, Ni, Mn, or a combination thereof, 0.90<a<1.10, 0<b<0.1, 0<c<0.1, 0<d<0.1, 0<z<0.1, [화학식 2-1] 상기 화학식 2ᅳ1에서, [Formula 2-1] In the above formula 2ᅳ1, M3는 Zr, Ti, Ca, V， Zn, Mo, Ni , Co, Mn, 또는 이들의 조합이고， 0<x<4 이고， M 3 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, and 0<x<4, [화학식 2-2] [Formula 2-2] M4Fy M 4 F y 상기 화학식 2ᅳ 2에서， ' In the above formula 2-2, ' M4는 Zr, Ti, Ca, V， Zn, Mo, Ni , Co, Mn, 또는 이들의 조합이고， 0<y<4 이고ᅳ M 4 is Zr, Ti, Ca, V, Zn, Mo, Ni, Co, Mn, or a combination thereof, and 0<y<4 and ᅳ 상기 양극 활물질 내 MVM2의 중량비는 0.8 내지 1.2이다. The weight ratio of MVM 2 in the positive electrode active material is 0.8 to 1.2. 【청구항 11】 【Claim 11】 제 10항에 있어서， In clause 10, 상기 Mg, M1 및 M2의 공급 물질은， 서로 독립적으로 수산화물, 옥시수산화물， 질산염， 할로겐화물， 탄산염 , 초산염， 옥살산염 또는 시트르산염 형태인 것인 리튬 이차 전지용 양극 활물질의 제조 방법. The supply materials of Mg, M 1 and M 2 are independently of each other in the form of hydroxide, oxyhydroxide, nitrate, halide, carbonate, acetate, oxalate or citrate. Method for producing a positive electrode active material for a lithium secondary battery. 【청구항 12] [Claim 12] 제 10항에 있어서， In clause 10, 상기 불소 공급 물질은 암모늄염， 리튬염 또는 금속염 형태인 것인 리튬 이차 전지용 양극 활물질의 제조 방법. A method of producing a positive electrode active material for a lithium secondary battery, wherein the fluorine supply material is in the form of ammonium salt, lithium salt, or metal salt. 【청구항 13】 【Claim 13】 제 10항에 있어서, According to clause 10, 상기 흔합물을 소성하는 단계 ;에서 , In the step of calcining the mixture, 소성 온도는 800 내지 1,050 °C인 것인 리튬 이차 전지용 양극 활물질의 제조 방법. A method for producing a positive electrode active material for a lithium secondary battery, wherein the sintering temperature is 800 to 1,050 ° C. 【청구항 14】 【Claim 14】 제 1항 내지 제 9항 중 어느 한.항에 따른 리튬 이차 전지용 양극 활물질을 포함하는 양극; The positive electrode active material for a lithium secondary battery according to any one of claims 1 to 9. Containing an anode; 음극 활물질을 포함하는 음극; 및 전해질; A negative electrode containing a negative electrode active material; and electrolytes; 을 포함하는 리튬 이차 전지 . Lithium secondary battery containing.
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