WO2015122690A1 - Matériau actif de cathode pour une batterie rechargeable au lithium, son procédé de préparation et batterie rechargeable au lithium contenant ce dernier - Google Patents

Matériau actif de cathode pour une batterie rechargeable au lithium, son procédé de préparation et batterie rechargeable au lithium contenant ce dernier Download PDF

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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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formula
active material
lithium secondary
secondary battery
positive electrode
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PCT/KR2015/001388
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Korean (ko)
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이승원
권혁원
홍진곤
정봉준
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주식회사 엘앤에프신소재
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Publication of WO2015122690A1 publication Critical patent/WO2015122690A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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—Cobaltates
    • C01G51/42—Cobaltates 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

La présente invention se rapporte à un matériau actif de cathode pour une batterie rechargeable au lithium, à un procédé de préparation associé et à une batterie rechargeable au lithium contenant ledit matériau actif de cathode et concerne un matériau actif de cathode pour une batterie rechargeable au lithium, comprenant : un noyau comprenant un composé représenté par la formule chimique suivante ; et une couche de revêtement placée sur la surface du noyau et comprenant un composé représenté par les formules chimiques 2-1 et/ou 2-2. [Formule chimique 1] LiaCo1-bMgbM1 cM2 dO2-zFz [formule chimique 2-1] M3Fx [formule chimique 2-2] M4Fy. La définition par rapport aux formules chimiques 1, 2-1 et 2-2 est présente dans la description.
PCT/KR2015/001388 2014-02-11 2015-02-11 Matériau actif de cathode pour une batterie rechargeable au lithium, son procédé de préparation et batterie rechargeable au lithium contenant ce dernier WO2015122690A1 (fr)

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KR20140008584A (ko) * 2012-07-09 2014-01-22 주식회사 엘지화학 양극 활물질 및 이를 포함하는 리튬 이차전지

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KR20060028408A (ko) * 2003-08-19 2006-03-29 세이미 케미칼 가부시끼가이샤 리튬 이차 전지용 양극 재료 및 그 제조방법
KR100751746B1 (ko) * 2004-04-30 2007-08-27 에이지씨 세이미 케미칼 가부시키가이샤 리튬 2차 전지 정극용 리튬 함유 복합 산화물의 제조 방법
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KR20150094551A (ko) 2015-08-19

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