WO2020175925A1 - 이차전지용 양극 활물질 전구체, 양극 활물질, 그 제조방법 및 이를 포함하는 리튬 이차전지 - Google Patents

이차전지용 양극 활물질 전구체, 양극 활물질, 그 제조방법 및 이를 포함하는 리튬 이차전지 Download PDF

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WO2020175925A1
WO2020175925A1 PCT/KR2020/002782 KR2020002782W WO2020175925A1 WO 2020175925 A1 WO2020175925 A1 WO 2020175925A1 KR 2020002782 W KR2020002782 W KR 2020002782W WO 2020175925 A1 WO2020175925 A1 WO 2020175925A1
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active material
cathode active
secondary battery
material precursor
positive electrode
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PCT/KR2020/002782
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English (en)
French (fr)
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이민준
이준원
전인국
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주식회사 엘지화학
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Priority to EP20763320.7A priority Critical patent/EP3915945A4/en
Priority to CN202080016380.1A priority patent/CN113474299B/zh
Priority to US17/433,345 priority patent/US20220048789A1/en
Priority to JP2021549856A priority patent/JP2022522164A/ja
Publication of WO2020175925A1 publication Critical patent/WO2020175925A1/ko

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/45—Aggregated particles or particles with an intergrown morphology
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

  • cathode active material precursor for secondary battery cathode active material precursor for secondary battery, cathode active material, its manufacturing method and lithium secondary battery technology field including the same
  • the present invention relates to a cathode active material precursor for a secondary battery, a cathode active material, a manufacturing method thereof, and a lithium secondary battery including the same.
  • lithium secondary batteries are light-weight. Due to its high energy density, it is attracting attention as a driving power source for portable devices. Accordingly, research and development efforts to improve the performance of lithium secondary batteries are actively progressing.
  • lithium secondary batteries when lithium ions are inserted/desorbed from the positive electrode and the negative electrode in a state in which an organic electrolyte or polymer electrolyte is charged between the positive electrode and the negative electrode made of an active material capable of intercalations and deintercalation of lithium ions. Electrical energy is produced by the oxidation and reduction reactions of
  • Lithium secondary battery cathode active materials include lithium cobalt oxide (LiCo0 2 ), lithium nickel oxide (LiNi0 2 ), lithium manganese oxide (LiMn0 2 or LiMn 2 0 4, etc.), lithium iron phosphate compound (LiFeP0 4 ), etc.
  • LiNi k CO a CMoczO.l OJ partially substituted with cobalt, exhibits excellent charging/discharging characteristics and lifetime characteristics, but has low thermal stability.
  • Ni nickel
  • Mn manganese
  • the cycle characteristics and thermal stability are relatively There are advantages to being excellent.
  • the precursor of the NCM-based cathode active material is synthesized through a coprecipitation method, mainly in the form of hydroxide or carbonate.
  • Hydroxide precursor P Co al Mn p1 (OH) 2 (0 ⁇ al ⁇ 1.0, 0
  • the primary particles are very large, about 1 to 3, and there are disadvantages of low ionic conductivity and poor electrochemical performance and density.
  • the primary particles are too small, about 10- ⁇ 111, and carbon dioxide is desorbed during the firing process, and the voids in the secondary particles become very large. There was a drawback of falling very much.
  • the primary particles are small and the secondary particles are dense, so that they exhibit high density, and the excellent particle strength prevents particle breakage when rolling, and when applied to secondary batteries, it will exhibit excellent battery performance such as high capacity, efficiency and rate characteristics.
  • the primary particles are small and the secondary particles are dense, so that they exhibit high density, and the excellent particle strength prevents particle breakage when rolling, and when applied to secondary batteries, it will exhibit excellent battery performance such as high capacity, efficiency and rate characteristics.
  • the present invention is to provide an NCM-based cathode active material precursor and its manufacturing method that can exhibit high density due to small primary particles and dense secondary particles, and excellent particle strength.
  • NCM-based positive electrode active material with an excess of lithium (Ni- ⁇ ) manufactured using the positive electrode active material precursor a positive electrode active material capable of exhibiting excellent battery performance such as high capacity, efficiency, and rate characteristics when applied to secondary batteries. And it is intended to provide a manufacturing method.
  • the present invention includes nickel (), cobalt ((3 ⁇ 4) and manganese (Mn), and the nickel () and cobalt ((3 ⁇ 4) are oxidized. It provides a cathode active material precursor for secondary batteries in an oxidized form.
  • the present invention is a step of continuously introducing a solution containing nickel (), cobalt ((3 ⁇ 4) and manganese (Mn) transition metal cation, an alkali solution and a solution containing ammonium ions into the reactor; And gas is supplied to the reactor.
  • the present invention uses the cathode active material precursor and lithium raw material prepared as described above. Mixing step; And after the mixing, lithium composite by firing at 750 to 1,000 °C
  • It provides a method for producing a cathode active material for a secondary battery comprising; forming a transition metal oxide.
  • the present invention provides a positive electrode active material manufactured as described above, a positive electrode and a lithium secondary battery including the same.
  • NCM-based anode active material precursors that exhibit high density and excellent particle strength due to small primary particles and dense secondary particles.
  • the lithium-rich NCM-based positive electrode active material manufactured by using the positive electrode active material precursor can exhibit excellent battery performance such as high capacity, efficiency, and rate characteristics when applied to a secondary battery.
  • Example 1 is an XPS data of the precursor of a positive electrode active material prepared in Example 1.
  • Figure 2 is a reference data of XPS data of manganese oxide.
  • Fig. 4 is XRD data of the precursor of the positive electrode active material prepared in Comparative Example 2.
  • FIG. 1 is an enlarged observation of the cathode active material precursor prepared in Example 1
  • FIG. 7 is an enlarged observation of the cathode active material precursor prepared in Comparative Example 2
  • the precursor of the cathode active material of the present invention is nickel (Ni), cobalt (Co) and manganese (Mn) in the reactor. 2020/175925 1»(:1 ⁇ 1 ⁇ 2020/002782 Transition metal cation-containing solution, alkali solution and ammonium ion-containing solution
  • the transition metal cation-containing solution contains nickel ()-containing raw material, cobalt ((3 ⁇ 4)-containing raw material and manganese (Mn)-containing raw material.
  • the above nickel ()-containing raw materials are, for example, nickel-containing acetate, nitrate,
  • It may be sulfate, halide, sulfide, hydroxide, oxide, or oxyhydroxide, and specifically, (03 ⁇ 4 2 , 0, 003 ⁇ 4 (that 0 3 ⁇ 2 (03 ⁇ 4 2 ⁇ 43 ⁇ 40, (that 2 0 2 ⁇ 23 ⁇ 40, uh0 3 ) 2 ⁇ 63 ⁇ 40, 30 4 , ⁇ 80 4 ⁇ 63 ⁇ 40, It may be a fatty acid nickel salt, nickel halide or a combination thereof, but is not limited thereto.
  • the cobalt ((3 ⁇ 4)-containing raw material material may be cobalt-containing acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide or oxyhydroxide, etc., specifically (3 ⁇ 4(03 ⁇ 4 2 ,(3 ⁇ 4003 ⁇ 4(3 ⁇ 4( It may be 0(:0(:3 ⁇ 4) 2 ⁇ 43 ⁇ 40, (3 ⁇ 4 eo 0 3 ) 2 ⁇ 63 ⁇ 40, 0080 4 , (3 ⁇ 4 0 4 ) 2 ⁇ 73 ⁇ 40 or a combination thereof, but is not limited thereto.
  • the manganese (Mn)-containing raw material may be, for example, manganese-containing acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide, oxyhydroxide or a combination thereof, specifically Mn 2 0 3 Manganese oxides such as, Mn 3 O 4 and the like;
  • Manganese salts such as Mn(N0 3 ) 2 , MnS0 4 , manganese acetate, manganese dicarboxylic acid, manganese citrate, and manganese fatty acid; may be manganese oxyhydroxide, manganese chloride or a combination thereof, but is not limited thereto.
  • the transition metal cation-containing solution is an organic material that can be uniformly mixed with nickel ()-containing raw material, cobalt ((3 ⁇ 4)-containing raw material and manganese (11)-containing raw material as a solvent, specifically water or water. It is manufactured by adding it to a mixed solvent of a solvent (for example, alcohol, etc.), or by mixing an aqueous solution of raw material containing nickel, an aqueous solution of raw material containing cobalt ((3 ⁇ 4), and raw material containing manganese (Mn).
  • a solvent for example, alcohol, etc.
  • the ammonium ion-containing solution is a complex forming agent, for example NH 4 OH, 3 ⁇ 4) 2 30 4 ,
  • the ammonium ion-containing solution may be used in the form of an aqueous solution, and in this case, the solvent is water or A mixture of water and an organic solvent (specifically, alcohol, etc.) that can be uniformly mixed with water can be used.
  • the solvent is water or A mixture of water and an organic solvent (specifically, alcohol, etc.) that can be uniformly mixed with water can be used.
  • the alkali solution is a precipitant, such as NaOH, 011 or 011) 2 , etc. of alkali metals or hydroxides of alkali earth metals, hydrates thereof, or alkalis of combinations thereof 2020/175925 1»(:1 ⁇ 1 ⁇ 2020/002782 May contain compounds.
  • the alkali solution can also be used in the form of an aqueous solution, and in this case, the solvent is water or evenly mixed with water.
  • a mixture of organic solvent (specifically, alcohol, etc.) and water may be used.
  • the alkali solution is added to control ! ⁇ of the reaction solution, and may be added in an amount of 11 to 13 of the metal solution.
  • nickel () and cobalt ((3 ⁇ 4) are in the form of non-oxidized hydroxide, An oxidized form of the anode active material precursor is formed.
  • the primary particles are small and the secondary particles are dense, resulting in high density.
  • a cathode active material precursor was produced by co-precipitation without introducing gas during the precursor co-precipitation reaction or by continuously introducing oxygen-containing gas.
  • nickel () and cobalt ((3 ⁇ 4) are in the form of unoxidized hydroxide and form the precursor of the positive electrode active material, which is an oxidized form.
  • nitrogen 2 ), argon ! ⁇ ) and carbonic acid (3 ⁇ 4(:0 3 ) gas may not be injected into the reactor during the co-precipitation reaction.
  • oxygen-containing gas can be continuously injected.
  • the input flow rate of the oxygen (0 2 ) gas may more specifically satisfy Equation 1 below.
  • the input flow rate of oxygen (0 2 ) gas can be 15. lL/h to 16.611 1. If the gas contains 20% by volume of oxygen (02) gas, The total gas input flow can be 75.51 1 to 83.051 ⁇ 1.
  • nickel () and cobalt ((3 ⁇ 4) are in the form of unoxidized hydroxide, and manganese (Mn) is in the form of oxidized anode active material. It can form precursors, through which the primary particles are small and the secondary particles are dense, resulting in high density and excellent particle strength.
  • the cathode active material precursor manufactured according to an embodiment of the present invention may be represented by Formula 1 below.
  • the cathode active material precursor manufactured according to the present invention is nickel (), cobalt ((3 ⁇ 4) and
  • nickel () and cobalt ((3 ⁇ 4) are not oxidized
  • the cathode active material precursor is in the form of secondary particles in which primary particles are aggregated
  • the particle diameter of the primary particles may be 50 to 50011111, more preferably 80 to 400, 11, and more preferably 100 to 30011111.
  • Sangik according to an embodiment of the present invention Even if ions do not react with alkali compounds after coordination with ammonium ions, they can be precipitated as oxides by combining with the introduced oxygen (0 2 ) gas or air. Because it is very fast, it can form smaller primary particles than conventional hydroxide-type precursors. As the cathode active material precursor satisfies the primary particle size range, the primary particles are small and the secondary particles are dense, resulting in high density, and excellent particles. May indicate strength.
  • the cathode active material precursor may have a tap density higher than ⁇ Aglcc, and more preferably 1.4 to 2. / ⁇ , more preferably 1.5 to 2.
  • the tap density is the same as when the positive electrode active material precursor 5 is placed in a 501111 mass cylinder and 1250 strokes are performed using a show ⁇ 2 tap density meter (I £13 ⁇ 4 ⁇ 11 1111 show ( 3)). It is the tap density.
  • the present invention provides a positive electrode active material manufactured using the positive electrode active material.
  • the cathode active material of the present invention is a step of mixing the cathode active material precursor and the lithium raw material material; And after the mixture is fired at 750 to 1,000° (:), a lithium composite transition metal It includes; forming an oxide.
  • the cathode active material precursor of the present invention and the lithium raw material are mixed.
  • the cathode active material precursor contains nickel (), cobalt ((3 ⁇ 4) and manganese, nickel () and cobalt ((3 ⁇ 4) are in the form of unoxidized hydroxide, and manganese is in the form of oxidized.
  • the lithium raw material material may include lithium-containing sulfate, nitrate, acetate, carbonate, oxalate, citrate, halide, hydroxide or oxyhydroxide, and is not particularly limited as long as it is soluble in water.
  • the lithium source Is 0 2 00 3 , ⁇ 0 3 , ⁇ 0 2 , 1G 03 ⁇ 4 1 011 ⁇ 3 ⁇ 40, U ⁇ ,, 001, UBr, 01,(:3 ⁇ 4 0000, 0 2 0, 0 2 80 4 ,(:3 ⁇ 4 (:001 ⁇ or 1 ⁇ 03 ⁇ 40 7 may be used, and any one or a mixture of two or more of them may be used.
  • the positive electrode active material precursor and the lithium raw material have lithium (Ni) of 1: 1.2 to 1: 1.6
  • the positive electrode active material of the present invention thus prepared is applied to all metals (M) except lithium.
  • pellet density is a transition metal oxide, and the pellet density can appear as high as 2. / ⁇ or more, more preferably 2.2 to 3.0 ⁇ 00, and even more preferably 2.3 to 2 /.
  • the pellet density is the positive electrode active material 5 Into the 22111111 mold
  • a cathode for a secondary battery and a lithium secondary battery including the cathode active material are provided.
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector and including the positive electrode active material.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery, for example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel. Surface treatment with carbon, nickel, titanium, silver, etc. can be used on the surface.
  • the positive electrode current collector may have a thickness of 3 to 500/ffli, and fine irregularities on the surface of the positive electrode current collector It is also possible to increase the adhesion of the positive electrode active material by forming, for example, it can be used in various forms such as film, sheet, foil, net, porous material, foam, and non-woven fabric.
  • the above conductive material is used to impart conductivity to the electrode, and can be used without particular limitation as long as it does not cause chemical changes and has electronic conductivity in the configured battery.
  • Specific examples include natural graphite or artificial graphite.
  • Graphite such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, carbon fiber, and other carbon-based materials; copper, nickel, aluminum, silver, and other metal powders or metal fibers; oxidation Conductive whiskey such as zinc and potassium titanate; conductive metal oxides such as titanium oxide; or conductive polymers such as polyphenylene derivatives, of which one alone or a mixture of two or more may be used.
  • it may be included in an amount of 1 to 30% by weight based on the total weight of the positive electrode active material layer.
  • the binder is attached between the positive electrode active material particles and the positive electrode active material and the positive electrode
  • PVDF Polyvinylidene fluoride
  • Vinylidene fluoride-hexafluoropropylene copolymer PVDF-co-HFP
  • polyvinyl alcohol polyacrylonitrile
  • Carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), alcohol Ponified-EPDM, styrene butadiene rubber (SBR), fluorine rubber, or various copolymers thereof, and one of them alone or a mixture of two or more may be used.
  • the binder is based on the total weight of the positive electrode active material layer. It may be included in 1 to 30% by weight.
  • the anode may be manufactured according to a conventional anode manufacturing method, except for using the cathode active material described above. Specifically, the cathode active material and the above-described cathode active material.
  • a composition for forming a positive electrode active material layer including a binder and a conductive material may be coated on a positive electrode current collector, followed by drying and rolling. At this time, the types and contents of the positive electrode active material, binder, and conductive material are as described above. same.
  • This solvent may be a solvent generally used in the relevant technical field, dimethyl sulfoxide (DMSO), isopropyl alcohol 2020/175925 1»(:1/10 ⁇ 020/002782
  • DMSO dimethyl sulfoxide
  • &1.01101 methylpyrrolidone (NMP), acetone (lime or water, etc., one of them alone or a mixture of two or more may be used.
  • the amount of the above solvent is the thickness of the slurry applied, In consideration of the manufacturing yield, it is sufficient to dissolve or disperse the positive electrode active material, the conductive material, and the binder, and then to have a viscosity that can exhibit excellent thickness uniformity when applied for manufacturing the positive electrode.
  • Silver may be produced by casting the composition for forming a positive electrode active material layer on a separate support and then laminating a film obtained by peeling from the support on the positive electrode current collector.
  • an electrochemical device including the positive electrode may specifically be a battery or a capacitor, and more specifically, a lithium secondary battery.
  • the lithium secondary battery specifically includes a positive electrode, a negative electrode positioned opposite to the positive electrode, a separator and an electrolyte interposed between the positive electrode and the negative electrode, and the positive electrode is as described above.
  • the lithium secondary battery includes the positive electrode and the negative electrode.
  • a battery container for storing the negative electrode and the electrode assembly of the separator, and a sealing member for sealing the battery container may be optionally further included.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector.
  • the cathode current collector has high conductivity without causing chemical changes to the battery.
  • the negative electrode current collector may be used. In general, it can have a thickness of 3 to 500//111, and like the positive electrode current collector, it is possible to strengthen the bonding strength of the negative electrode active material by forming fine irregularities on the surface of the current collector.
  • film, sheet, foil, It can be used in various forms such as net, porous material, foam, and non-woven fabric.
  • the negative electrode active material layer selectively includes a binder and a conductive material together with the negative electrode active material.
  • the negative electrode active material layer is an example coated with a negative electrode active material on the negative electrode current collector, and a composition for forming a negative electrode, optionally including a binder and a conductive material. And dry, or cast the composition for forming the cathode on a separate support, and then peel the film obtained from this support on the cathode current collector.
  • the cathode active material a compound capable of reversible intercalation and deintercalation of lithium may be used. Specific examples include carbon materials such as artificial graphite, natural graphite, graphitized carbon fiber, and amorphous carbon; Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd,
  • Metallic compounds capable of alloying with lithium such as Si alloy, Sn alloy, or A1 alloy; SiO p (0 ⁇ (3 ⁇ 2), Sn0 2 , vanadium oxide, a metal oxide capable of dope and undoping lithium such as lithium vanadium oxide; or the above metal nitride compound and carbon, such as Si-C complex or Sn-C complex.
  • a composite including a material may be mentioned, and any one or a mixture of two or more of them may be used.
  • a metal lithium thin film may be used as the cathode active material.
  • the carbon material is low crystalline carbon and high crystalline carbon.
  • Low crystalline carbon is typically soft carbon and hard carbon, and high crystalline carbon is amorphous, plate-like, scale, spherical or fibrous natural explosive or artificial width.
  • High temperature calcination carbons such as (petroleum or coal tar pitch derived cokes) are representative.
  • binder and conductive material may be the same as described in the previous anode.
  • the separator separates the cathode and the anode and provides a passage for lithium ions.
  • the separator separates the cathode and the anode and provides a passage for lithium ions.
  • a separator it can be used without special restrictions, and in particular, it is preferable that it has a low resistance to ion migration of the electrolyte and has excellent electrolyte moisture content.
  • a porous polymer film such as ethylene homopolymer, propylene homopolymer, ethylene/ Butene copolymer, ethylene/hexene copolymer, and
  • Porous polymer films made of polyolefin-based polymers such as ethylene/methacrylate copolymers, or a laminated structure of two or more layers thereof may be used.
  • conventional porous non-woven fabrics, for example high melting point glass fibers, may be used.
  • a nonwoven fabric made of polyethylene terephthalate fiber, etc. may be used.
  • a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and optionally, a single layer or a multilayer structure may be used.
  • the electrolyte used in the present invention can be used when manufacturing lithium secondary batteries.
  • Organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel polymer electrolytes, solid inorganic electrolytes, molten inorganic electrolytes, etc. may be mentioned, but are not limited to these.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of a battery can move.
  • organic solvent methyl acetate, ethyl
  • Acetate ethyl acetate
  • butyrolactone y-butyrolactone
  • Ester solvents such as 8-caprolactone; Ether solvents, such as dibutyl ether or tetrahydrofuran;
  • Ketone solvents such as cyclohexanone; benzene,
  • Aromatic hydrocarbon-based solvents such as fluorobenzene
  • DMC Dimethylcarbonate
  • DEC diethylcarbonate
  • MEC methylethylcarbonate
  • Carbonate-based solvents such as ethylmethylcarbonate (EMC), ethylene carbonate (EC), and propylene carbonate (PC); alcohol-based solvents such as ethyl alcohol and isopropyl alcohol; Nitriles such as R-CN (R is a hydrocarbon group having a C2 to C20 linear, branched or cyclic structure, and may contain a double bonded aromatic ring or an ether bond); amides such as dimethylformamide; 1,3 -Dioxolanes such as dioxolane; or sulfolane, etc., among them, carbonate-based solvents are preferable, and a cyclic type having high ionic conductivity and high dielectric constant that can increase the charging/discharging performance of the battery.
  • Carbonate for example, ethylene carbonate or propylene carbonate
  • a mixture of carbonate-based compounds (e.g., ethylmethyl carbonate, dimethyl carbonate, or diethyl carbonate) is more preferable.
  • the cyclic carbonate and the chain carbonate are mixed in a volume ratio of about 1:1 to about 1:9.
  • the electrolyte performance can be excellent.
  • the lithium salt is capable of providing lithium ions used in lithium secondary batteries.
  • any compound may be used without particular limitation.
  • the lithium salt LiPF 6 , LiC10 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiA10 4 , L1AICI 4 , LiCF 3 S0 3 , LiC 4 F 9 S0 3 , LiN (C 2 F 5 S0 3 ) 2 , LiN(C 2 F 5 S0 2 ) 2 , LiN(CF 3 S0 2 ) 2 .
  • LiCl, Lil, or LiB(C 2 0 4 ) 2 may be used.
  • the concentration of the lithium salt is preferably within the range of 0.1 to 2.0 M. When the concentration of the lithium salt falls within the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can move effectively.
  • the electrolyte includes, for example, a haloalkylene carbonate-based compound such as difluoroethylene carbonate, for the purpose of improving the lifespan of the battery, suppressing the reduction of battery capacity, and improving the discharge capacity of the battery.
  • a haloalkylene carbonate-based compound such as difluoroethylene carbonate
  • Pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylenediamine
  • additives such as dye, N-substituted oxazolidinone, N,N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol or aluminum trichloride may be included.
  • the additive may be included in an amount of 0.1 to 5% by weight based on the total weight of the electrolyte.
  • the lithium secondary battery containing the positive electrode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention rate, portable devices such as mobile phones, notebook computers, digital cameras, and hybrids
  • HEVs hybrid electric vehicles
  • the lithium secondary battery [119] Accordingly, according to another embodiment of the present invention, the lithium secondary battery
  • a battery module including a cell and a battery pack including the same are provided.
  • the battery module or battery pack includes a power tool; an electric vehicle (Elec ic Vehicle, EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV). It can be used as a power source for any one or more medium and large devices of electric vehicles;
  • EV Electric Vehicle
  • PHEV plug-in hybrid electric vehicle
  • 300 ml/hr, 28 wt% aqueous ammonia solution was continuously added to the reactor at 42 ml/hr.
  • the impeller speed was stirred at 400 rpm, and a pH of 9.5 was maintained by using 40 wt% sodium hydroxide solution to maintain the pH.
  • a 28% by weight aqueous ammonia solution was continuously added to the reactor at 42 sen/.
  • the impeller speed was stirred at 400 111.
  • a 28% by weight aqueous ammonia solution was continuously added to the reactor at 42 ml/hr.
  • the impeller speed was stirred at 400 rpm. 20% by weight to maintain pH
  • the precursor particles of Ni Q.2 Co Q.2 Mn Q.6 C0 3 were formed by co-precipitation reaction for 24 hours. The precursor particles were separated, washed, and dried in a 130 O C oven to prepare a cathode active material precursor.
  • Example 1 The cathode active material precursors prepared in Example 1 and Comparative Examples 1 to 2 were subjected to XPS and XRD.
  • XPS analysis was performed using ESCALAB 250 (Thermo Fisher Scientific) equipment with an acceleration voltage of 15kV (power: 150W), energy resolution of about l.OeV, and analysis.
  • XPS spectroscopy test was performed by obtaining a survey scan spectrum and a narrow scan spectrum under the analysis conditions of a 500 micrometer area diameter and a sputter rate of O.lnm/sec.
  • XRD diffraction measurements were performed at a rate of 3° per minute within the range of W to 90° with an acceleration voltage of 40 kV and an acceleration current of 40 mA.
  • Comparative Example 1 is Ni, Co, Mn 2020/175925 1»(:1 ⁇ 1 ⁇ 2020/002782 It is a hydroxide form, and Comparative Example 2 was confirmed to be a carbonate form of Ni, Co, and Mn.
  • Figures 5 to 7 are enlarged photographs of observation with a scanning electron microscope £ ⁇ 1).
  • Figure 5 is a precursor of the positive electrode active material of Comparative Example 1 in the form of a hydroxyl, showing that the primary particles are large and the secondary particles are not dense.
  • 6 is a positive electrode active material precursor of Comparative Example 2 in carbonate form, and it can be seen that the primary particles are too small and the pores in the particles are large.
  • FIG. 7 is a positive electrode active material precursor of Example 1, 1 It can be confirmed that the borrower is small and has a dense secondary particle shape.
  • the tap density was measured by performing 1250 strokes. The results are shown in Table 1 below.
  • the tap density is significantly higher than that of the precursor of the positive electrode active material of Comparative Examples 1 and 2 in the form of hydroxide/carbonate.
  • Example 2 Each of the positive electrode active materials prepared in Example 2 and Comparative Examples 3 to 4 was molded with a diameter of 22111111 5 silver, and the pellet density was measured at a pressure of 2 tons using HPRM-A2 (Hantech Co., Ltd.). The results are shown in Table 2 below. [152] [Table 2]
  • the positive electrode active material of Example 2 is hydroxide/carbonate
  • pellet density is significantly higher than that of the positive electrode active material of Comparative Examples 3 to 4 prepared using the positive electrode active material precursor in the form.
  • Example 2 The cathode active material, carbon black conductive material, and PVdF binder prepared in Example 2 and Comparative Examples 3 to 4 were mixed in a weight ratio of 96:2:2 in an N-methylpyrrolidone solvent, A mixture was prepared, coated on one side of an aluminum current collector, dried at 130 O C, and rolled to produce a positive electrode.
  • Lithium metal was used as the cathode.
  • An electrode assembly was manufactured by interposing a porous polyethylene separator between the positive electrode and the negative electrode prepared as described above, and after placing the electrode assembly inside the case, an electrolyte was injected into the case to manufacture a lithium secondary battery. .At this time, the electrolyte
  • LiPF 6 lithium nuclear tetrafluorophosphate

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Abstract

본 발명은 반응기에 니켈(Ni), 코발트(Co) 및 망간(Mn) 전이금속 양이온 함유 용액, 알칼리 용액 및 암모늄 이온 함유 용액을 연속적으로 투입하는 단계; 및 상기 반응기에 가스를 투입하지 않거나, 산소 함유 가스를 연속적으로 투입하면서 공침시켜, 니켈(Ni) 및 코발트(Co)는 산화되지 않은 하이드록사이드 형태이고, 망간(Mn)은 산화된 형태인 양극 활물질 전구체를 형성하는 단계;를 포함하는 이차전지용 양극 활물질 전구체의 제조방법을 제공한다. 또한, 본 발명은 니켈(Ni), 코발트(Co) 및 망간(Mn)을 포함하며, 상기 니켈(Ni) 및 코발트(Co)는 산화되지 않은 하이드록사이드 형태이고, 망간(Mn)은 산화된 형태인 이차전지용 양극 활물질 전구체를 제공한다.

Description

2020/175925 1»（：1/10公020/002782 명세서
발명의 명칭:이차전지용양극활물질전구체，양극활물질，그 제조방법 및이를포함하는리튬이차전지 기술분야
[1] 과려츰워과의상호이용
[2] 본출원은 2019년 2월 28일자한국특허출원제 10-2019-0024312호에기초한 우선권의이익을주장하며,해당한국특허출원의문헌에개시된모든내용은 본명세서의일부로서포함된다.
[3] 기숨분야
[4] 본발명은이차전지용양극활물질전구체,양극활물질,그제조방법및이를 포함하는리튬이차전지에관한것이다.
[5]
배경기술
[6] 최근휴대전화,노트북컴퓨터,전기자동차등전지를사용하는전자기구의 급속한보급에수반하여소형경량이면서도상대적으로고용량인이차전지의 수요가급속히증대되고있다.특히,리튬이차전지는경량이고고에너지밀도를 가지고있어휴대기기의구동전원으로서각광을받고있다.이에따라,리튬 이차전지의성능향상을위한연구개발노력이활발하게진행되고있다.
[7] 리튬이차전지는리튬이온의삽입 (intercalations)및탈리 (deintercalation)가 가능한활물질로이루어진양극과음극사이에유기전해액또는폴리머 전해액을충전시킨상태에서리튬이온이양극및음극에서삽입/탈리될때의 산화와환원반응에의해전기에너지가생산된다.
[8] 리튬이차전지의양극활물질로는리튬코발트산화물 (LiCo02),리튬니켈 산화물 (LiNi02),리튬망간산화물 (LiMn02또는 LiMn204등),리튬인산철 화합물 (LiFeP04)등이주로사용된다.또한, LiNi02의우수한가역용량을 유지하면서도낮은열안정성을개선하기위한방법으로서,니켈어 의일부를 코발트 (Co)나망간 (Mn)으로치환하는방법이제안되었다.그러나니켈의일부를 코발트로치환한 LiNikCOaCMoczO.l OJ)의경우우수한충·방전특성과 수명특성을보이나,열적안정성이낮다.한편,니켈 (Ni)의일부를열적안정성이 뛰어난망간 (Mn)으로치환한니켈망간계리튬복합금속산화물및망간 (Mn)과 코발트 (Co)로치환한니켈코발트망간계리튬복합금속산화물 (이하간단히 ’NCM계리튬산화물’이라함)의경우상대적으로사이클특성및열적안정성이 우수하다는장점이있다.
[9] 그러나,최근코발트 (Co)의가격상승으로인해상대적으로적은코발트 (Co) 함량을포함하면서도높은용량에부합할수있는리튬과량 (Li-rich) NCM계 양극활물질의개발이이루어지고있다.리튬과량 (Li-rich)의 NCM계양극 2020/175925 1»（：1^1{2020/002782 활물질은높은에너지 밀도와가격에서의 이점을가진다.
[1이 일반적으로 NCM계 양극활물질의 전구체는공침법을통해합성되는데,주로 하이드록사이드또는카보네이트형태를가진다.하이드록사이드전구체 삐 CoalMnp1(OH)2(0<al<1.0, 0<(31<1.0)의경우 1차입자가약 1~3 정도로매우 크고조밀하지못해 이온전도도가낮고전기화학적성능및밀도가떨어지는 단점이 있었다.카보네이트전구체 ᅦ께 2(¾12 (：03(0<0[2<1.0, 0<(32<1.0)의 경우 1차입자가약 10-^111정도로너무작고소성과정중에 이산화탄소가 탈리되어 2차입자내의공극이 매우커지기 때문에강도가낮아져 압연시 입자가분쇄되고밀도가매우떨어지는단점이 있었다.
[11] 이에 , 1차입자가작고 2차입자가조밀하여높은밀도를나타내고,우수한입자 강도로압연시 입자깨짐을방지하며,이차전지에 적용시높은용량,효율및 율특성등의우수한전지성능을나타낼수있는양극활물질및그전구체의 개발이 여전히필요한실정이다.
[12]
발명의상세한설명
기술적과제
[13] 본발명은 1차입자가작고 2차입자가조밀하여높은밀도를나타내고,우수한 입자강도를나타낼수있는 NCM계 양극활물질전구체 및그제조방법을 제공하고자하는것이다.
[14] 또한,상기 양극활물질전구체를사용하여제조된리튬과량 (니 - 油)의 NCM계 양극활물질로서 이차전지에 적용시높은용량,효율및율특성등의우수한 전지성능을나타낼수있는양극활물질및그제조방법을제공하고자하는 것이다.
[15]
과제해결수단
[16] 본발명은니켈( ),코발트 ((¾)및망간 (Mn)을포함하며 ,상기니켈( )및 코발트 ((¾)는산화되
Figure imgf000004_0001
산화된 형태인이차전지용양극활물질전구체를제공한다.
[17]
[18] 또한,본발명은반응기에니켈 ( ),코발트 ((¾)및망간 (Mn)전이금속양이온 함유용액,알칼리용액 및암모늄이온함유용액을연속적으로투입하는단계; 및상기반응기에 가스를투입하지 않거나,산소함유가스를연속적으로 투입하면서 공침시켜,니켈 ( )및코발트 ((¾)는산화되지 않은하이드록사이드 형태이고,망간 은산화된형태인양극활물질전구체를형성하는단계 ;를 포함하는이차전지용양극활물질전구체의 제조방법을제공한다.
[19]
[2이 또한,본발명은상기와같이 제조된양극활물질전구체와리튬원료물질을 혼합하는단계 ;및상기혼합후 750내지 1,000°C로소성하여리튬복합
전이금속산화물을형성하는단계;를포함하는이차전지용양극활물질의 제조방법을제공한다.
[21]
[22] 또한,본발명은상기와같이제조된양극활물질,이를포함하는양극및리튬 이차전지를제공한다.
[23]
발명의효과
[24] 본발명에따르면, 1차입자가작고 2차입자가조밀하여높은밀도를나타내고, 우수한입자강도를나타낼수있는 NCM계양극활물질전구체를제조할수 있다.
[25] 또한,상기양극활물질전구체를사용하여제조된리튬과량 (Li-rich)의 NCM계 양극활물질은이차전지에적용시높은용량,효율및율특성등의우수한전지 성능을나타낼수있다.
[26]
도면의간단한설명
[27] 도 1은실시예 1에서제조된양극활물질전구체의 XPS데이터이다.
[28] 도 2는망간산화물의 XPS데이터참고자료이다.
[29] 도 3은비교예 1에서제조된양극활물질전구체의 XRD데이터이다.
[3이 도 4는비교예 2에서제조된양극활물질전구체의 XRD데이터이다.
[31] 도 5는실시예 1에서제조된양극활물질전구체를확대관찰한
주사전자현미경 (SEM, Scanning Electron Microscope)사진이다.
[32] 도 6은비교예 1에서제조된양극활물질전구체를확대관찰한
주사전자현미경 (SEM, Scanning Electron Microscope)사진이다.
[33] 도 7은비교예 2에서제조된양극활물질전구체를확대관찰한
주사전자현미경 (SEM, Scanning Electron Microscope)사진이다.
[34]
발명의실시를위한형태
[35] 이하,본발명에대한이해를돕기위해본발명을더욱상세하게설명한다. 이때,본명세서및청구범위에사용된용어나단어는통상적이거나사전적인 의미로한정해서해석되어서는아니되며,발명자는그자신의발명을가장 최선의방법으로설명하기위해용어의개념을적절하게정의할수있다는 원칙에입각하여본발명의기술적사상에부합하는의미와개념으로
해석되어야만한다.
[36]
[37] <양극활물짐진구체 >
[38] 본발명의양극활물질전구체는반응기에니켈 (Ni),코발트 (Co)및망간 (Mn) 2020/175925 1»（：1^1{2020/002782 전이금속양이온함유용액,알칼리용액및암모늄이온함유용액을
연속적으로투입하는단계 ;및상기반응기에가스를투입하지않거나,산소 함유가스를연속적으로투입하면서공침시켜,니켈（ ）및코발트（（¾）는 산화되지않은하이드록사이드형태이고,망간（Mn）은산화된형태인양극 활물질전구체를형성하는단계;를포함하여제조한다.
[39]
[4이 상기양극활물질전구체의제조방법을단계별로구체적으로설명한다.
[41] 먼저 ,반응기에니켈（ ）,코발트（（¾）및망간（Mn）전이금속양이온함유용액 , 알칼리용액및암모늄이온함유용액을연속적으로투입한다.
[42] 상기전이금속양이온함유용액은니켈（ ）함유원료물질,코발트（（¾）함유 원료물질및망간（Mn）함유원료물질을포함한다.
[43] 상기니켈（ ）함유원료물질은예를들면,니켈함유아세트산염,질산염,
황산염,할라이드,황화물,수산화물,산화물또는옥시수산화물등일수있으며, 구체적으로는, （0¾2, 0, 00¾ （그03 · 2 （0¾2 · 4¾0, （그202 · 2¾0, 어03）2 · 6¾0, 304, ^804 · 6¾0,지방산니켈염 ,니켈할로겐화물또는 이들의조합일수있으나,이에한정되는것은아니다.
[44] 상기코발트（（¾）함유원료물질은코발트함유아세트산염 ,질산염 ,황산염 , 할라이드,황화물,수산화물,산화물또는옥시수산화물등일수있으며, 구체적으로는（¾（0¾2,（¾00¾（¾（0（：0（：¾）2 · 4¾0,（¾어03）2 · 6¾0, 00804, （¾ 04）2 · 7¾0또는이들의조합일수있으나,이에한정되는것은아니다.
[45] 상기망간（Mn）함유원료물질은예를들면,망간함유아세트산염 ,질산염 , 황산염 ,할라이드,황화물,수산화물,산화물,옥시수산화물또는이들의조합일 수있으며 ,구체적으로는 Mn203, Mn304등과같은망간산화물;
Mn（N03）2, MnS04,아세트산망간,디카르복실산망간염,시트르산망간,지방산 망간염과같은망간염 ;옥시수산화망간,염화망간또는이들의조합일수 있으나,이에한정되는것은아니다.
[46] 상기전이금속양이온함유용액은니켈（ ）함유원료물질,코발트（（¾）함유 원료물질및망간（1 11）함유원료물질을용매,구체적으로는물,또는물과 균일하게혼합될수있는유기용매（예를들면,알코올등）의혼합용매에 첨가하여제조되거나,또는니켈어 함유원료물질의수용액,코발트（（¾）함유 원료물질의수용액및망간（Mn）함유원료물질을혼합하여제조된것일수있다.
[47] 상기암모늄이온함유용액은착물형성제로서 ,예를들면 NH4OH,어¾）2304,
NH4N03, NH4a, NH4C03또는이들의조합을포함할수있으나, 이에한정되는것은아니다.한편,상기암모늄이온함유용액은수용액의 형태로사용될수도있으며,이때용매로는물,또는물과균일하게혼합가능한 유기용매（구체적으로,알코올등）와물의혼합물이사용될수있다.
[48] 상기알칼리용액은침전제로서 NaOH, 011또는 0 011）2등과같은알칼리 금속또는알칼리토금속의수산화물,이들의수화물또는이들의조합의알칼리 2020/175925 1»（：1^1{2020/002782 화합물을포함할수있다.상기알칼리용액역시수용액의형태로사용될수도 있으며,이때용매로는물,또는물과균일하게혼합가능한
유기용매 (구체적으로,알코올등)와물의혼합물이사용될수있다.상기알칼리 용액은반응용액의 !^를조절하기위해첨가되는것으로,금속용액의 가 11 내지 13이되는양으로첨가될수있다.
[49]
[5이 다음으로,상기반응기에가스를투입하지않거나,산소함유가스를
연속적으로투입하면서공침시켜,니켈 ( )및코발트 ((¾)는산화되지않은 하이드록사이드형태이고,
Figure imgf000007_0001
산화된형태인양극활물질전구체를 형성한다.
[51] 종래에일반적인 NCM계양극활물질의전구체공침반응에서는질소어2)또는 아르곤 ]·)가스를투입하여비활성분위기하에서하이드록사이트형태의 전구체를합성하거나,질소 (此),아르곤 ]·)또는탄산 (¾(：(¾)가스를투입하여 카보네이트형태의전구체를합성하였다.그러나,종래의하이드록사이드 형태의전구체는 1차입자가약 1-3^111정도로매우크고조밀하지못해이온 전도도가낮고전기화학적성능및밀도가떨어지는단점이있었고,카보네이트 형태의전구체는 1차입자가약 10-^111정도로너무작고소성과정중에 이산화탄소가탈리되어입자내의공극이매우커지기때문에강도가낮아져 압연시입자가분쇄되고밀도가매우떨어지는단점이있었다.
[52] 이에 ,본발명에서는 1차입자가작고 2차입자가조밀하여높은밀도를
나타내고우수한입자강도를나타낼수있는 NCM계양극활물질전구체를 제공하기위하여 ,전구체공침반응시가스를투입하지않거나,산소함유 가스를연속적으로투입하면서공침시켜양극활물질전구체를제조하였다. 이를통해,니켈 ( )및코발트 ((¾)는산화되지않은하이드록사이드형태이고, 산화된형태인양극활물질전구체를형성한다.
[53]
Figure imgf000007_0002
서는공침반응시가스를투입하지않거나,산소함유가스를
연속적으로투입한다.이를통해,망간 이온이암모늄이온과배위결합 후에알칼리화합물과반응하지않아도투입되는산소 (02)가스혹은공기내 산소 (02)가스와결합하여산화물로침전이가능하고,또는알칼리화합물과 반응하여침전하여도반응기내에서산화되어반응속도가매우빠를수있으며, 작은 1차입자가형성되게된다.
[54] 종래에는공침반응시질소 (此),아르곤 ]·)및/또는탄산 (¾(：(¾)가스를
투입하던것과달리,본발명에서는공침반응시상기반응기에질소어2), 아르곤 !·)및탄산 (¾(：03)가스를투입하지않을수있다.또는,산소함유 가스를연속적으로투입할수있는데,본발명의일실시예에따르면,산소 (02) 가스의투입유량은보다구체적으로하기식 1을만족할수있다.
Figure imgf000007_0003
가스의투입유량 (1九) 2020/175925 1»（：1^1{2020/002782
< 1 { (시간당망간 (Mn)투입량 (11101)x2)/0.089}
[57] 예를들어,니켈 ( ),코발트 ((¾),망간 (Mn)을 2: 1 :7로포함하는전이금속
양이온함유용액 3.211101 를시간당 0. 연속투입할경우,산소 (02)가스의 투입유량은 15. lL/h내지 16.611 1일수있다.만약,산소 (02)가스를 20부피 % 함유하는가스일경우전체가스투입유량은 75.51 1내지 83.051^1일수있다.
[58] 상기산소 (02)가스의투입유량 (1 1)을만족함으로써 니켈 ( )및코발트 ((¾)는 산화되지 않은하이드록사이드형태이고,망간 (Mn)은산화된형태인양극 활물질전구체를형성할수있으며,이를통해 1차입자가작고 2차입자가 조밀하여높은밀도를나타내고우수한입자강도를나타낼수있다.
[59] 본발명의 일실시예에 따라제조된상기 양극활물질전구체는하기화학식 1로표시될수있다.
[6이 [화학식 1]
[61] 0
[62] 상기화학식 1
Figure imgf000008_0001
이루어진군에서선택된적어도하나이상이며, 0.25£ £0.5, 0.5£ £0.75,
+ =1이고, 0<&<0.6, 0<15<0.4.
[63]
[64] 본발명에 따라제조된상기 양극활물질전구체는니켈( ),코발트 ((¾)및
Figure imgf000008_0002
포함하며,상기니켈 ( )및코발트 ((¾)는산화되지 않은
하이드록사이드형태이고,망간 은산화된형태이다.
[65] 또한,상기 양극활물질전구체는 1차입자가응집된 2차입자형태이며 ,상기
1차입자의 입경은 50내지 50011111일수있고,보다바람직하게는 80내지 400며11, 더욱바람직하게는 100내지 30011111일수있다.본발명의 일실시예에따른상긱
Figure imgf000008_0003
이온이 암모늄이온과배위결합후에 알칼리 화합물과반응하지 않아도투입되는산소 (02)가스혹은공기와결합하여 산화물로침전이가능하고,또는알칼리화합물과반응하여침전하여도반응기 내에서산화되어반응속도가매우빠르므로,종래의하이드록사이드형태의 전구체보다작은 1차입자를형성할수있다.상기 양극활물질전구체가상기 1차입자입경 범위를만족함으로써 1차입자가작고 2차입자가조밀하여높은 밀도를나타내고,우수한입자강도를나타낼수있다.
[66] 또한,상기 양극활물질전구체는탭밀도가 \Aglcc이상으로높게나타날수 있으며,보다바람직하게는 1.4내지 2. /¥,더욱바람직하게는 1.5내지
일수있다.상기 탭밀도는양극활물질전구체 5 을 501111매스실린더에 넣고 쇼\^2탭밀도측정기 (I £1¾此11 1111쇼(3)를사용하여 1250회스트로크를 행하여 탭밀도를측정하였을때의 탭밀도이다.
[67]
[68] <양극활물짐 >
[69] 또한,본발명은상기 양극활물질을사용하여 제조된양극활물질을제공한다. 2020/175925 1»（：1/10公020/002782 본발명의 양극활물질은상기 양극활물질전구체와리튬원료물질을 혼합하는단계 ;및상기혼합후 750내지 1,000ᄋ（:로소성하여 리튬복합 전이금속산화물을형성하는단계 ;를포함한다.
[기] 먼저,본발명의상기 양극활물질전구체와리튬원료물질을혼합한다.
[72] 상기 양극활물질전구체는니켈（ ）,코발트（（¾）및망간 을포함하며, 상기 니켈（ ）및코발트（（¾）는산화되지 않은하이드록사이드형태이고, 망간 은산화된형태이다.
상기 리튬원료물질은리튬함유황산염,질산염,아세트산염,탄산염, 옥살산염,시트르산염,할라이드,수산화물또는옥시수산화물등이사용될수 있으며,물에용해될수있는한특별히 한정되지 않는다.구체적으로상기 리튬 소스는 02003, ^03, ^02, 1그0¾ 1 011 · ¾0, U¥ί, , 001, UBr, 01,（：¾ 0000, 020, 02804,（：¾（：001文또는 1山0¾07등일수있으며,이들중어느 하나또는둘이상의혼합물이사용될수있다.
[74] 상기 양극활물질전구체와리튬원료물질의 리튬（니）이 1 : 1.2내지 1 : 1.6의
몰비가되도록혼합할수있으며,보다바람직하게는 1 : 1.2내지 1 : 1.55,더욱 바람직하게는 1 : 1.25내지 1 : 1.5일수있다.상기몰비로양극활물질전구체와 리튬원료물질을혼합함으로써 리튬과량（1 -난 ）의 리튬복합전이금속 산화물을형성할수있으며,이를통해높은용량을구현할수있다.
다음으로,상기혼합후 750내지 1,000ᄋ（:로소성하여 리튬복합전이금속 산화물을형성한다.보다바람직하게는 800내지 975 ,더욱바람직하게는 850 내지 950ᄋ（:로소성할수있고, 5내지 20시간,보다바람직하게는 7내지 15시간 소성할수있다.
[76] 이와같이 제조된본발명의 양극활물질은리튬을제외한전체금속（M）에
0 ] ] ]1 대한리튬（1山의몰비율（Li/M）이 1.2내지 1.6인리튬과량（니 -난此）의 리튬복합 79 20811
7777888 7 735 전이금속산화물이면서 ,펠렛밀도가 2. /¥이상으로높게나타날수있으며 , 보다바람직하게는 2.2내지 3.0^00,더욱바람직하게는 2.3내지 2 / 일수 있다.상기 펠렛밀도는양극활물질 5은을직경 22111111몰드에 넣고
1^-쇼2（（주）한테크）사용하여 2톤의 압력으로측정하였을때의 펠렛밀도이다.
＜양극및리륨이차진지＞
본발명의또다른일실시예에 따르면상기 양극활물질을포함하는 이차전지용양극및리튬이차전지를제공한다. 구체적으로,상기 양극은양극집전체 및상기 양극집전체위에 형성되며,상기 양극활물질을포함하는양극활물질층을포함한다.
상기 양극에 있어서,양극집전체는전지에화학적 변화를유발하지 않으면서 도전성을가진것이라면특별히제한되는것은아니며,예를들어스테인리스 스틸,알루미늄，니켈,티탄,소성 탄소또는알루미늄이나스테인레스스틸 표면에탄소,니켈,티탄,은등으로표면처리한것등이사용될수있다.또,상기 양극집전체는통상적으로 3내지 500/ffli의두께를가질수있으며,상기양극 집전체표면상에미세한요철을형성하여양극활물질의접착력을높일수도 있다.예를들어필름,시트,호일,네트,다공질체,발포체,부직포체등다양한 형태로사용될수있다.
[83]
[84] 또,상기양극활물질층은앞서설명한양극활물질과함께,도전재및
바인더를포함할수있다.
[85] 이때,상기도전재는전극에도전성을부여하기위해사용되는것으로서, 구성되는전지에있어서,화학변화를야기하지않고전자전도성을갖는것이면 특별한제한없이사용가능하다.구체적인예로는천연흑연이나인조흑연등의 흑연;카본블랙,아세틸렌블랙,케첸블랙,채널블랙,퍼네이스블랙,램프블랙, 서머블랙,탄소섬유등의탄소계물질;구리,니켈,알루미늄,은등의금속분말 또는금속섬유;산화아연,티탄산칼륨등의도전성위스키 ;산화티탄등의 도전성금속산화물;또는폴리페닐렌유도체등의전도성고분자등을들수 있으며,이들중 1종단독또는 2종이상의혼합물이사용될수있다.상기 도전재는통상적으로양극활물질층총중량에대하여 1내지 30중량%로포함될 수있다.
[86]
[87] 또,상기바인더는양극활물질입자들간의부착및양극활물질과양극
집전체와의접착력을향상시키는역할을한다.구체적인예로는
폴리비닐리덴플로라이드 (PVDF),
비닐리덴플루오라이드-핵사플루오로프로필렌코폴리머 (PVDF-co-HFP), 쓸리비닐알코올,쓸리아크릴로니트릴 (polyacrylonitrile),
카르복시메틸셀룰로우즈 (CMC),전분,히드록시프로필셀룰로우즈,재생 셀룰로우즈,폴리비닐피롤리돈,테트라플루오로에틸렌,폴리에틸렌, 폴리프로필렌,에틸렌-프로필렌-디엔폴리머 (EPDM),술폰화- EPDM,스티렌 부타디엔고무 (SBR),불소고무,또는이들의다양한공중합체등을들수 있으며,이들중 1종단독또는 2종이상의혼합물이사용될수있다.상기 바인더는양극활물질층총중량에대하여 1내지 30중량%로포함될수있다.
[88]
[89] 상기양극은상기한양극활물질을이용하는것을제외하고는통상의양극 제조방법에따라제조될수있다.구체적으로,상기한양극활물질및
선택적으로,바인더및도전재를포함하는양극활물질층형성용조성물을양극 집전체상에도포한후,건조및압연함으로써제조될수있다.이때상기양극 활물질,바인더,도전재의종류및함량은앞서설명한바와같다.
[9이 상기용매로는당해기술분야에서일반적으로사용되는용매일수있으며 , 디메틸셀폭사이드 (dimethyl sulfoxide, DMSO),이소프로필알코올 (isopropyl 2020/175925 1»（：1/10公020/002782
&1。01101),此메틸피롤리돈 (NMP),아세톤 ( 라이떠또는물등을들수있으며 ,이들 중 1종단독또는 2종이상의혼합물이사용될수있다.상기용매의사용량은 슬러리의도포두께,제조수율을고려하여상기 양극활물질,도전재 및 바인더를용해또는분산시키고,이후양극제조를위한도포시우수한두께 균일도를나타낼수있는점도를갖도록하는정도면충분하다. 또,다른방법으로,상기 양극은상기 양극활물질층형성용조성물을별도의 지지체상에 캐스팅한다음,이지지체로부터 박리하여 얻은필름을양극집전체 상에 라미네이션함으로써제조될수도있다.
[93]
[94] 본발명의또다른일실시예에 따르면,상기 양극을포함하는전기화학소자가 제공된다.상기 전기화학소자는구체적으로전지또는커패시터등일수있으며, 보다구체적으로는리튬이차전지일수있다. 상기 리튬이차전지는구체적으로양극,상기 양극과대향하여위치하는음극, 상기 양극과음극사이에 개재되는세퍼레이터 및전해질을포함하며,상기 양극은앞서설명한바와같다.또,상기 리튬이차전지는상기 양극,음극, 세퍼레이터의 전극조립체를수납하는전지용기 ,및상기 전지용기를밀봉하는 밀봉부재를선택적으로더포함할수있다.
[97]
[98] 상기 리튬이차전지에 있어서,상기 음극은음극집전체및상기음극집전체 상에 위치하는음극활물질층을포함한다.
[99] 상기음극집전체는전지에 화학적 변화를유발하지 않으면서높은도전성을
] ] ] ] 가지는것이라면특별히 제한되는것은아니며,예를들어,구리,스테인레스 56
9999 스틸,알루미늄,니켈,티탄,소성 탄소,구리나스테인레스스틸의표면에 탄소, 니켈,티탄,은등으로표면처리한것,알루미늄-카드뮴합금등이사용될수 있다.또,상기 음극집전체는통상적으로 3내지 500//111의두께를가질수있으며, 양극집전체와마찬가지로,상기 집전체표면에 미세한요철을형성하여 음극활물질의 결합력을강화시킬수도있다.예를들어,필름,시트,호일,네트, 다공질체,발포체,부직포체등다양한형태로사용될수있다.
Figure imgf000011_0001
상기음극활물질층은음극활물질과함께선택적으로바인더 및도전재를 포함한다.상기 음극활물질층은일례로서 음극집전체상에음극활물질,및 선택적으로바인더 및도전재를포함하는음극형성용조성물을도포하고 건조하거나,또는상기음극형성용조성물을별도의지지체상에 캐스팅한 다음,이지지체로부터박리하여 얻은필름을음극집전체상에
라미네이션함으로써 제조될수도있다. [103] 상기음극활물질로는리튬의가역적인인터칼레이션및디인터칼레이션이 가능한화합물이사용될수있다.구체적인예로는인조흑연,천연흑연,흑연화 탄소섬유,비정질탄소등의탄소질재료; Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd,
Si합금, Sn합금또는 A1합금등리튬과합금화가가능한금속질화합물; SiOp(0 < (3 < 2), Sn02,바나듐산화물,리튬바나듐산화물과같이리튬을도프및 탈도프할수있는금속산화물;또는 Si-C복합체또는 Sn-C복합체과같이상기 금속질화합물과탄소질재료를포함하는복합물등을들수있으며,이들중 어느하나또는둘이상의혼합물이사용될수있다.또한,상기음극활물질로서 금속리튬박막이사용될수도있다.또,탄소재료는저결정탄소및고결정성 탄소등이모두사용될수있다.저결정성탄소로는연화탄소 (soft carbon)및 경화탄소 (hard carbon)가대표적이며,고결정성탄소로는무정형,판상,인편상, 구형또는섬유형의천연폭연또는인조폭연,키시폭연 (Kish graphite),열분해 탄소 (pyrolytic carbon),액정피치계탄소섬유 (mesophase pitch based carbon fiber), 탄소미소구체 (meso-carbon microbeads),액정피치 (Mesophase pitches)및석유와 석탄계코크스 (petroleum or coal tar pitch derived cokes)등의고온소성탄소가 대표적이다.
[104] 또,상기바인더및도전재는앞서양극에서설명한바와동일한것일수있다.
[105]
[106] 한편,상기리튬이차전지에있어서 ,세퍼레이터는음극과양극을분리하고 리튬이온의이동통로를제공하는것으로,통상리튬이차전지에서
세퍼레이터로사용되는것이라면특별한제한없이사용가능하며 ,특히 전해질의이온이동에대하여저저항이면서전해액함습능력이우수한것이 바람직하다.구체적으로는다공성고분자필름,예를들어에틸렌단독중합체, 프로필렌단독중합체,에틸렌/부텐공중합체,에틸렌/핵센공중합체및
에틸렌/메타크릴레이트공중합체등과같은폴리올레핀계고분자로제조한 다공성고분자필름또는이들의 2층이상의적층구조체가사용될수있다.또 통상적인다공성부직포,예를들어고융점의유리섬유,
폴리에틸렌테레프탈레이트섬유등으로된부직포가사용될수도있다.또, 내열성또는기계적강도확보를위해세라믹성분또는고분자물질이포함된 코팅된세퍼레이터가사용될수도있으며 ,선택적으로단층또는다층구조로 사용될수있다.
[107]
[108] 또,본발명에서사용되는전해질로는리튬이차전지제조시사용가능한
유기계액체전해질,무기계액체전해질,고체고분자전해질,겔형고분자 전해질,고체무기전해질,용융형무기전해질등을들수있으며,이들로 한정되는것은아니다.
[109]
[110] 구체적으로,상기전해질은유기용매및리튬염을포함할수있다. [111] 상기유기용매로는전지의전기화학적반응에관여하는이온들이이동할수 있는매질역할을할수있는것이라면특별한제한없이사용될수있다.
구체적으로상기유기용매로는,메틸아세테이트 (methyl acetate),에틸
아세테이트 (ethyl acetate), 부티로락톤 (y-butyrolactone),
8 -카프로락톤 (8-caprolactone)등의에스테르계용매 ;디부틸에테르 (dibutyl ether) 또는테트라히드로퓨란 (tetrahydrofuran)등의에테르계용매;
시클로핵사논 (cyclohexanone)등의케톤계용매;벤젠 (benzene),
늘루오로벤젠 (fluorobenzene)등의방향족탄화수소계용매;
디메틸카보네이트 (dimethylcarbonate, DMC),디에틸카보네이트 (diethylcarbonate, DEC),메틸에틸카보네이트 (methylethylcarbonate, MEC),
에틸메틸카보네이트 (ethylmethylcarbonate, EMC),에틸렌카보네이트 (ethylene carbonate, EC),프로필렌카보네이트 (propylene carbonate, PC)등의카보네이트계 용매 ;에틸알코올,이소프로필알코올등의알코올계용매 ; R-CN(R은 C2내지 C20의직쇄상,분지상또는환구조의탄화수소기이며,이중결합방향환또는 에테르결합을포함할수있다)등의니트릴류;디메틸포름아미드등의 아미드류; 1,3 -디옥솔란등의디옥솔란류;또는설포란 (sulfolane)류등이사용될 수있다.이중에서도카보네이트계용매가바람직하고,전지의충방전성능을 높일수있는높은이온전도도및고유전율을갖는환형카보네이트 (예를들면, 에틸렌카보네이트또는프로필렌카보네이트등)와,저점도의선형
카보네이트계화합물 (예를들면,에틸메틸카보네이트,디메틸카보네이트또는 디에틸카보네이트등)의혼합물이보다바람직하다.이경우환형카보네이트와 사슬형카보네이트는약 1:1내지약 1:9의부피비로혼합하여사용하는것이 전해액의성능이우수하게나타날수있다.
[112]
[113] 상기리튬염은리튬이차전지에서사용되는리튬이온을제공할수있는
화합물이라면특별한제한없이사용될수있다.구체적으로상기리튬염은, LiPF6, LiC104, LiAsF6, LiBF4, LiSbF6, LiA104, L1AICI4, LiCF3S03, LiC4F9S03, LiN(C2 F5S03)2, LiN(C2F5S02)2, LiN(CF3S02)2. LiCl, Lil,또는 LiB(C204)2등이사용될수 있다.상기리튬염의농도는 0.1내지 2.0M범위내에서사용하는것이좋다. 리튬염의농도가상기범위에포함되면,전해질이적절한전도도및점도를 가지므로우수한전해질성능을나타낼수있고,리튬이온이효과적으로이동할 수있다.
[114]
[115] 상기전해질에는상기전해질구성성분들외에도전지의수명특성향상,전지 용량감소억제,전지의방전용량향상등을목적으로예를들어,디플루오로 에틸렌카보네이트등과같은할로알킬렌카보네이트계화합물,피리딘, 트리에틸포스파이트,트리에탄올아민,환상에테르,에틸렌디아민,
n-글라임 (glyme),핵사인산트리아미드,니트로벤젠유도체,유황,퀴논이민 염료, N-치환옥사졸리디논, N,N-치환이미다졸리딘,에틸렌글리콜디알킬 에테르,암모늄염,피롤, 2 -메톡시에탄올또는삼염화알루미늄등의첨가제가 1종이상더포함될수도있다.이때상기첨가제는전해질총중량에대하여 0.1 내지 5중량%로포함될수있다.
[116]
[117] 상기와같이본발명에따른양극활물질을포함하는리튬이차전지는우수한 방전용량,출력특성및용량유지율을안정적으로나타내기때문에,휴대전화, 노트북컴퓨터,디지털카메라등의휴대용기기,및하이브리드
전기자동차 (hybrid electric vehicle, HEV)등의전기자동차분야등에유용하다.
[118]
[119] 이에따라,본발명의다른일구현예에따르면,상기리튬이차전지를단위
셀로포함하는전지모듈및이를포함하는전지팩이제공된다.
[120] 상기전지모듈또는전지팩은파워툴 (Power Tool);전기자동차 (Elec仕 ic Vehicle, EV),하이브리드전기자동차,및플러그인하이브리드전기자동차 (Plug-in Hybrid Electric Vehicle, PHEV)를포함하는전기차;또는전력저장용시스템중 어느하나이상의중대형디바이스전원으로이용될수있다.
[121]
[122] 이하,본발명이속하는기술분야에서통상의지식을가진자가용이하게
실시할수있도록본발명의실시예에대하여상세히설명한다.그러나본 발명은여러가지상이한형태로구현될수있으며여기에서설명하는실시예에 한정되지않는다.
[123]
[124] 심시예 1
[125] 공침반응기 (용량 20L)에증류수 4리터를넣은뒤 50OC온도를유지시키며
28중량%농도의암모니아수용액 100ml를투입한후, NiS04, CoS04, MnS04를 니켈:코발트:망간의몰비가 2:2:6가되도록혼합된 3.2mol/L농도의전이금속 양이온함유용액을 300ml/hr, 28중량%의암모니아수용액을 42ml/hr로반응기에 연속적으로투입하였다.임펠러의속도는 400rpm으로교반하였고, pH유지를 위해 40중량%의수산화나트륨용액을이용하여 pH 9.5가유지되도록
투입하였다.
[126] 이때 ,산소 (02)가스를 13.0L/hr로공급하면서 24시간공침반응시켜 0.4(Ni0.5Co 0.5(OH)2).0.6(MnO2)의전구체입자를형성하였다.상기전구체입자를분리하여 세척후 130OC의오븐에서건조하여양극활물질전구체를제조하였다.
[127]
[128] 비교예 1
[129] 공침반응기 (용량 20L)에증류수 4리터를넣은뒤 50OC의온도를유지시키며 질소 (N2)가스를반응기에 2L/min의속도로 1시간퍼징하여반응기내의산소를 제거하여반응기내를비산화분위기로조성하였다 . 28중량%농도의암모니아 수용액 10011111-투입한후, ^804, 00804,■ 04를니켈:코발트:망간의몰비가 2:2:6이되도록혼합된 3.211101凡의농도의금속수용액을 3001111/ 으로,
28중량%의암모니아수용액을 42센/ 으로반응기에연속적으로투입하였다. 임펠러의속도는 400 111으로교반하였다.
Figure imgf000015_0001
수산화나트륨용액을이용하여
Figure imgf000015_0002
.0으로유지되도록투입하였다. 24시간 공침반응시켜 。.2（：0。.2^1¾6（01¾의전구체입자를형성하였다.상기전구체 입자를분리하여세척후 130ᄋ（:의오븐에서건조하여양극활물질전구체를 제조하였다.
[B이
[131] 비교예 2
[132] 공침반응기（용량 20L）에증류수 4리터를넣은뒤 50OC의온도를유지시키며 질소（N2）가스를반응기에 2L/min의속도로 1시간퍼징하여반응기내의산소를 제거하여반응기내를비산화분위기로조성하였다 . 28중량%농도의암모니아 수용액 100ml를투입한후, NiS04, CoS04, MnS04를니켈:코발트:망간의몰비가 2:2:6이되도록혼합된 3.2mol/L의농도의금속수용액을 300ml/hr으로,
28중량%의암모니아수용액을 42ml/hr으로반응기에연속적으로투입하였다. 임펠러의속도는 400rpm으로교반하였다. pH유지를위해 20중량%의
탄산나트륨용액을이용하여 pH가 7.5로유지되도록투입하였다. 24시간 공침반응시켜 NiQ.2CoQ.2MnQ.6C03의전구체입자를형성하였다.상기전구체 입자를분리하여세척후 130OC의오븐에서건조하여양극활물질전구체를 제조하였다.
[133]
[134] r심험예 1:진구체 입자확이 1
[135] 실시예 1및비교예 1~2에서제조된양극활물질전구체를 XPS및 XRD를
사용하여확인하였다.그결과를도 1~4에나타내었다.구체적으로, XPS분석은 ESCALAB 250（Thermo Fisher Scientific）장비를사용하여가속전압 15kV（전력 : 150W）,에너지분해능약 l.OeV,분석영역직경 500마이크로미터（micrometer） 그리고 sputter rate O.lnm/sec의분석조건하에서 survey scan spectrum과 narrow scan spectrum을얻어 XPS분광시험을실시되었고, XRD분석은 D4 ENDEAVOR （Bruker AXS GmbH）장비를사용하여 Cu타겟（target）을사용하여 40kV의 가속전압과 40mA의가속전류로 W~90ᄋ범위내에서분당 3ᄋ의속도로 XRD회절 측정을실시하였다.
[136]
[137] 도 1~2（실시예 1의 XPS（도 1）및참고자료（도 2））를참조하면, Mn의 3s XPS
스펙트럼에서분리된 2개의 peak의에너지차이로 Mn의산화수를알수있는데 도 2의참고자료를보면알수있듯이 Mn이 4가인 Mn02형태를갖는것을 확인할수있다.
[138] 도 3~4（비교예 1~2의 XRD）를참조하면,비교예 1은 Ni, Co, Mn의 2020/175925 1»（：1^1{2020/002782 하이드록사이드형태이고,비교예 2는 Ni, Co, Mn의카보네이트형태임을 확인할수있었다.
[139] 한편,실시예 1및비교예 1~2에서제조된양극활물질전구체를
주사전자현미경 £^1）으로확대관찰한사진을도 5~7에나타내었다.도 5는 하이드록사이트형태인비교예 1의 양극활물질전구체로, 1차입자가크고 2차 입자가조밀하지못한것을확인할수있고,도 6은카보네이트형태인비교예 2의 양극활물질전구체로, 1차입자가너무작고입자내의 공극이큰것을 확인할수있다.반면에,도 7은실시예 1의 양극활물질전구체로, 1차입자가 작으면서조밀한 2차입자형상인것을확인할수있다.
[14이
[141] 『심험예 2:탭밀도측정 1
[142] 실시예 1및비교예 1~2에서제조된각각의 양극활물질전구체 5 을 501111 매스실린더에 넣고 탭밀도측정기（1. £1¾ 11 1111쇼（3）를사용하여
1250회스트로크를행하여 탭밀도를측정하였다.그결과를하기표 1에 나타내었다.
[143]
[144] [표 1]
Figure imgf000016_0001
[145] 표 1을참조하면,실시예 1의 양극활물질전구체가
하이드록사이드/카보네이트형태인비교예 1~2의 양극활물질전구체보다탭 밀도가현저히높게나타난것을확인할수있다.
[146]
[147] 심시예 2및비교예 3~4
[148] 상기실시예 1및비교예 1~2에서 제조된각각의 양극활물질전구체및리튬 원료물질 0011의 리튬（1山이 1 : 1.35의몰비가되도록혼합한뒤에분말을 알루미나도가니에 넣고,대기（ ]·）분위기하에서 550ᄋ（:까지승온시킨후 5시간 동안가소성후에상온까지 냉각시켜 가소성품을분쇄 및체질한후, 900ᄋ（:까지 승온시킨후 시간동안소성하여실시예 2및비교예 3~4의 양극활물질을 제조하였다.
[149]
[150] 『심험예 3:펨렛밀도측정 1
[151] 실시예 2및비교예 3~4에서제조된각각의 양극활물질을 5은을직경 22111111 몰드넣고 HPRM-A2（（주）한테크）사용하여 2톤의 압력으로펠렛밀도를 측정하였다.그결과를하기표 2에 나타내었다. [152] [표 2]
Figure imgf000017_0001
[153] 표 2를참조하면,실시예 2의 양극활물질이하이드록사이드/카보네이트
형태인양극활물질전구체를사용하여 제조된비교예 3~4의 양극활물질보다 펠렛밀도가현저히높게나타난것을확인할수있다.
[154]
[155] 『심험예 4:리륨이차진지성능평가 1
[156] 상기실시예 2및비교예 3~4에서 제조된각각의 양극활물질,카본블랙도전재 및 PVdF바인더를 N-메틸피롤리돈용매중에서중량비로 96:2:2의비율로 혼합하여 양극합재를제조하고,이를알루미늄집전체의 일면에도포한후, 130OC에서 건조후,압연하여 양극을제조하였다.
[157] 음극은리튬메탈을사용하였다.
[158] 상기와같이 제조된양극과음극사이에다공성폴리에틸렌의 세퍼레이터를 개재하여 전극조립체를제조하고,상기 전극조립체를케이스내부에위치시킨 후,케이스내부로전해액을주입하여 리튬이차전지를제조하였다.이때 전해액은
에틸렌카보네이트/에틸메틸카보네이트/디에틸카보네이트/（EC/EMC/DEC의 혼합부피비 =3/5/2）로이루어진유기용매에 1.0M농도의
리튬핵사플루오로포스페이트（LiPF6）를용해시켜제조하였다.
[159] 상기와같이 제조된각리튬이차전지하프셀（half cell）에 대해 , 25OC에서
CCCV모드로 0.1C, 4.65V가될때까지충전（종료전류 0.05C）하고, 0.1C의 정전류로 2.0V가될때까지 방전하여초기충방전용량및효율을측정하였다. 또한, C-rate를측정하였으며,이는 0.1C로충전하고 0.1C로방전했을때의 용량과각각 0.5C, 1CC로방전했을때의용량의 비이다.그결과를표 3에 나타내었다.
[16이 [표 3]
Figure imgf000017_0002
[161] 표 3을참조하면,실시예 2의 양극활물질을사용한경우에 비교예 3~4의 양극 2020/175925 1»（：1/10公020/002782 활물질을사용한경우에비하여조기용량,효율및
Figure imgf000018_0001
우수하게나타났다.

Claims

2020/175925 1»（：1/10公020/002782 청구범위
［청구항 1］ 니켈（ ）,코발트（（¾）및망간 을포함하며 ,
상기니켈（ ）및코발트（（¾）는산화되지않은하이드록사이드형태이고,
Figure imgf000019_0001
산화된형태인이차전지용양극활물질전구체.
［청구항 2］ 제 1항에 있어서,
상기양극활물질전구체는하기화학식 1로표시되는이차전지용양극 활물질전구체;
［화학식 1］
（:0 0¾2切 1102）
상기화학식 1에서 , M1는므 V, Mo, , Na, II, 01, &,
Figure imgf000019_0002
Mg및 X로 이루어진군에서선택된적어도하나이상이며, 0.25£ £0.5, 0.5£ £0.75, + =1이고, 0<&<0.6, 0<15<0.4.
［청구항 3］ 제 1항에 있어서,
상기양극활물질전구체는 1차입자가응집된 2차입자형태이며 ,상기 1차입자의입경은 50내지 50011111인이차전지용양극활물질전구체. ［청구항 4］ 제 1항에 있어서,
상기양극활물질전구체는탭밀도가 \Aglcc이상인이차전지용양극 활물질
［청구항 5］ 반응기
Figure imgf000019_0003
이금속양이온함유용액 , 알칼리용액및암모늄이온함유용액을연속적으로투입하는단계;및 상기반응기에가스를투입하지않거나,산소함유가스를연속적으로 투입하면서공침시켜,니켈（ ）및코발트（（¾）는산화되지않은
하이드록사이드형태이고,
Figure imgf000019_0004
산화된형태인양극활물질 전구체를형성하는단계;
를포함하는이차전지용양극활물질전구체의제조방법.
［청구항 6］ 제 5항에 있어서,
상기반응기에질소（凡）,아르곤 ］·）및탄산（¾（：03）가스를투입하지 않는이차전지용양극활물질전구체의제조방법.
［청구항 7］ 제 5항에 있어서,
상기산소함유가스를투입시,산소（02）가스의투입유량은하기식 1을 만족하는이차전지용양극활물질전구체의제조방법.
［식 1］
（시간당망간 11）투입량（11101）x2）/0.089 <산소（02）가스의투입유량（1 1） <1.1 {（시간당망간（Mn）투입량（11101）x2）/0.089}
［청구항 8］ 제 5항에 있어서,
상기반응기에
Figure imgf000019_0005
양이온함유용액을더투입하여공침시키는
이차전지용양극활물질전구체의제조방법. 2020/175925 1»（：1^1{2020/002782
[청구항 9] 제 5항에 있어서,
상기양극활물질전구체는하기화학식 1로표시되는이차전지용양극 활물질전구체의제조방법;
[화학식 1]
（¾>1 0¾2切 1102）
상기화학식 1에서 , M1는므 V, Mo, , Na, II, 01, &,
Figure imgf000020_0001
Mg및 X로 이루어진군에서선택된적어도하나이상이며, 0.25£ £0.5, 0.5£ £0.75, + =1이고, 0<&<0.6, 0<15<0.4.
[청구항 10] 제 5항에따라제조된양극활물질전구체와리튬원료물질을혼합하는 단계;및
상기혼합후 750내지 1,000ᄋ（:로소성하여리튬복합전이금속산화물을 형성하는단계 ;
를포함하는이차전지용양극활물질의제조방법.
[청구항 11] 제 항에 있어서,
상기양극활물질전구체와리튬원료물질의리튬（1山이 1: 1.2내지 1: 1.6의 몰비가되도록혼합하는이차전지용양극활물질의제조방법.
[청구항 12] 제 10항에따라제조된이차전지용양극활물질.
[청구항 13] 제 12항에 있어서,
상기양극활물질은펠렛밀도가 2. /¥이상인이차전지용양극활물질. [청구항 14] 제 12항에따른양극활물질을포함하는이차전지용양극.
[청구항 15] 제 14항에따른양극을포함하는리튬이차전지 .
PCT/KR2020/002782 2019-02-28 2020-02-27 이차전지용 양극 활물질 전구체, 양극 활물질, 그 제조방법 및 이를 포함하는 리튬 이차전지 WO2020175925A1 (ko)

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