WO2018124781A1 - Matériau actif d'électrode positive pour accumulateur, son procédé de préparation, électrode positive le comprenant pour accumulateur, et accumulateur - Google Patents

Matériau actif d'électrode positive pour accumulateur, son procédé de préparation, électrode positive le comprenant pour accumulateur, et accumulateur Download PDF

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WO2018124781A1
WO2018124781A1 PCT/KR2017/015666 KR2017015666W WO2018124781A1 WO 2018124781 A1 WO2018124781 A1 WO 2018124781A1 KR 2017015666 W KR2017015666 W KR 2017015666W WO 2018124781 A1 WO2018124781 A1 WO 2018124781A1
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active material
cobalt
positive electrode
secondary battery
lithium
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PCT/KR2017/015666
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English (en)
Korean (ko)
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채화석
박상민
박신영
박홍규
강성훈
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주식회사 엘지화학
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Priority to CN201780080266.3A priority Critical patent/CN110140242B/zh
Publication of WO2018124781A1 publication Critical patent/WO2018124781A1/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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • 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
    • C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a positive electrode active material for a secondary battery, a method for manufacturing the same, a positive electrode for a secondary battery and a secondary battery including the same, and more particularly, a high concentration having a low amount of lithium by-products remaining on the surface of the active material, and having excellent high temperature stability, capacity characteristics, and lifetime characteristics.
  • the present invention relates to a nickel (Ni-rich) cathode active material, a method of manufacturing the same, and a cathode and a secondary battery for a secondary battery including the same.
  • lithium secondary batteries having high energy density and voltage, long cycle life, and low self discharge rate have been commercialized and widely used.
  • Lithium transition metal composite oxide is used as a positive electrode active material of a lithium secondary battery, and among these, lithium cobalt composite metal oxide of LiCoO 2 having a high operating voltage and excellent capacity characteristics is mainly used.
  • LiCoO 2 is very poor in thermal properties due to destabilization of crystal structure due to de-lithium and is expensive, there is a limit to using LiCoO 2 as a power source in fields such as electric vehicles.
  • lithium manganese composite metal oxides such as LiMnO 2 or LiMn 2 O 4
  • lithium iron phosphate compounds such as LiFePO 4
  • lithium nickel composite metal oxides such as LiNiO 2
  • research and development of lithium nickel composite metal oxides having a high reversible capacity of about 200 mAh / g and easy to implement a large-capacity battery have been actively studied.
  • LiNiO 2 has a poor thermal stability compared to LiCoO 2, and when an internal short circuit occurs due to pressure from the outside in a charged state, the positive electrode active material itself decomposes, causing a battery to rupture and ignite.
  • a nickel cobalt manganese-based lithium composite metal oxide in which a part of Ni is substituted with Mn and Co (hereinafter, simply referred to as 'NCM-based lithium oxide') has been developed.
  • 'NCM-based lithium oxide' a nickel cobalt manganese-based lithium composite metal oxide in which a part of Ni is substituted with Mn and Co
  • the present invention is to solve the above problems, a low amount of lithium by-products, cobalt-rich layer (Co-rich layer) is formed on the surface of the high-concentration nickel cathode active material that can simultaneously realize excellent capacity characteristics and high temperature stability And, to provide a manufacturing method, and a positive electrode and a secondary battery for a secondary battery comprising the same.
  • the present invention is a lithium composite metal oxide represented by the formula (1); And a cobalt-rich layer formed on the surface of the lithium composite metal oxide and having a higher cobalt content than the lithium composite metal oxide.
  • M is one metal element selected from the group consisting of Al, Mg, Ge, V, Mo, Nb, Si, Ti, Zr and W, and X is P or F.
  • the ratio of the number of atoms of cobalt to the sum of the number of atoms of nickel, cobalt, manganese and M in the cobalt-rich layer and the number of atoms of cobalt to the sum of the number of atoms of nickel, cobalt, manganese and M in the lithium composite metal oxide may be 0.05 to 0.2, preferably 0.05 to 0.15.
  • the ratio of the number of atoms of cobalt to the sum of the number of atoms of nickel, cobalt, manganese and M in the cobalt-rich layer may be 0.05 to 0.45, and preferably 0.05 to 0.35.
  • the cobalt rich layer may have a thickness of 10 to 100 nm, preferably 10 to 70 nm.
  • the positive electrode active material when the heat flow measured by differential scanning calorimetry (DSC)
  • a peak appears in the temperature range of 230 °C to 250 °C, preferably 235 °C to 245 °C
  • the maximum value of the heat flow may be 1000 mW or less, preferably 600 mW or less, and more preferably 400 mW or less.
  • the lithium by-product content in the positive electrode active material may be 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.3% by weight or less.
  • the present invention comprises the steps of preparing a lithium composite metal oxide represented by the formula (1); Washing the lithium composite metal oxide; And it provides a method for producing a positive electrode active material for a secondary battery comprising the step of mixing the washed lithium composite metal oxide and cobalt-containing raw material and heat treatment at an temperature of 700 °C or more in an oxidizing atmosphere.
  • the step of preparing a lithium composite metal oxide represented by the formula (1), a nickel-cobalt precursor, a manganese-containing raw material, M-containing raw material, and a lithium-containing raw material mixed and fired at 600 °C to 900 °C It can be performed as.
  • the washing step may be performed at a temperature of 20 °C or less.
  • the cobalt-containing raw material may be mixed to 0.001 to 0.01 parts by weight, preferably 0.002 to 0.008 parts by weight based on 100 parts by weight of the lithium composite metal oxide.
  • the heat treatment may be performed within 10 hours at 700 °C to 800 °C temperature.
  • the present invention provides a secondary battery positive electrode including the positive electrode active material for a secondary battery according to the present invention, and a secondary battery comprising the positive electrode for the secondary battery.
  • a cobalt-rich layer including a high content of cobalt having excellent output characteristics and stability is formed on the surface thereof, unlike the conventional high concentration nickel positive electrode active material, it is not only structurally stable but also repeatedly charged. Even when the secondary battery is excellent in capacity characteristics and has a small resistance increase rate.
  • a positive electrode active material can be manufactured.
  • Example 1 is a graph showing the heat flow (Heat Flow) according to the temperature of the positive electrode active material of Example 1 and Comparative Example 3.
  • FIG. 2 is a graph showing pH titration curves of the positive electrode active materials of Example 1, Comparative Examples 1 and 4 to 6.
  • FIG. 2 is a graph showing pH titration curves of the positive electrode active materials of Example 1, Comparative Examples 1 and 4 to 6.
  • FIG. 3 is a graph showing capacity retention rates according to charge and discharge cycles of battery cells prepared using the cathode active materials of Example 1 and Comparative Examples 2 and 3.
  • FIG. 3 is a graph showing capacity retention rates according to charge and discharge cycles of battery cells prepared using the cathode active materials of Example 1 and Comparative Examples 2 and 3.
  • Example 4 is a graph showing the resistance increase rate according to the charge and discharge cycle of the battery cell prepared using the positive electrode active material of Example 1 and Comparative Examples 2 and 3.
  • the inventors of the present invention have been researched to produce a high-density nickel-based positive electrode active material having a low residual amount of lithium by-products and excellent high temperature stability.
  • a lithium composite metal oxide containing a specific metal element M in an appropriate composition ratio together with nickel, cobalt, and manganese is used. After washing with water, the mixture was mixed with the cobalt-containing raw material and then heat treated at an temperature of 700 ° C. or higher in an oxidizing atmosphere to find a high concentration nickel-based cathode active material having low residual amount of lithium by-product and excellent high temperature stability. It was.
  • Method for producing a positive electrode active material comprises the steps of (1) preparing a lithium composite metal oxide represented by the formula (1), (2) washing the lithium composite metal oxide and (3) the washed lithium composite metal oxide Mixing the cobalt-containing raw material and heat-treating at an temperature of 700 ° C. or higher in an oxidizing atmosphere.
  • each step of the present invention will be described in more detail.
  • a lithium composite metal oxide is prepared.
  • the lithium composite metal oxide used in the present invention is nickel, cobalt, manganese, and four components of M, which is one metal element selected from the group consisting of Al, Mg, Ge, V, Mo, Nb, Si, Ti, Zr, and W. It is a four-component lithium composite metal oxide containing essential as a high concentration nickel (high-nickel) four-component lithium composite metal oxide in which the molar ratio of nickel in the said four components exceeds 0.7.
  • the lithium composite metal oxide may be a lithium composite metal oxide represented by Formula 1 below.
  • M is one metal element selected from the group consisting of Al, Mg, Ge, V, Mo, Nb, Si, Ti, Zr, and W
  • X is P or F.
  • a represents an atomic fraction of nickel among the metal elements excluding lithium, and a may be greater than 0.7 but less than 1, preferably 0.8 to 0.95, and more preferably 0.8 to 0.9.
  • B represents an atomic fraction of cobalt among metal elements excluding lithium, and b may be greater than 0 and less than 0.3, preferably 0.001 to 0.25, more preferably 0.01 to 0.2.
  • C represents an atomic fraction of manganese among metal elements excluding lithium, and c may be greater than 0 and less than 0.1, preferably 0.001 to 0.05.
  • the d represents an atomic fraction of the M element among the metal elements excluding lithium, and d may be greater than 0 and less than 0.1, preferably 0.001 to 0.05.
  • x represents the extent to which some of the metal elements except lithium are replaced by lithium
  • y represents the extent to which oxygen is replaced by the X element, 0 ⁇ x ⁇ 0.1, 0 ⁇ y ⁇ 0.5.
  • the lithium composite metal oxide having the composition as shown in [Formula 1] is relatively high in structural stability, while implementing a high capacity characteristic compared to the conventional NMC-based lithium oxide.
  • the lithium composite metal oxide of [Formula 1] has a high nickel content having a high capacity characteristic, thereby realizing excellent capacity characteristics, and Mn and M elements are doped inside the active material, compared to the conventional NMC-based lithium oxide. Structurally stable.
  • oxygen is replaced with P or F, desorption of oxygen is prevented during charge and discharge of the lithium secondary battery, and interfacial reaction with the electrolyte is suppressed, thereby improving surface stability.
  • the lithium composite metal oxide of [Formula 1] is not limited thereto, but for example, a nickel-cobalt precursor, a manganese-containing raw material, a M-containing raw material, and a lithium-containing raw material are mixed, and 700 ° C. to 900 ° C. It may be prepared by the method of firing at °C.
  • the nickel-cobalt precursor may be, for example, nickel-cobalt hydroxide, specifically, a compound represented by Ni a ' Co b' OOH, wherein a 'is 0.7 to 0.95, preferably Preferably it may be 0.8 to 0.95, the b 'may be 0.05 to 0.3, preferably 0.05 to 0.2.
  • the nickel-cobalt precursor may be purchased by using a commercially available nickel-cobalt hydroxide, or may be prepared according to a method for preparing a nickel-cobalt precursor well known in the art.
  • the nickel-cobalt precursor may be prepared by coprecipitation reaction by adding an ammonium cation-containing complex former and a basic compound to a metal solution containing a nickel-containing raw material and a cobalt-containing raw material.
  • the nickel-containing raw material may be, for example, nickel-containing acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide or oxyhydroxide, and the like, specifically, Ni (OH) 2 , NiO, NiOOH, NiCO 3. 2Ni (OH) 2 4H 2 O, NiC 2 O 2 2H 2 O, Ni (NO 3 ) 2 6H 2 O, NiSO 4 , NiSO 4 6H 2 O, fatty acid nickel salts, nickel halides or their It may be a combination, but is not limited thereto.
  • the cobalt-containing raw material may be cobalt-containing acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide or oxyhydroxide, and the like, specifically, Co (OH) 2 , CoOOH, Co (OCOCH 3 ) 2 ⁇ 4H 2 O , Co (NO 3 ) 2 ⁇ 6H 2 O, Co (SO 4 ) 2 ⁇ 7H 2 O or a combination thereof, but is not limited thereto.
  • the metal solution is prepared by adding a nickel-containing raw material and a cobalt-containing raw material to a solvent, in particular water, or a mixed solvent of an organic solvent (eg, alcohol, etc.) that can be mixed uniformly with water, or It may be prepared by mixing an aqueous solution of the nickel-containing raw material and an aqueous solution of the cobalt-containing raw material.
  • a solvent in particular water, or a mixed solvent of an organic solvent (eg, alcohol, etc.) that can be mixed uniformly with water, or It may be prepared by mixing an aqueous solution of the nickel-containing raw material and an aqueous solution of the cobalt-containing raw material.
  • the ammonium cation-containing complex former may be, for example, NH 4 OH, (NH 4 ) 2 SO 4 , NH 4 NO 3 , NH 4 Cl, CH 3 COONH 4 , NH 4 CO 3, or a combination thereof. It is not limited to this.
  • the ammonium cation-containing complex forming agent may be used in the form of an aqueous solution, wherein a solvent may be a mixture of water or an organic solvent (specifically, alcohol, etc.) that can be uniformly mixed with water.
  • the basic compound may be a hydroxide of an alkali metal or alkaline earth metal such as NaOH, KOH or Ca (OH) 2 , a hydrate thereof, or a combination thereof.
  • the basic compound may also be used in the form of an aqueous solution, and as the solvent, a mixture of water or an organic solvent (specifically, alcohol, etc.) that can be uniformly mixed with water may be used.
  • the basic compound may be used by dissolving an anionic compound including the X element, that is, P and / or F.
  • an anionic compound including the X element that is, P and / or F.
  • the X element derived from the anionic compound is partially substituted at the oxygen position of the precursor, it is possible to obtain the effect of suppressing oxygen desorption and reaction with the electrolyte during charging and discharging of the secondary battery.
  • the basic compound is added to adjust the pH of the reaction solution, and may be added in an amount such that the pH of the metal solution is 11 to 13.
  • the coprecipitation reaction may be carried out at a temperature of 40 °C to 70 °C under an inert atmosphere such as nitrogen or argon.
  • nickel-cobalt hydroxide particles are produced and precipitated in the reaction solution.
  • the precipitated nickel-cobalt hydroxide particles can be separated according to a conventional method and dried to obtain a nickel-cobalt precursor.
  • the nickel cobalt precursor prepared by the above method, a manganese-containing raw material, an M-containing raw material and a lithium-containing raw material are mixed and calcined at 600 ° C to 900 ° C, preferably 600 ° C to 800 ° C to form a lithium composite metal oxide. You can get it.
  • the manganese-containing raw material may be, for example, manganese-containing acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide, oxyhydroxide or a combination thereof, and specifically Mn 2 O 3 , MnO 2 Manganese oxides such as Mn 3 O 4 and the like; Manganese salts such as MnCO 3 , Mn (NO 3 ) 2 , MnSO 4 , manganese acetate, manganese dicarboxylic acid, manganese citrate, fatty acid manganese; Manganese oxy hydroxide, manganese chloride or a combination thereof, but is not limited thereto.
  • the M-containing raw material may be acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide, oxyhydroxide or a combination thereof containing M element, specifically, Al 2 O 3 , AlSO 4 , AlCl 3 , Al-isopropoxide, AlNO 3 , or a combination thereof, but is not limited thereto.
  • the lithium-containing raw material may be a lithium-containing carbonate (e.g., lithium carbonate), a hydrate (e.g., lithium hydroxide I hydrate (LiOH, H 2 O), etc.), a hydroxide (e.g., lithium hydroxide, etc.), a nitrate ( For example, lithium nitrate (LiNO 3 ), etc.), chlorides (for example, lithium chloride (LiCl), etc.), and the like may be used alone, or a mixture of two or more thereof may be used.
  • a lithium-containing carbonate e.g., lithium carbonate
  • a hydrate e.g., lithium hydroxide I hydrate (LiOH, H 2 O), etc.
  • a hydroxide e.g., lithium hydroxide, etc.
  • a nitrate For example, lithium nitrate (LiNO 3 ), etc.
  • chlorides for example, lithium chloride (LiCl), etc.
  • the mixing of the nickel-cobalt precursor, the manganese containing raw material, the M containing raw material, and the lithium containing raw material may be made by solid phase mixing such as jet milling. Meanwhile, the mixing ratio of the nickel-cobalt precursor, the manganese-containing raw material, the M-containing raw material, and the lithium-containing raw material may be determined in a range satisfying the atomic fraction of each metal component in the finally manufactured lithium composite metal oxide.
  • the X-containing raw material may be further mixed during the firing.
  • the X-containing raw material may be, for example, Na 3 PO 4 , K 3 PO 4 , Mg 3 (PO 4 ) 2 , AlF 3 , NH 4 F, LiF, and the like, but is not limited thereto.
  • the lithium composite metal oxide is prepared in the same manner as above, the lithium composite metal oxide is washed with water to remove lithium by-products remaining in the lithium composite metal oxide.
  • Lithium composite metal oxides containing high concentrations of nickel are more structurally unstable than lithium composite metal oxides with low nickel content, resulting in more lithium byproducts such as unreacted lithium hydroxide or lithium carbonate in the manufacturing process.
  • the amount of lithium byproducts after synthesis is about 0.5 to 0.6 wt%, whereas in the case of a lithium composite metal oxide having a nickel fraction of 80 atomic% or more, lithium after synthesis The amount of by-products appears as high as 1% by weight.
  • the washing step may be performed, for example, by adding a lithium composite metal oxide to ultrapure water and stirring the mixture.
  • the washing temperature may be 20 °C or less, preferably 10 °C to 20 °C, the washing time may be about 10 minutes to 1 hour.
  • the water washing temperature and the water washing time satisfy the above range, lithium by-products can be effectively removed.
  • the washed lithium composite metal oxide and the cobalt-containing raw material are mixed and heat-treated.
  • the heat treatment is performed at a temperature of 700 °C or more in an oxidizing atmosphere.
  • the heat treatment step is to improve the structural stability and thermal stability by further removing lithium by-products, and recrystallization of the metal elements in the positive electrode active material through high temperature heat treatment.
  • the cobalt-containing raw material may include cobalt-containing acetates, nitrates, sulfates, halides, sulfides, hydroxides, oxides, or oxyhydroxides, and specifically, Co (OH) 2 , CoOOH, Co (OCOCH 3 ) 2 ⁇ 4H. 2 O, Co (nO 3) 2 and 6H 2 O, Co (SO 4 ) 2 and 7H 2 O, or the like may be used a combination thereof, and the like.
  • the cobalt-containing raw material may be mixed in an amount of 0.001 to 0.01 parts by weight, preferably 0.002 to 0.008 parts by weight, based on 100 parts by weight of the lithium composite metal oxide.
  • the content of the cobalt-containing raw material satisfies the above range, the output characteristics can be effectively improved without inhibiting the capacity characteristics of the lithium composite metal oxide.
  • the amount is less than 0.001 part by weight, the effect of improving the output is insignificant.
  • nickel in the lithium composite metal oxide may be replaced with cobalt to deteriorate capacity characteristics.
  • the cobalt component When the heat treatment is performed by additionally adding the cobalt-containing raw material, the cobalt component is coated on the surface of the lithium composite metal oxide during the heat treatment process, and thus the cobalt-rich layer having a relatively higher cobalt content than the inside of the lithium composite metal oxide ( Cobalt-Rich Layer is formed. As such, when the cobalt-rich layer is formed on the surface of the lithium composite metal oxide, an output characteristic may be improved.
  • the heat treatment is carried out in an oxidizing atmosphere, for example, an oxygen atmosphere.
  • the heat treatment may be performed while supplying oxygen at a flow rate of 0.5 to 10 L / min, preferably 1 to 5 L / min.
  • the heat treatment is performed in an oxidizing atmosphere as in the present invention, lithium by-products are effectively removed.
  • the effect of removing lithium by-products is remarkably decreased when heat treatment is performed in the air.
  • heat treatment is performed at 700 or more in the air, the amount of lithium by-products increases rather than before heat treatment.
  • the heat treatment is preferably performed within 10 hours, for example, 1 hour to 10 hours at 700 °C or more, for example, 700 °C to 800 °C temperature.
  • the heat treatment temperature and time satisfy the above range, the effect of improving the thermal stability is excellent. According to the researches of the present inventors, it was found that when the heat treatment temperature is less than 700 ° C., there is little effect of improving thermal stability.
  • the cathode active material for a secondary battery of the present invention manufactured according to the above method includes a lithium composite metal oxide represented by the following Chemical Formula 1, and a cobalt-rich layer formed on the surface of the lithium composite metal oxide.
  • M is one metal element selected from the group consisting of Al, Mg, Ge, V, Mo, Nb, Si, Ti, Zr and W
  • the cobalt-rich layer is a layer formed by coating a surface of a lithium composite metal oxide with a cobalt component derived from a cobalt-containing raw material in a process of mixing and heat treating a lithium composite metal oxide and a cobalt-containing raw material. It is a layer containing more cobalt than metal oxide.
  • the cobalt atomic fraction of the lithium composite metal oxide may be 0.05 to 0.2, preferably 0.05 to 0.15.
  • the atomic fraction of cobalt among nickel, cobalt, manganese, and M in the cobalt-rich layer ie, the ratio of the number of atoms of cobalt to the sum of the number of atoms of nickel, cobalt, manganese, and M
  • the output characteristics can be effectively improved without disturbing the capacity characteristics of the lithium composite metal oxide.
  • the cobalt rich layer may have a thickness of 10 to 100nm, preferably 30nm to 70nm.
  • the thickness of the cobalt rich layer satisfies the above range, when the thickness of the cobalt rich layer exceeds 100 nm, the initial discharge capacity may decrease, and when the thickness of the cobalt rich layer is less than 10 nm, output and cycle characteristics may be degraded. Can be.
  • the cathode active material according to the present invention as described above is manufactured through a process of high temperature heat treatment in an oxidizing atmosphere after washing with water, the residual amount of lithium by-products is significantly less than the conventional high concentration nickel-containing cathode active material, it is possible to implement excellent high temperature stability.
  • the positive electrode active material according to the present invention when the heat flow (Heat Flow) is measured by differential scanning calorimetry (DSC), in the temperature range of 230 °C to 250 °C, preferably in the temperature range of 235 °C to 245 °C A peak appears, and the maximum value of the heat flow is 1000 mW or less, preferably 600 mW or less, more preferably 400 mW or less. If the heat treatment is not performed after washing, or even if the heat treatment temperature and atmosphere does not satisfy the conditions of the present invention, the peak appears at a lower temperature, that is, less than 230 °C, a high heat flow value of more than 1000mW.
  • DSC differential scanning calorimetry
  • the positive electrode active material of the present invention has a relatively high temperature range in which peaks appear and a small maximum amount of heat flow, so that the explosion risk is small even when the internal temperature of the battery rises due to overcharge or the like.
  • the positive electrode active material according to the present invention has a lithium byproduct content of 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.3% by weight or less. Therefore, when the secondary battery is manufactured using the cathode active material according to the present invention, gas generation and swelling phenomenon during charging and discharging can be effectively suppressed.
  • the positive electrode active material for a secondary battery according to the present invention may be usefully used for the production of a positive electrode for a secondary battery.
  • the secondary battery positive electrode according to the present invention includes a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector, wherein the positive electrode active material layer comprises a positive electrode active material according to the present invention.
  • the positive electrode may be manufactured according to a conventional positive electrode manufacturing method except using the positive electrode active material according to the present invention.
  • the positive electrode may be prepared by dissolving or dispersing components constituting the positive electrode active material layer, that is, the positive electrode active material, a conductive material and / or a binder, etc. in a solvent, and manufacturing the positive electrode mixture to the positive electrode current collector. After coating on at least one surface, it may be produced by drying and rolling, or by casting the positive electrode mixture on a separate support, and then laminating the film obtained by peeling from the support onto a positive electrode current collector.
  • 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 carbon or nickel on the surface of aluminum or stainless steel Surface treated with titanium, silver, or the like can be used.
  • the positive electrode current collector may have a thickness of typically 3 ⁇ m to 500 ⁇ m, and may form fine irregularities on the surface of the current collector to increase adhesion of the positive electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • At least one surface of the current collector includes a cathode active material according to the present invention, and optionally a cathode active material layer further comprising at least one of a conductive material and a binder.
  • the cathode active material includes a cathode active material according to the present invention, that is, a lithium composite metal oxide represented by Chemical Formula 1 and a cobalt-rich layer formed on the surface of the lithium composite metal oxide.
  • a cathode active material according to the present invention that is, a lithium composite metal oxide represented by Chemical Formula 1 and a cobalt-rich layer formed on the surface of the lithium composite metal oxide.
  • Specific details of the positive electrode active material according to the present invention are the same as described above, so a detailed description thereof will be omitted.
  • the cathode active material may be included in an amount of 80 to 99% by weight, more specifically 85 to 98% by weight, based on the total weight of the cathode active material layer. When included in the above content range may exhibit excellent capacity characteristics.
  • the conductive material is used to impart conductivity to the electrode, and in the battery constituted, any conductive material may be used as long as it has electronic conductivity without causing chemical change. Specific examples thereof include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black and carbon fiber; Metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Or conductive polymers such as polyphenylene derivatives, and the like, or a mixture of two or more kinds thereof may be used.
  • the conductive material may be included in an amount of 1 wt% to 30 wt% with respect to the total weight of the positive electrode active material layer.
  • the binder serves to improve adhesion between the cathode active material particles and adhesion between the cathode active material and the current collector.
  • specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC).
  • the binder may be included in an amount of 1% by weight to 30% by weight based on the total weight of the positive electrode active material layer.
  • the solvent used to prepare the positive electrode mixture may be a solvent generally used in the art, for example, dimethyl sulfoxide (DMSO), isopropyl alcohol (isopropyl alcohol), N-methylpyrroli Don (NMP), acetone (acetone) or water or the like may be used alone or in combination thereof.
  • DMSO dimethyl sulfoxide
  • NMP N-methylpyrroli Don
  • acetone acetone
  • water or the like may be used alone or in combination thereof.
  • the amount of the solvent used may be appropriately adjusted in consideration of the coating thickness of the slurry, the production yield, the viscosity, and the like.
  • the secondary battery according to the present invention includes a positive electrode, a negative electrode positioned to face the positive electrode, a separator and an electrolyte interposed between the positive electrode and the negative electrode, wherein the positive electrode is the positive electrode according to the present invention described above.
  • the secondary battery may further include a battery container accommodating the electrode assembly of the positive electrode, the negative electrode, and the separator, and a sealing member sealing the battery container.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer positioned on at least one surface of the negative electrode current collector.
  • the negative electrode may be prepared according to a conventional negative electrode manufacturing method generally known in the art.
  • the negative electrode may be prepared by dissolving or dispersing components constituting the negative electrode active material layer, that is, the negative electrode active material, a conductive material and / or a binder, and the like in a solvent, and preparing the negative electrode mixture of the negative electrode current collector. After coating on at least one surface, it may be produced by drying and rolling, or by casting the negative electrode mixture on a separate support, and then laminating the film obtained by peeling from the support onto a negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • the negative electrode current collector may be formed on a surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper, or stainless steel. Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy and the like can be used.
  • the negative electrode current collector may have a thickness of 3 ⁇ m to 500 ⁇ m, and similarly to the positive electrode current collector, fine concavities and convexities may be formed on the surface of the current collector to enhance the bonding force of the negative electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used.
  • Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fibers, and amorphous carbon;
  • Metallic compounds capable of alloying with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys or Al alloys;
  • a composite including the metallic compound and the carbonaceous material such as a Si-C composite or a Sn-C composite, and any one or a mixture of two or more thereof may be used.
  • a metal lithium thin film may be used as the anode active material.
  • the carbon material both low crystalline carbon and high crystalline carbon can be used. Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is amorphous, plate, scaly, spherical or fibrous natural graphite or artificial graphite, Kish graphite (Kish) graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar pitch High-temperature calcined carbon such as derived cokes is typical.
  • the binder and the conductive material may be the same as described above in the positive electrode.
  • the separator separates the negative electrode and the positive electrode and provides a passage for the movement of lithium ions, and can be used without particular limitation as long as it is usually used as a separator in the secondary battery, in particular with respect to the ion movement of the electrolyte It is preferable that it is resistance and excellent in electrolyte solution moisture-wetting ability.
  • a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer or the like Laminate structures of two or more layers may be used.
  • a porous nonwoven fabrics such as nonwoven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers and the like 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 may be optionally used as a single layer or a multilayer structure.
  • the electrolyte may be an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, or the like, which can be used in manufacturing a secondary battery, but is not limited thereto.
  • 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 the battery can move.
  • the organic solvent may be an ester solvent such as methyl acetate, ethyl acetate, ⁇ -butyrolactone or ⁇ -caprolactone; Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate, Carbonate solvents such as PC); Alcohol solvents such as ethyl alcohol and isopropyl alcohol; R a -CN nitriles, such as (R a may include a straight, branched, or a hydrocarbon group
  • carbonate-based solvents are preferable, and cyclic carbonates having high ionic conductivity and high dielectric constant (for example, ethylene carbonate or propylene carbonate) that can improve the charge and discharge performance of a battery, and low viscosity linear carbonate compounds (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate and the like is more preferable.
  • the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of about 1: 1 to 9, so that the performance of the electrolyte may be excellent.
  • the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 .
  • LiCl, LiI, or LiB (C 2 O 4 ) 2 and the like can be used.
  • the concentration of the lithium salt is preferably used within the range of 0.1M to 2.0M. When the concentration of the lithium salt is included in 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, in addition to the electrolyte components, haloalkylene carbonate-based compounds such as difluoroethylene carbonate for the purpose of improving the life characteristics of the battery, suppressing the reduction of the battery capacity, and improving the discharge capacity of the battery; Or pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N
  • One or more additives such as -substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol or aluminum trichloride may be included. In this case, the additive may be included in an amount of 0.1% by weight to 5% by weight based on the total weight of the electrolyte.
  • the secondary battery including the cathode active material according to the present invention has excellent capacity characteristics and high temperature stability, such as a portable device such as a mobile phone, a notebook computer, a digital camera, and a hybrid electric vehicle (HEV). It can be usefully applied to the electric vehicle field.
  • a portable device such as a mobile phone, a notebook computer, a digital camera, and a hybrid electric vehicle (HEV). It can be usefully applied to the electric vehicle field.
  • HEV hybrid electric vehicle
  • the secondary battery according to the present invention can be used as a unit cell of the battery module, the battery module can be applied to a battery pack.
  • the battery module or the battery pack is a power tool (Power Tool); Electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Or it can be used as a power source for any one or more of the system for power storage.
  • Power Tool Power Tool
  • Electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs)
  • PHEVs plug-in hybrid electric vehicles
  • a positive electrode active material was prepared in the same manner as in Example 1 except that heat treatment was not performed.
  • a positive electrode active material was prepared in the same manner as in Example 1 except that Co (OH) 2 was not added during the heat treatment.
  • a positive electrode active material was manufactured in the same manner as in Example 1, except that Co (OH) 2 was not added during the heat treatment and heat-treated at 300 ° C. without oxygen supply.
  • a positive electrode active material was manufactured in the same manner as in Example 1, except that Co (OH) 2 was not added during the heat treatment and heat-treated at 500 ° C. without oxygen supply.
  • a positive electrode active material was manufactured in the same manner as in Example 1, except that Co (OH) 2 was not added during the heat treatment and heat-treated at 600 ° C. without oxygen supply.
  • a positive electrode active material was manufactured in the same manner as in Example 1, except that Co (OH) 2 was not added during the heat treatment and heat-treated at 700 ° C. without oxygen supply.
  • the positive electrode active material of Example 1 showed a peak at 240 ° C., and the maximum amount of heat flow was less than 200 mW, whereas the positive electrode active material of Comparative Example 3 showed a peak at 225 ° C., and the maximum value of heat flow exceeded 1000 mW. can confirm.
  • Residual LiOH and LiCO 3 residues in each cathode active material were calculated using the pH titration curve, and the sum of these values was evaluated as total lithium byproduct residues, and is shown in Table 1 below.
  • the lithium by-product residual amount of the positive electrode active material of Example 1 satisfying the heat treatment conditions of the present invention does not perform the heat treatment process (Comparative Example 1), or when the heat treatment is performed without oxygen supply (Comparative Example Compared to 4 ⁇ 6) it can be seen that significantly falling.
  • the heat treatment is performed in the air atmosphere without supplying oxygen as in Comparative Examples 4 to 6, it can be seen that the residual amount of lithium by-products increases rather than Comparative Example 1 without heat treatment.
  • Each positive electrode active material, carbon black conductive material, and PVdF binder prepared by Example 1, Comparative Example 2 and Comparative Example 3 were mixed in an N-methylpyrrolidone solvent in a ratio of 95: 2.5: 2.5 by weight in a positive electrode mixture (Viscosity: 5000 mPa ⁇ s) was prepared, which was applied to one surface of an aluminum current collector, dried at 130 ° C., and rolled to prepare a positive electrode.
  • a negative electrode active material a natural graphite, a carbon black conductive material, and a PVdF binder were mixed in an N-methylpyrrolidone solvent in a ratio of 85: 10: 5 in a weight ratio to prepare a composition for forming a negative electrode active material layer, and the copper current collector It was applied to one side of to prepare a negative electrode.
  • An electrode assembly was manufactured between the positive electrode and the negative electrode prepared as described above through a separator of porous polyethylene, the electrode assembly was placed in a case, and an electrolyte solution was injected into the case to prepare a lithium secondary battery.
  • the measurement results are shown in FIGS. 3 and 4. 3 is a graph showing a capacity retention rate, and FIG. 4 is a graph showing a resistance increase rate.

Abstract

La présente invention porte sur un matériau actif d'électrode positive pour un accumulateur, son procédé de préparation, une électrode positive le comprenant, et un accumulateur, le matériau actif d'électrode positive comprenant : un oxyde de métal composite de lithium représenté par la formule chimique (1) ; et une couche riche en cobalt formée sur une surface de l'oxyde de métal composite de lithium et dont la teneur en cobalt est supérieure à celle de l'oxyde de métal composite de lithium.
PCT/KR2017/015666 2016-12-28 2017-12-28 Matériau actif d'électrode positive pour accumulateur, son procédé de préparation, électrode positive le comprenant pour accumulateur, et accumulateur WO2018124781A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111600017A (zh) * 2019-02-20 2020-08-28 日亚化学工业株式会社 非水电解质二次电池用正极活性物质及其制造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115072806B (zh) * 2022-07-22 2024-05-07 宁波容百新能源科技股份有限公司 一种正极活性材料、正极浆料、正极片及二次电池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003331845A (ja) * 2002-05-13 2003-11-21 Samsung Sdi Co Ltd リチウム二次電池用正極活物質の製造方法
KR20140081663A (ko) * 2012-12-13 2014-07-01 주식회사 에코프로 리튬 이차 전지용 양극활물질의 제조 방법 및 이에 의하여 제조된 리튬 이차 전지용 양극활물질
KR20150080199A (ko) * 2013-12-31 2015-07-09 주식회사 에코프로 2차 전지용 양극 활물질의 제조방법 및 이에 의하여 제조되는 2차 전지용 양극 활물질
KR101568263B1 (ko) * 2014-08-07 2015-11-11 주식회사 에코프로 리튬 이차 전지용 양극활물질 및 이를 포함하는 리튬 이차 전지
KR20160074236A (ko) * 2014-12-18 2016-06-28 삼성에스디아이 주식회사 복합 양극 활물질, 그 제조방법, 이를 포함한 양극 및 리튬 전지

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101615413B1 (ko) * 2012-11-30 2016-04-25 주식회사 엘지화학 리튬 이차 전지용 양극, 이의 제조방법, 및 이를 포함하는 리튬 이차 전지
CN103700821B (zh) * 2013-12-18 2016-01-13 宁夏科捷锂电池股份有限公司 Co、Mn包覆高镍层状LiNi0.92Co0.04Mn0.04O2锂电池正极材料的制备方法
CN105406036B (zh) * 2015-11-02 2019-03-05 湖南长远锂科有限公司 一种锂离子电池高电压钴酸锂正极材料及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003331845A (ja) * 2002-05-13 2003-11-21 Samsung Sdi Co Ltd リチウム二次電池用正極活物質の製造方法
KR20140081663A (ko) * 2012-12-13 2014-07-01 주식회사 에코프로 리튬 이차 전지용 양극활물질의 제조 방법 및 이에 의하여 제조된 리튬 이차 전지용 양극활물질
KR20150080199A (ko) * 2013-12-31 2015-07-09 주식회사 에코프로 2차 전지용 양극 활물질의 제조방법 및 이에 의하여 제조되는 2차 전지용 양극 활물질
KR101568263B1 (ko) * 2014-08-07 2015-11-11 주식회사 에코프로 리튬 이차 전지용 양극활물질 및 이를 포함하는 리튬 이차 전지
KR20160074236A (ko) * 2014-12-18 2016-06-28 삼성에스디아이 주식회사 복합 양극 활물질, 그 제조방법, 이를 포함한 양극 및 리튬 전지

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111600017A (zh) * 2019-02-20 2020-08-28 日亚化学工业株式会社 非水电解质二次电池用正极活性物质及其制造方法

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