WO2011081422A2 - Oxyde composite de lithium et procédé de production de celui-ci - Google Patents

Oxyde composite de lithium et procédé de production de celui-ci Download PDF

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WO2011081422A2
WO2011081422A2 PCT/KR2010/009456 KR2010009456W WO2011081422A2 WO 2011081422 A2 WO2011081422 A2 WO 2011081422A2 KR 2010009456 W KR2010009456 W KR 2010009456W WO 2011081422 A2 WO2011081422 A2 WO 2011081422A2
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lithium
composite oxide
oxide
lithium composite
tio
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Korean (ko)
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WO2011081422A9 (fr
WO2011081422A3 (fr
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신경
김직수
최문호
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주식회사 에코프로
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Publication of WO2011081422A2 publication Critical patent/WO2011081422A2/fr
Publication of WO2011081422A3 publication Critical patent/WO2011081422A3/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lithium composite oxide for a cathode active material of a lithium secondary battery and a method of manufacturing the same.
  • lithium secondary battery having a high energy density.
  • lithium cobalt oxide for example, LiCoO 2
  • Lithium cobalt oxide has a high potential for lithium, is excellent in safety, and relatively easy to synthesize.
  • LiNiO 2 lithium nickel oxide
  • Nickel is rich in resources, easy to reduce cost, and suitable for high capacity.
  • LiNiO 2 has a high capacity, but the crystal has low thermal stability, and there is room for improvement in cycle characteristics and high temperature storage characteristics. Therefore, the following proposal is made.
  • the active material of the composition which can obtain the improvement effect of cycling characteristics and high temperature storage characteristic has a problem that it is not practical because a capacity becomes small.
  • the present invention by improving the lithium nickel oxide for lithium secondary battery positive electrode active material to solve the above problems, a lithium secondary battery positive electrode active material having a cycle capacity and high temperature storage characteristics and at the same time having a high capacity lithium secondary battery comprising the same It aims to provide.
  • the present invention in the lithium composite oxide, SiO 2 , SnO 2 , Al 2 O 3 , TiO 2 , MgO, Fe 2 O 3 , Bi on the surface of the lithium composite oxide represented by the following formula (1) At least one oxide particle selected from 2 O 3 , Sb 2 O 3 , and ZrO 2 provides a lithium composite oxide coated by a dry coating method.
  • M is at least one metal element selected from the group consisting of Al, Zn, Ti, V, Cr, Mn, Fe and Y)
  • the Al 2 O 3 , TiO 2 , SiO 2 , SnO 2 , MgO, Fe 2 O 3 , Bi 2 O 3 , Sb 2 O 3 , ZrO 2 At least one oxide selected from Al is 2 O 3 Or TiO 2 Being It provides a lithium composite oxide.
  • the lithium composite oxide represented by Formula 1 is composed of primary particles, the primary particles to form secondary particles, the average particle diameter of the primary particles is 0.1 ⁇ m 3 ⁇ m or less, The average particle diameter of the primary particles is 5 ⁇ m or more and 15 ⁇ m or less, and the tap density is 2.2 g / cm 3 or more and 2.8 g / cm 3 or less.
  • the present invention provides a lithium composite oxide of M in the lithium composite oxide represented by the formula (1).
  • the present invention also provides a lithium ion secondary battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte solution, wherein the positive electrode comprises a positive electrode active material comprising the lithium composite oxide.
  • the present invention also provides
  • Nickel-cobalt which forms primary amorphous particles by adding primary coarse particles to the mixed aqueous solution of cobalt salt, nickel salt and aluminum salt by adding ammonia water as a complex and an alkaline solution providing a hydroxyl group as a pH adjusting agent, followed by extraction.
  • the present invention relates to a method for producing a lithium composite oxide, which comprises mixing one kind of oxide particles and performing a second heat treatment at 300 to 500 ° C. under an inert gas atmosphere.
  • the concentration of the aqueous ammonia solution provides a method for producing a lithium composite oxide of 30 to 60% of the concentration of the mixed aqueous solution of cobalt salt, nickel salt, aluminum salt. .
  • step i) the alkaline aqueous solution is preferably added so that the pH in the reactor is 9.0 to 11.5.
  • step iii) at least selected from Al 2 O 3 , TiO 2 , SiO 2 , SnO 2 , MgO, Fe 2 O 3 , Bi 2 O 3 , Sb 2 O 3 , ZrO 2 It is preferable that one type of oxide particle has a size of 100 nm or less.
  • At least one oxide particle selected from Al 2 O 3 , TiO 2 , SiO 2 , SnO 2 , MgO, Fe 2 O 3 , Bi 2 O 3 , Sb 2 O 3 , ZrO 2 is Al. It provides a method for producing a lithium composite oxide, which is 2 O 3 or TiO 2 .
  • step iii) at least selected from SiO 2 , SnO 2 , Al 2 O 3 , TiO 2 , MgO, Fe 2 O 3 , Bi 2 O 3 , Sb 2 O 3 , ZrO 2 It is preferable that one type of oxide particles are mixed at 1 to 3% by weight relative to the lithium-containing composite oxide represented by the formula (1).
  • the concentration of the aqueous ammonia solution is preferably 30 to 60% of the concentration of the mixed aqueous solution of cobalt salt, nickel salt and aluminum salt.
  • the residence time in the reactor of the mixed aqueous solution of the cobalt salt, nickel salt and aluminum salt is preferably 12 to 24 hours.
  • the coating element-containing compound having a size of 100 nm or less formed on the surface of the active material of the present invention can reduce the internal resistance of the active material, thereby preventing the lowering of the discharge potential, thereby maintaining high discharge potential characteristics according to a change in current density (C-rate). Characteristics. Therefore, when the active material having such improved surface properties is applied to a battery, better life characteristics and lowering discharge potentials may be exhibited, thereby showing power improvement characteristics.
  • Figure 3 shows the rate characteristics of the coin cells made of the positive electrode active material of Examples 1 to 4 and Comparative Examples.
  • Figure 4 shows the life characteristics of the coin cells made of the positive electrode active material of Examples 1 to 4 and Comparative Examples.
  • Figure 5 shows the DSC characteristics of the coin cells made of the positive electrode active material of Examples 1 to 4 and Comparative Examples.
  • the positive electrode active material of the present invention is a) lithium composite oxide as the core particles and b) Al 2 O 3 , TiO 2 , SiO 2 , SnO 2 , MgO, Fe 2 O 3 , Bi 2 O 3 , Sb 2 O 3 coated thereon And at least one oxide particle selected from ZrO 2 .
  • the a) nickel-cobalt-aluminum composite hydroxide as the core particle may be prepared by coprecipitation using each metal-containing salt and a basic substance.
  • the coprecipitation method is a method of preparing two or more kinds of transition metal elements simultaneously by using a precipitation reaction in an aqueous solution.
  • a composite hydroxide containing two or more transition metals is prepared by mixing metal-containing salts in a desired molar ratio in consideration of the metal content to prepare an aqueous solution, followed by a strong base such as sodium hydroxide, and optionally ammonia. It may be prepared by adding an additive such as a source or the like and coprecipitation while keeping the pH basic. At this time, by appropriately controlling the temperature, pH, reaction time, slurry concentration, ion concentration, and the like, desired average particle diameter, particle diameter distribution, and particle density can be adjusted.
  • the pH range is 9-13 and preferably 10-12.
  • ammonia water and an alkaline solution are added to a mixed aqueous solution containing cobalt salt, nickel salt and aluminum salt.
  • the aqueous ammonia serves to control the shape of the complex hydroxide formed as a complex
  • the alkaline solution serves to maintain a pH suitable for coprecipitation in the mixed aqueous solution as a pH adjusting agent.
  • Preferred pH ranges are maintained to be basic as 10.5 to 11.5.
  • the metal-containing salt may be a sulfate or nitrate, preferably having an anion that is easily decomposed and volatilized upon firing.
  • nickel sulfate, cobalt sulfate, manganese sulfate, nickel nitrate, cobalt nitrate, manganese nitrate, and the like but are not limited thereto.
  • As a compound containing an aluminum salt only aluminum hydroxide, aluminum oxide, aluminum nitrate, aluminum fluoride, aluminum chloride, etc. may be mixed.
  • the alkaline solution may include sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like, preferably sodium hydroxide, but is not limited thereto.
  • additives and / or alkali carbonates which may form complexes with metal salts in the coprecipitation process may be further added.
  • an ammonium ion source for example, an ethylene diamine compound, a citric acid compound, or the like can be used.
  • the ammonium ion source include aqueous ammonia, aqueous ammonium sulfate solution and aqueous ammonium nitrate salt.
  • the alkali carbonate may be selected from the group consisting of ammonium carbonate, sodium carbonate, potassium carbonate and lithium carbonate. In some cases, these may be used by mixing two or more thereof.
  • the addition amount of the additive and alkali carbonate can be appropriately determined in consideration of the amount of transition metal-containing salt, pH, and the like.
  • the lithium composite according to the present invention is added to the spherical nickel-cobalt-aluminum metal composite hydroxide by adding a compound containing lithium and performing a first heat treatment at 600-800 ° C. under a dry air blowing condition and then cooling to room temperature. An oxide is formed.
  • the primary heat treatment is preferably performed at 600 ° C. or higher and 850 ° C. or lower, and more preferably 700 ° C. or higher and 800 ° C. or lower.
  • the firing time depends on the firing temperature, it is advantageous to control the shape of the particles, for example, for 10 to 20 hours in a dry air atmosphere.
  • the first heat treatment is performed at a temperature lower than 600 ° C., the reaction between the compounds used is not sufficient, and when the temperature is higher than 850 ° C., an unstable structure is formed by evaporation of Li in the crystal structure. have.
  • blowing gas it is also desirable to inject blowing gas at this time to increase the drying rate.
  • an inert gas such as nitrogen gas or argon gas may be preferably used as a gas having no CO 2 or moisture.
  • the drying rate can be increased by maintaining a vacuum instead of the blowing gas.
  • Lithium carbonate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium oxide and the like can be used for the compound containing lithium.
  • lithium carbonate and lithium hydroxide are most advantageous in terms of environment and cost. It is preferable that the average particle diameter of the compound containing lithium is 5 micrometers or less. If the average particle diameter of the compound containing lithium is too large, the reaction may not proceed uniformly.
  • the cathode active material when the cathode active material is manufactured, it is synthesized using a solid phase synthesis method and a wet method.
  • the solid phase reaction method When the solid phase reaction method is used, starting materials for synthesizing the positive electrode active material and secondary phases generated at a low temperature remain at a high temperature. If the size of the particles used as a material is large, it is difficult to control the homogeneous distribution and size of the particles.
  • the size of the particles to be coated and the post-coating heat treatment temperature are controlled to enable the synthesis of single particles even at low temperatures.
  • At least one oxide particle selected from 2 is mixed to be coated by the dry coating method.
  • the metal oxide coated on the surface suppresses the change of the crystal structure, thereby improving cycling stability during charge and discharge.
  • At least one oxide particle selected from Al 2 O 3 , TiO 2 , SiO 2 , SnO 2 , MgO, Fe 2 O 3 , Bi 2 O 3 , Sb 2 O 3 , ZrO 2 may be Al 2 O 3 , TiO 2.
  • the particle size was 100 nm or less to allow single particles to be synthesized even at a uniform coating and low temperature.
  • the mixing process for the dry coating method can be carried out by homogenizing for 1 to 3 hours using an automatic mixer.
  • Secondary heat treatment after coating is preferably performed at 300 to 500 °C. If the temperature is low, even coated oxides of 100 nm or less do not crystallize, and therefore, the application of the active material to the battery may interfere with the movement of lithium ions. In addition, when the heat treatment temperature is higher, the evaporation of lithium and the crystallinity of the metal oxide layer formed on the surface become high, which causes a problem in the movement of Li + .
  • the nonaqueous electrolyte secondary battery of the present invention is characterized by a positive electrode active material, and other components are not particularly limited.
  • the present invention provides a lithium secondary battery comprising a positive electrode active material prepared by the above manufacturing method.
  • the above-mentioned positive electrode active material may be mixed with other positive electrode active materials other than the positive electrode active material according to the present invention, and the present invention also provides a lithium secondary battery including such a positive electrode.
  • Methods for producing a lithium secondary battery by the construction of a positive electrode, a negative electrode, a separator, and a lithium salt-containing nonaqueous electrolyte are known in the art.
  • the positive electrode is prepared by applying a mixture of a positive electrode mixture of a positive electrode active material, a conductive agent and a binder and a ferroelectric material on a positive electrode current collector, and then drying it, and optionally adding a filler to the mixture. do.
  • the positive electrode current collector is generally made to a thickness of 3 to 500 ⁇ m. Such a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery. For example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like may be used.
  • the current collector may form fine irregularities on its surface to increase the adhesion of the positive electrode active material, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the conductive agent is typically added in an amount of 1 to 50 wt% based on the total weight of the mixture including the positive electrode active material.
  • a conductive agent is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • the conductive agent include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the binder is a component that assists in bonding the active material and the conductive agent to the current collector, and is generally added in an amount of 1 to 50 wt% based on the total weight of the mixture including the positive electrode active material.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, Polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers, and the like.
  • the filler is optionally used as a component for inhibiting expansion of the positive electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
  • the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
  • the negative electrode is produced by applying and drying the negative electrode material on the negative electrode current collector.
  • a conductive agent, a binder, a filler, or the like as in the positive electrode mixture may be optionally included.
  • the negative electrode current collector is generally made to a thickness of 3 to 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • the 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.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the separator is interposed between the cathode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used.
  • the pore diameter of the separator is generally from 0.01 to 10 ⁇ m ⁇ m, thickness is generally 5 ⁇ 300 ⁇ m.
  • a separator for example, olefin polymers such as chemical resistance and hydrophobic polypropylene; Sheets made of glass fibers or polyethylene, nonwoven fabrics, and the like are used.
  • a solid electrolyte such as a polymer is used as the electrolyte, the solid electrolyte may also serve as a separator.
  • the lithium salt-containing non-aqueous electrolyte consists of a nonaqueous electrolyte and lithium.
  • a nonaqueous electrolyte a nonaqueous electrolyte, a solid electrolyte, an inorganic solid electrolyte, and the like are used.
  • organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymers containing ionic dissociating groups and the like can be used.
  • Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates, and the like of Li, such as Li 4 SiO 4 —LiI-LiOH, Li 3 PO 4 —Li 2 S-SiS 2 , and the like, may be used.
  • Lithium salt is a material that is good to dissolve in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2NLi, lithium chloroborane, lower aliphatic lithium carbonate, lithium tetraphenylborate, imide and the like can be used.
  • the non-aqueous electrolyte includes pyridine, triethyl phosphite, triethanol amine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, for the purpose of improving charge / discharge characteristics, flame retardancy, and the like.
  • halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics.
  • the produced Ni-Co hydroxide overflowed, concentrated in a concentration tank connected to the overflow tube, circulated through the reaction tank, and 40 hours until the concentration of Ni-Co-Al hydroxide in the reaction tank and the settling tank became 4 mol / l.
  • the reaction was carried out.
  • the taken out suspension was washed with 5 times the amount of water using a filter press, and the Ni-Co-Al hydroxide concentration was adjusted to 2 mol / l.
  • the concentration of coexisting soluble salt in the filtrate immediately before the end of washing was checked by an infrared moisture meter, and the concentration was 15%.
  • Lithium hydroxide 784g was mixed with the obtained Ni-Co-Al coprecipitated hydroxide 3, and calcined at a temperature of 750 ° C for 10 hours in an atmosphere having an oxygen partial pressure of 0.5 atm, and a lithium composite oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) Got.
  • the lithium nickel composite oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) thus obtained was mixed with 1 wt% of alumina (Al 2 O 3 ) particles having a size of 100 nm, and subjected to a solid phase reaction under inert gas N 2 injection, followed by 300 ° C. It baked in the oxygen atmosphere for 3 hours at the temperature of.
  • Example 1 1 wt% of Al 2 O 3 compared to lithium composite oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) and coated by solid phase reaction, and then calcined at 500 ° C. for 3 hours to be the same as in Example 1 It was prepared by the method.
  • Example 3 NCA heat-treated at 300 with 1% weight titanium dioxide (TiO 2 )
  • TiO 2 was prepared in the same manner as in Example 1, except that 1 wt% of the lithium composite oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) was added thereto to be coated by solid phase reaction.
  • 1 wt% of the lithium composite oxide LiNi 0.8 Co 0.15 Al 0.05 O 2
  • Example 4 NCA heat treated at 300 with 3% weight titanium dioxide (TiO 2 )
  • TiO 2 was prepared in the same manner as in Example 1, except that 3 wt% of the lithium composite oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) was added and subjected to solid phase reaction.
  • 3 wt% of the lithium composite oxide LiNi 0.8 Co 0.15 Al 0.05 O 2
  • a lithium composite oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) powder that was not coated as a cathode active material was used in the same manner as in Example 1.
  • the active material has a spherical active material of about 7 ⁇ m having uniform primary particles.
  • Examples 1 to 4 show a uniform particle shape as in Comparative Example, but the nano-sized coating material was uniformly coated on the surface, and it can be observed that the morphology changes as the amount of coating increases. have.
  • the cell obtained as described above is represented by [Li 2 MnO 4 / LiPF 6 (1 M) in EC +2 EMC / Li], and the rate (C-rate), life, and safety characteristics of the cell were evaluated.
  • FIG. 4 The evaluation of the life characteristics is shown in FIG. 4 by measuring the change in irreversible capacity with high temperature 60 cycles in the range of 3.4 to 4.3 V. As shown in FIG. 4, it can be seen that Examples 1 to 4 are excellent in high temperature cycle life characteristics because there is almost no capacity decrease with increasing cycle as compared with Comparative Example 1. These results indicate that Al 2 O 3 and TiO 2 coated on the surface of the active material suppress side reactions of residual lithium and electrolyte generated on the surface of the electrode as the battery cycle progresses, thereby minimizing the increase in resistance of the electrode, thereby preventing lithium consumption. It is thought that the lifespan performance is improved by giving.
  • the thermal stability of the active material prepared according to the present invention was evaluated by the following method.
  • Coin cells prepared according to Comparative Example 1 and Examples 1 to 4 were charged to the 4.5V and then disassembled in a dry room to separate the electrode plates.
  • About 10mg of the active material coated on the Al-foil was collected from the separated plate and about 10mg of the active material coated on the Al-foil was collected from the separated electrode plate. DSC analysis was performed.
  • DSC analysis was performed by scanning at an elevated temperature rate of 3 ° C./min in the temperature range between 100 ° C. and 300 ° C. under air atmosphere. DSC analysis results are shown in FIG. 5.
  • the exothermic peak that appears as a result of DSC analysis is such a phenomenon that deteriorates the safety of the battery.
  • the area of the exothermic peak of the active material prepared according to Example 3 of the present invention was much reduced than that of Comparative Example 1. This reduction in heat generation results in the thermal stability of the positive electrode active material by suppressing side reactions of residual lithium and electrolyte generated on the surface of the electrode as Al 2 O 3 , TiO 2, etc. coated on the surface of the active material as the battery cycle progresses. To show that this is excellent.
  • the coating element-containing compound having a size of 100 nm or less formed on the surface of the active material can reduce the internal resistance of the active material, thereby preventing the lowering of the discharge potential, thereby maintaining high discharge potential characteristics according to the current density (C-rate) change. It can be usefully used as a lithium composite oxide for a cathode active material and a manufacturing method of a lithium secondary battery exhibiting characteristics.

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Abstract

L'invention se réfère à un oxyde composite de lithium s'utilisant comme matière active d'anode pour une pile rechargeable au lithium et à un procédé de production de celui-ci. L'invention concerne plus spécifiquement une matière active d'anode destinée à une pile rechargeable au lithium comprenant un oxyde composite de lithium: dans le procédé de production de l'oxyde composite de lithium, on utilise un procédé de revêtement à sec pour revêtir des particules d'oxyde d'au moins un type de composé sélectionné dans le groupe comprenant SiO2, SnO2, Al2O3, TiO2, MgO, Fe2O3, Bi2O3, Sb2O3 et ZrO2, ledit composé étant appliqué sur la surface d'un oxyde composite de lithium-nickel représenté par la formule chimique 1 indiquée ci-dessous. L'invention concerne également un procédé de production de cet oxyde composite de lithium. [Formule chimique 1] LixNi1-y-zCoyMzO2 (dans laquelle 0,98=x=1,1, 0,05=y=0,2, 0,05=z=0,2, et M représente au moins un type d'élément métallique sélectionné dans le groupe constitué par Al, An, Ti, V, Cr, Mn, Fe et Y).
PCT/KR2010/009456 2009-12-31 2010-12-29 Oxyde composite de lithium et procédé de production de celui-ci WO2011081422A2 (fr)

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CN103779535A (zh) * 2012-10-18 2014-05-07 三星精密化学股份有限公司 锂金属氧化物复合物、其制备方法和包括其的锂二次电池
CN109742344A (zh) * 2018-12-21 2019-05-10 贵州振华新材料股份有限公司 低游离锂的氧化铝包覆高镍正极材料、制法和应用
CN110190256A (zh) * 2019-05-23 2019-08-30 广东工业大学 一种氧化锑/氮掺杂石墨烯复合材料及其制备方法和应用
EP3547432A4 (fr) * 2016-11-25 2020-07-22 Shenzhen Capchem Technology Co., Ltd. Batterie au lithium-ion
CN112194175A (zh) * 2020-09-25 2021-01-08 广东工业大学 一种锂离子电池用二氧化锡/氧化锆掺杂碳复合材料及其制备方法和应用

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KR101338371B1 (ko) * 2011-11-28 2014-01-10 주식회사 포스코이에스엠 리튬-니켈-코발트-알루미늄 복합 산화물의 제조 방법, 이에 의하여 제조된 리튬-니켈-코발트-알루미늄 복합 산화물 및 이를 포함하는 리튬 이차 전지
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WO2016053051A1 (fr) * 2014-10-02 2016-04-07 주식회사 엘지화학 Matériau actif d'électrode positive pour batterie secondaire au lithium, son procédé de fabrication, et batterie secondaire lithium comprenant celui-ci
KR101758992B1 (ko) 2014-10-02 2017-07-17 주식회사 엘지화학 리튬 이차전지용 양극활물질, 이의 제조방법 및 이를 포함하는 리튬 이차전지
KR101823729B1 (ko) * 2015-03-13 2018-01-30 주식회사 엘지화학 리튬 금속 산화물 및 이를 포함하는 리튬 이차전지용 음극 활물질, 및 이의 제조방법
JP6848172B2 (ja) * 2015-10-01 2021-03-24 株式会社豊田自動織機 リチウム複合金属酸化物部、中間部及び導電性酸化物部を有する材料
KR102059978B1 (ko) * 2015-11-30 2019-12-30 주식회사 엘지화학 이차전지용 양극활물질 및 이를 포함하는 이차전지
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KR102237951B1 (ko) * 2017-03-21 2021-04-08 주식회사 엘지화학 이차 전지용 양극 활물질, 그 제조방법, 이를 포함하는 양극 및 이차 전지
KR102327530B1 (ko) 2018-05-21 2021-11-17 주식회사 엘지화학 이차 전지용 양극 및 이를 포함하는 이차 전지
KR20200046749A (ko) 2018-10-25 2020-05-07 삼성전자주식회사 복합양극활물질, 이를 포함한 양극, 리튬전지 및 그 제조 방법

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CN103779535A (zh) * 2012-10-18 2014-05-07 三星精密化学股份有限公司 锂金属氧化物复合物、其制备方法和包括其的锂二次电池
CN103456943A (zh) * 2013-08-29 2013-12-18 合肥国轩高科动力能源股份公司 锂离子电池复合正极材料及其制备方法
EP3547432A4 (fr) * 2016-11-25 2020-07-22 Shenzhen Capchem Technology Co., Ltd. Batterie au lithium-ion
CN109742344A (zh) * 2018-12-21 2019-05-10 贵州振华新材料股份有限公司 低游离锂的氧化铝包覆高镍正极材料、制法和应用
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CN112194175A (zh) * 2020-09-25 2021-01-08 广东工业大学 一种锂离子电池用二氧化锡/氧化锆掺杂碳复合材料及其制备方法和应用
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