WO2014021626A1 - 이차전지용 양극 활물질 및 이를 포함하는 리튬 이차전지 - Google Patents
이차전지용 양극 활물질 및 이를 포함하는 리튬 이차전지 Download PDFInfo
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- WO2014021626A1 WO2014021626A1 PCT/KR2013/006872 KR2013006872W WO2014021626A1 WO 2014021626 A1 WO2014021626 A1 WO 2014021626A1 KR 2013006872 W KR2013006872 W KR 2013006872W WO 2014021626 A1 WO2014021626 A1 WO 2014021626A1
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- 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
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- 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
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- H—ELECTRICITY
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- 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
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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
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a cathode active material for a secondary battery and a lithium secondary battery including the same, and more particularly, a cathode active material for a secondary battery having an operating voltage range of 2.50 V to 4.35 V, including lithium cobalt oxide and surface treated lithium nickel
- a positive electrode active material comprising a lithium oxide and having a high rolling density by a bimodal form in which the average particle diameter of the cobalt oxide and the average particle diameter of the lithium nickel-based composite oxide are different from each other, and a lithium secondary including the same. It relates to a battery.
- LiCoO 2 is widely used because of its excellent physical properties such as excellent cycle characteristics, but it is low in stability and expensive due to resource limitations of cobalt as a raw material.
- the charge / discharge current amount is about 150 mAh / g, and has various problems such as unstable crystal structure at a voltage of 4.3 V or higher, and reaction with the electrolyte, resulting in the risk of ignition.
- a lithium transition metal oxide of a form in which a part of nickel is replaced with another transition metal such as manganese and cobalt has been proposed as a cathode active material for a lithium secondary battery.
- metal-substituted nickel-based lithium transition metal oxides have advantages in that they have relatively excellent cycle characteristics and capacity characteristics.
- the cycle characteristics deteriorate rapidly during long-term use and swelling due to gas generation. Problems such as phenomenon and low chemical stability have not been sufficiently solved.
- impurities formed by remaining raw materials for the production of active materials in nickel-based lithium transition metal oxides reduce battery capacity or decompose in the battery to generate gas to cause swelling of the battery.
- the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
- the inventors of the present application include lithium cobalt oxide and surface-treated lithium nickel oxide, and the average particle diameter of the cobalt oxide and the average particle diameter of the lithium nickel composite oxide are different from each other.
- a lithium secondary battery is manufactured using another bimodal type positive electrode active material, it is found that the capacity of the battery is increased and the high temperature storage characteristics are improved, and thus the present invention has been completed.
- the cathode active material according to the present invention is a cathode active material for secondary batteries having an operating voltage range of 2.50 V to 4.35 V, including lithium cobalt oxide and surface-treated lithium nickel oxide, and having an average particle diameter of the cobalt oxide
- the average particle diameter of the lithium nickel-based composite oxide is characterized by having a high rolling density by different bimodal forms.
- the inventors of the present application have a bimodal form including lithium cobalt oxide having excellent cycle characteristics having different average particle diameters, and lithium nickel based oxide which is stable at high voltage and has a high potential operating range and excellent capacity characteristics.
- the positive electrode active material of not only the capacity per volume increases as the rolling density of the positive electrode active material is improved as compared to the case of using the oxides alone, or using a mixed positive electrode active material having a similar average particle diameter
- the operating voltage range is expanded to 2.50V to 4.35V compared with the conventional 3.0V to 4.35V, and the discharge end voltage is lowered, thereby maximizing the capacity.
- the rolling density of the positive electrode active material may be higher than the rolling density of the positive electrode active material composed of lithium cobalt oxide and lithium nickel-based oxide having a similar average particle diameter that is not the bimodal form, and the rolling density is detailed.
- the rolling density of the mixed positive electrode active material of the two lithium cobalt oxide and lithium nickel-based oxide having a similar average particle diameter, but not the bimodal form is significantly increased compared to 3.6 to 3.7 g / cc.
- the positive electrode active material 100 includes a bimodal in which particles of lithium nickel-manganese-cobalt oxide 110 are filled in an interstitial volume between particles of the lithium cobalt oxide 120. It is in the form of (bimodal).
- the particle diameter of the lithium cobalt oxide 120 is approximately 3 to 4 times larger than the particle diameter of the lithium nickel-manganese-cobalt oxide 110.
- the lithium cobalt oxide may be a single particle in a potato shape, and the lithium nickel-based oxide may be in an agglomerated structure, that is, in the form of an aggregate of fine powders.
- the average particle diameter of the lithium cobalt-based oxide is 16 to 25 ⁇ m
- the average particle diameter of the fine powder particles of the lithium nickel-based oxide may be 2 to 4 ⁇ m
- the average particle diameter of its aggregate phase is 2 ⁇ 10 ⁇ m.
- the average particle diameter of the said lithium cobalt-type oxide may be 2-10 micrometers, and the average particle diameter of the aggregate phase of the said lithium nickel-type composite oxide may be 16-25 micrometers.
- the lithium cobalt-based oxide may be doped with a dissimilar metal element in order to improve stability, electron conductivity, and rate characteristics of the cathode active material structure.
- the lithium cobalt-based oxide may be represented by the following formula (1).
- M is at least one element selected from the group consisting of Mg, Ti, Zr, Al, and Si.
- M may be Mg and / or Ti, more specifically Mg and Ti.
- the inventors of the present application confirmed that when Mg is doped with lithium cobalt-based oxide, the structural stability of the positive electrode active material is improved, and when doping Ti, the electron conductivity and rate characteristics are improved compared to the conventional one.
- the content of Mg and / or Ti may be 1000 to 2500 ppm based on the total weight of the lithium cobalt oxide.
- the entire surface of the lithium cobalt oxide may be coated with Al 2 O 3 .
- a coating layer 140 of Al 2 O 3 is formed on the surface of the lithium cobalt oxide 120.
- the content of Al may be, in detail, 0.001 to 2000 ppm relative to the total weight of the lithium cobalt oxide, and more specifically, 350 to 500 ppm.
- the coating thickness of Al 2 O 3 may be, for example, 0.5 nm to 2 nm.
- the resistance of the surface is relatively increased so that a desired capacity cannot be obtained, and the rate characteristic may be lowered. If it is too low or the coating thickness is too thin, the desired high temperature storage property improvement effect cannot be obtained.
- the Al 2 O 3 may be coated on the entire surface of the lithium cobalt oxide by a wet coating method.
- the lithium nickel-based oxide may be represented by the following formula (2).
- lithium nickel-based oxides in which a part of nickel is substituted with other transition metals such as manganese and cobalt exhibit relatively high capacity and high cycle stability.
- the content of cobalt (1- (a + b)) may be, for example, 0.1 to 0.3.
- the high content of cobalt increases the overall cost of the raw material and slightly reduces the reversible capacity, while the cobalt content is too low ( At 1- (a + b) ⁇ 0.1), it is difficult to simultaneously achieve sufficient rate characteristics and electron conductivity effects.
- the content (a) of nickel (Ni) may be relatively higher than that of manganese and cobalt, and in detail, may be 0.5 to 0.6. If the nickel content is less than 0.5, it is difficult to expect a high capacity, on the contrary, if it exceeds 0.6, the stability is lowered, and a high temperature swelling problem may occur due to an increase in side reactions during high temperature storage.
- the entire surface of the lithium nickel-based oxide may be reacted with a fluorine-containing polymer to form a coating layer or may be coated with a metal oxide.
- the fluorine-containing polymer may be PVdF or PVdF-HFP, more specifically PVdF.
- the metal oxide may be aluminum oxide (Al 2 O 3 ).
- a coating layer 130 formed using a fluorine-containing polymer or a metal oxide is formed on the surface of the lithium nickel-manganese-cobalt oxide 110.
- the lithium secondary battery using lithium nickel-based oxide has a reduction in battery capacity due to impurities formed by remaining raw materials for manufacturing the active material, and swelling in which impurities are decomposed in the battery to generate gas during a cycle. ) Has a problem.
- the lithium nickel-based oxide surface when the lithium nickel-based oxide surface is reacted with a fluorine-containing polymer to form a coating layer or coated with Al 2 O 3 , it exhibits excellent cycle characteristics and high battery capacity with a stable crystal structure and high nickel content.
- a fluorine-containing polymer when the lithium nickel-based oxide surface is reacted with a fluorine-containing polymer to form a coating layer or coated with Al 2 O 3 , it exhibits excellent cycle characteristics and high battery capacity with a stable crystal structure and high nickel content.
- Li-containing by-products Li 2 CO 3 , LiOH, etc. caused by the excess Li source used in the process of producing the lithium nickel-based oxide, they decompose or react with the electrolyte at high temperature It is possible to suppress the generated gas.
- Inhibiting the reactivity of the Li-containing by-products means reducing the residual amount of the Li-containing by-products, chemically blocking the reaction sites of the Li-containing by-products, or physically wrapping the Li-containing by-products. It can be used as a concept that includes both self-response, induced reaction to other substances, and interaction with other substances.
- the coating method may vary, but preferably a dry method or a wet method may be used.
- the coating using the fluorine-containing polymer of the lithium nickel-based oxide may be made by blending the fluorine-containing polymer and the lithium nickel-based oxide, firing at high temperature to burn carbon and leaving only fluorine on the surface. have.
- Al 2 O 3 is coated with an Al-isopropoxide (Al-isopropoxide) solution in an alcohol solvent as an Al supply precursor, and then mixed with lithium nickel-based oxide and calcined in the range of 600 to 620 °C It can be made by forming a coating layer on the surface of.
- Al-isopropoxide Al-isopropoxide
- the content of the fluorine or metal element of the coating layer may be 0.001 to 3000 ppm with respect to the total weight of the lithium nickel-based oxide, in detail may be 1000 to 2000 ppm.
- the coating thickness may be, for example, 0.5 nm to 2 nm.
- the coating layer contains more than 3000 ppm of fluorine or metal element or is coated with the coating thickness or more, the amount of lithium nickel-based oxide is relatively reduced to obtain a desired capacity, and the content is too low or the coating thickness is too thin. In this case, the desired gas generation suppression effect cannot be obtained.
- the lithium nickel-based oxide may be included in 10 to 50% by weight relative to the total weight of the positive electrode active material, more specifically may be included in 20 to 40% by weight.
- the rolling density is increased compared to the case where the lithium nickel oxide is used alone. As shown.
- the present invention also provides a lithium secondary battery including the bimodal positive electrode active material.
- the lithium secondary battery may have an operating voltage range of 2.50 to 4.35V.
- the operating voltage range is 3.0V to 4.35V
- the lithium secondary battery of the present invention has an operating voltage range of 2.50V to 4.35V, so the operating voltage range is extended to obtain an effect of increasing cell capacity. Can be.
- the lithium secondary battery is composed of a positive electrode, a negative electrode, a separator and a lithium salt-containing nonaqueous electrolyte.
- the positive electrode is prepared by, for example, applying a mixture of the positive electrode active material, the conductive material, and the binder onto a positive electrode current collector, followed by drying, and optionally, a filler is further added.
- 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 material is typically added in an amount of 1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
- a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof 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 the bonding of the active material and the conductive material to the current collector, and is generally added in an amount of 1 to 30 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 manufactured by coating, drying, and pressing a negative electrode active material on a negative electrode current collector, and optionally, the conductive material, binder, filler, etc. may be further included as necessary.
- the negative electrode current collector is generally made of a thickness of 3 ⁇ 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 negative electrode active material may be, for example, carbon such as hardly graphitized carbon or graphite carbon; Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1-x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me' Metal complex oxides such as Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen, 0 ⁇ x ⁇ 1, 1 ⁇ y ⁇ 3, 1 ⁇ z ⁇ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , Metal oxides such as Bi 2 O 5 ; Conduct
- the separator is interposed between the electrode 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 0.01 to 10 ⁇ m ⁇ m, thickness is generally 5 ⁇ 30 ⁇ m.
- olefin polymers such as chemical resistance and hydrophobic polypropylene; Sheet or nonwoven fabric made of glass fiber or polyethylene; Kraft paper or the like is used.
- Typical examples currently on the market include Celgard series (Celgard R 2400, 2300 (manufactured by Hoechest Celanese Corp.), polypropylene separator (manufactured by Ube Industries Ltd. or Pall RAI), and polyethylene series (Tonen or Entek).
- a gel polymer electrolyte may be coated on the separator to increase battery safety.
- Representative examples of such gel polymers include polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, and the like.
- the solid electrolyte may also serve as a separator.
- the lithium salt-containing nonaqueous electrolyte is composed of a nonaqueous electrolyte and lithium.
- a nonaqueous organic solvent, an organic solid electrolyte, an inorganic solid electrolyte and the like are used as the nonaqueous electrolyte, but are not limited thereto.
- non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and gamma Butyl lactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxorone, formamide, dimethylformamide, dioxolon , Acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbo Aprotic organic solvents such as nate derivatives, tetrahydrofuran derivatives, ethers, methyl pyroionate and ethyl propionate can be
- organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymerizers 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.
- the lithium salt is a good material to be dissolved 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 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide.
- pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added. .
- a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (Fluoro-Ethylene) may be further included. Carbonate), PRS (Propene sultone) may be further included.
- lithium salts such as LiPF 6 , LiClO 4 , LiBF 4 , LiN (SO 2 CF 3 ) 2, and the like, may be prepared by cyclic carbonate of EC or PC as a highly dielectric solvent and DEC, DMC or EMC as a low viscosity solvent.
- Lithium salt-containing non-aqueous electrolyte can be prepared by adding to a mixed solvent of linear carbonate.
- FIG. 1 is a partial schematic view of a positive electrode active material according to one embodiment of the present invention.
- FIG. 2 is a SEM photograph of a positive electrode active material according to one embodiment of the present invention.
- LiNi 0.55 Mn 0.3 0Co 0.15 O 2 and PVdF were mixed and then heated for 9 hours in a temperature range of 150 ° C. to 600 ° C. to prepare LiNi 0.55 Mn 0.30 Co 0.15 O 2 , the surface of which was coated with F (2000 ppm). It was.
- a mixed cathode active material was prepared by mixing LiCoO 2 having a D50 of 16 to 25 ⁇ m and LiNi 0.55 Mn 0.30 Co 0.15 O 2 having a D50 of about 2 to 10 ⁇ m in a ratio of 70:30.
- a mixed cathode active material was prepared by mixing LiCoO 2, which is not a bimodal mixed cathode active material, and LiNi 0.55 Mn 0.30 Co 0.15 O 2 having an average particle diameter similar to that of LiCoO 2 .
- the bimodal type positive electrode active material has a rolling density of about 0.4 g / cc higher than that of the positive electrode active material composed of non-bimodal LiCoO 2 and a lithium nickel-based oxide having an average particle diameter similar to that of LiCoO 2. You can see that.
- Bimodal form in the same manner as in Example 1, except that LiCoO 2 doped with Mg (1000 ppm) and Ti (1000 ppm) and the entire surface was coated with Al (400 ppm)
- the bimodal positive active material was mixed with Super P as a conductive material and polyvinylidene fluoride as a binder in a weight ratio of 96: 2: 2, and then NMP (N-methyl pyrrolidone) Slurry was prepared by the addition.
- the positive electrode slurry was applied to an aluminum current collector and then dried in a vacuum oven at 120 ° C. to prepare a positive electrode.
- SiO 1-x manufactured by Shin - Etsu Co., Ltd.
- MAG-V2 Haitashi Co., Ltd.
- AGM01 Mitsubishi Co., Ltd.
- the negative electrode was prepared by mixing and dispersing the prepared negative active material as a conductive material, Super P (or DB), SBR as a binder, and CMC as a thickener in a ratio (weight ratio) of 96.55: 0.7: 1.75: 1, and coating it on a copper foil. It was.
- An electrode assembly was prepared through a separator between the prepared cathode and anode.
- the electrode assembly thus prepared is placed in an aluminum can or an aluminum pouch and the electrode leads are connected.
- a carbonate-based composite solution containing 1 M LiPF 6 is injected into the electrolyte, followed by sealing to assemble the lithium secondary battery. It was.
- Example 1 uses LiCoO 2 doped with Mg (1000 ppm) and Ti (1000 ppm) and coated the entire surface with Al (400 ppm) and LiNi 0.55 Mn 0.30 Co 0.15 O 2 without surface coating Except that, a positive electrode, a negative electrode, an electrolyte and a lithium secondary battery were prepared in the same manner as in Example 2.
- Example 1 uses LiCoO 2 doped with Mg (1000 ppm) and Ti (1000 ppm) and the entire surface is coated with Al (400 ppm) and LiNi 0.55 Mn 0.30 Co coated with F (100 ppm)
- a positive electrode, a negative electrode, an electrolyte solution, and a lithium secondary battery were prepared in the same manner as in Example 2 except that 0.15 O 2 was used.
- Example 1 uses LiCoO 2 doped with Mg (1000 ppm) and Ti (1000 ppm) and the entire surface is coated with Al (400 ppm) and LiNi 0.55 Mn 0.30 Co coated with F (3500 ppm)
- a positive electrode, a negative electrode, an electrolyte solution, and a lithium secondary battery were prepared in the same manner as in Example 2 except that 0.15 O 2 was used.
- the cathode active material according to the present invention is a bimodal form in which lithium cobalt oxide and lithium nickel oxide having different average particle diameters are mixed in a specific mixing ratio, when the oxides are used alone, or Rolling density is larger than that of a mixed positive electrode active material having a similar average particle diameter, thereby increasing the capacity of the lithium secondary battery including the positive electrode active material.
- the electron conductivity and rate of the secondary battery Not only can improve the rate and cycle characteristics, but also suppress the generation of gas during high temperature storage, thereby improving safety at high temperatures.
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
Claims (22)
- 2.50V 내지 4.35V의 작동 전압 영역을 갖는 이차전지용 양극 활물질로서, 리튬 코발트계 산화물 및 표면 처리된 리튬 니켈계 산화물을 포함하고, 상기 양극 활물질은 상기 코발트계 산화물의 평균 입경과 리튬 니켈계 복합 산화물의 평균 입경이 서로 다른 바이모달(bimodal) 형태에 의해 높은 압연 밀도를 가지는 것을 특징으로 하는 양극 활물질.
- 제 1 항에 있어서, 상기 양극 활물질의 압연 밀도는 상기 바이모달 형태가 아닌 평균 입경이 유사한 리튬 코발트 산화물과 리튬 니켈계 산화물로 구성된 양극 활물질의 압연 밀도 보다 높은 것을 특징으로 하는 양극 활물질.
- 제 2 항에 있어서, 상기 양극 활물질의 압연 밀도는 3.8 내지 4.0 g/cc 인 것을 특징으로 하는 양극 활물질.
- 제 1 항에 있어서, 상기 리튬 코발트계 산화물의 평균 입경은 16 ~ 25 ㎛이고, 상기 리튬 니켈계 산화물의 평균 입경은 2 ~ 10 ㎛인 것을 특징으로 하는 양극 활물질.
- 제 1 항에 있어서, 상기 리튬 코발트계 산화물의 평균 입경은 2 ~ 10 ㎛이고, 상기 리튬 니켈계 산화물의 평균 입경은 16 ~ 25 ㎛인 것을 특징으로 하는 양극 활물질.
- 제 1 항에 있어서, 상기 리튬 코발트계 산화물은 하기 화학식 1로 표현되는 것을 특징으로 하는 양극 활물질:Li(Co(1-a)Ma)O2 (1)상기 식에서,0.1≤a≤0.2이고,상기 M은 Mg, Ti, Zr, Al 및 Si로 이루어진 군에서 선택되는 적어도 하나의 이상의 원소이다.
- 제 6 항에 있어서, 상기 M은 Mg 및/또는 Ti인 것을 특징으로 하는 양극 활물질.
- 제 1 항에 있어서, 상기 리튬 코발트계 산화물은 표면 전체에 Al2O3이 코팅되어 있고, Al의 함유량은 리튬 코발트계 산화물 전체 중량에 대해 0.001 내지 2000 ppm인 것을 특징으로 하는 양극 활물질.
- 제 8 항에 있어서, 상기 Al의 함유량은 350 내지 500 ppm인 것을 특징으로 하는 양극 활물질.
- 제 8 항에 있어서, 상기 Al2O3의 코팅 두께는 0.5 ~ 2 ㎚인 것을 특징으로 하는 양극 활물질.
- 제 8 항에 있어서, 상기 Al2O3은 습식법에 의해 리튬 코발트계 산화물의 표면에 코팅된 것을 특징으로 하는 양극 활물질.
- 제 1 항에 있어서, 상기 리튬 니켈계 산화물은 하기 화학식 2로 표현되고 양극 활물질의 전체 중량 대비 10 내지 50 중량%로 포함되어 있는 것을 특징으로 하는 양극 활물질:Li1+xNiaMnbCo1-(a+b)O2 (2)상기 식에서,-0.2≤x≤0.2, 0.5≤a≤0.6, 0.2≤b≤0.3이다.
- 제 12 항에 있어서, 상기 리튬 니켈계 산화물은 양극 활물질의 전체 중량 대비 20 내지 40 중량%로 포함되어 있는 것을 특징으로 하는 양극 활물질.
- 제 1 항에 있어서, 상기 리튬 니켈계 산화물은 불소 함유 폴리머와 반응하여 리튬 니켈계 산화물 표면 전체에 코팅층을 형성하고, 상기 코팅층의 불소 함유량은 리튬 니켈계 산화물 전체 중량에 대해 0.001 내지 3000 ppm인 것을 특징으로 하는 양극 활물질.
- 제 14 항에 있어서, 상기 불소 함유 폴리머는 PVdF 또는 PVdF-HFP인 것을 특징으로 하는 양극 활물질.
- 제 15 항에 있어서, 상기 불소 함유 폴리머는 PVdF인 것을 특징으로 하는 양극 활물질.
- 제 1 항에 있어서, 상기 리튬 니켈계 산화물은 표면 전체에 금속 산화물이 코팅되어 있고, 상기 금속의 함유량은 리튬 니켈계 산화물 전체 중량에 대해 0.001 내지 3000 ppm인 것을 특징으로 하는 양극 활물질.
- 제 17 항에 있어서, 상기 금속 산화물은 Al2O3인 것을 특징으로 하는 양극 활물질.
- 제 14 항 또는 제 17 항에 있어서, 상기 불소 또는 금속의 함유량은 리튬 니켈계 산화물 전체 중량에 대해 1000 내지 2000 ppm인 것을 특징으로 하는 양극 활물질.
- 제 14 항 또는 제 17 항에 있어서, 상기 코팅은 0.5 ~ 2 ㎚ 범위의 두께로 코팅 된 것을 특징으로 하는 양극 활물질.
- 제 14 항 또는 제 17 항에 있어서, 상기 코팅은 습식법 또는 건식법에 의해 이루어진 것을 특징으로 하는 양극 활물질.
- 제 1 항에 따른 상기 양극 활물질을 포함하는 것으로 구성되고, 작동 전압 영역이 2.50V ~ 4.35V인 것을 특징으로 하는 리튬 이차전지.
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EP13825083.2A EP2882014A4 (en) | 2012-08-03 | 2013-07-31 | ANODEACTIVE MATERIAL FOR A SECONDARY BATTERY AND LITHIUM SUBSTITUTING BATTERY THEREWITH |
CN201380037640.3A CN104471759B (zh) | 2012-08-03 | 2013-07-31 | 二次电池用正极活性材料和包含其的锂二次电池 |
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KR20240092338A (ko) * | 2022-12-14 | 2024-06-24 | 삼성에스디아이 주식회사 | 복합양극활물질, 이를 채용한 양극과 리튬전지 및 이의 제조방법 |
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- 2013-07-31 US US14/409,532 patent/US9825283B2/en active Active
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Also Published As
Publication number | Publication date |
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KR101540673B1 (ko) | 2015-07-30 |
US20150162598A1 (en) | 2015-06-11 |
US9825283B2 (en) | 2017-11-21 |
EP2882014A1 (en) | 2015-06-10 |
CN104471759A (zh) | 2015-03-25 |
KR20140018685A (ko) | 2014-02-13 |
EP2882014A4 (en) | 2016-04-06 |
CN104471759B (zh) | 2018-01-12 |
JP2015528181A (ja) | 2015-09-24 |
JP6099741B2 (ja) | 2017-03-22 |
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