WO2023018277A1 - 양극 활물질의 제조방법 및 양극 활물질 - Google Patents
양극 활물질의 제조방법 및 양극 활물질 Download PDFInfo
- Publication number
- WO2023018277A1 WO2023018277A1 PCT/KR2022/012082 KR2022012082W WO2023018277A1 WO 2023018277 A1 WO2023018277 A1 WO 2023018277A1 KR 2022012082 W KR2022012082 W KR 2022012082W WO 2023018277 A1 WO2023018277 A1 WO 2023018277A1
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- WIPO (PCT)
- Prior art keywords
- active material
- transition metal
- metal oxide
- positive electrode
- phosphorus
- Prior art date
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Classifications
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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
-
- 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
- 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
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 method for manufacturing a cathode active material for a lithium secondary battery and a cathode active material.
- the nickel-based cathode active material is prepared by mixing a nickel-based cathode active material precursor and a lithium-containing raw material and then firing it. In this process, unreacted lithium-containing raw material and by-products, such as LiOH and Li 2 CO 3 A problem of remaining on the surface of the active material occurs. In particular, in the case of a nickel-based cathode active material containing a high amount of nickel, there is a problem in that a large amount of residual lithium is present.
- the present invention is to solve the above problems, and when manufacturing a cathode active material, by forming a coating layer containing phosphorus on the surface of the cathode active material in a water washing process, the residual lithium can be effectively controlled to improve the thermal stability of the cathode active material,
- it is intended to provide a method for manufacturing a positive electrode active material capable of minimizing degradation of battery performance.
- the present invention provides a method for manufacturing a positive electrode active material and a positive electrode active material.
- the present invention (A) preparing a lithium transition metal oxide; and (B) mixing the lithium transition metal oxide and the washing solution, washing with water, and then drying the washing solution, wherein the washing solution contains a phosphorus-based compound and is a basic solution, and the phosphorus-based compound is added to the washing solution. It provides a method for producing a positive electrode active material that is included so that the phosphorus content is 100 ppm to 1,000 ppm by weight relative to the lithium transition metal oxide.
- the present invention provides a method for producing a cathode active material according to (1), wherein the phosphorus-based compound includes phosphate (PO 4 3- ).
- the phosphorus-based compound is (NH 4 ) 2 HPO 4 , Li 3 PO 4 and Na 3 PO 4
- the present invention provides a method for producing a cathode active material according to any one of (1) to (4) above, wherein the washing solution has a pH of 7.00 to 9.00.
- the present invention provides a method for producing a cathode active material according to any one of (1) to (5) above, wherein the solvent of the washing solution is at least one selected from deionized water, distilled water and ethanol.
- the present invention provides a method for producing a cathode active material according to any one of (1) to (6) above, wherein the lithium transition metal oxide is represented by Formula 1 below.
- M 1 is at least one selected from Mn and Al;
- M 2 is one or more selected from among Zr, B, W, Mo, Cr, Nb, Mg, Hf, Ta, La, Ti, Sr, Ba, Ce, F, P, S, and Y.
- the present invention is a lithium transition metal oxide; and a coating layer containing phosphorus (P) formed on the lithium transition metal oxide, wherein the phosphorus is included in a weight of 100 ppm to 1,000 ppm relative to the lithium transition metal oxide.
- the present invention provides the cathode active material according to (9) above, wherein the cathode active material has a calorific value of 1400 J/g or less as measured by differential scanning calorimetry (DSC).
- the positive electrode active material prepared by the method according to the present invention may have excellent thermal stability, and a battery using the positive electrode active material may have excellent performance.
- the term "on” means not only the case where a certain component is formed directly on top of another component, but also includes the case where a third component is interposed between these components.
- the inventors of the present invention in the case of using a washing solution that contains a specific amount of a phosphorus-based compound and is a basic solution in the washing process during the manufacturing process of the positive electrode active material, can minimize surface deterioration of the positive electrode active material generated in the washing process and effectively remove residual lithium. It was found that it could be removed and the present invention was completed.
- a method for producing a cathode active material according to the present invention includes (A) preparing a lithium transition metal oxide; and (B) mixing the lithium transition metal oxide and the washing solution, washing with water, and then drying the washing solution, wherein the washing solution contains a phosphorus-based compound and is a basic solution, and the phosphorus-based compound is added to the washing solution. It is included so that the phosphorus content is 100 ppm to 1,000 ppm by weight relative to the lithium transition metal oxide.
- the manufacturing method of the cathode active material according to the present invention includes (C) mixing a raw material containing a coating element with the lithium transition metal oxide (dried lithium transition metal oxide) that has undergone step (B) and heat-treating to form a coating layer; can include more.
- the method for preparing a cathode active material according to the present invention includes preparing a lithium transition metal oxide.
- the preparing of the lithium transition metal oxide may include preparing a lithium transition metal oxide by mixing and calcining a cathode active material precursor with a lithium-containing raw material.
- the cathode active material precursor may be, for example, represented by Chemical Formula A or Chemical Formula B below.
- M 1 is at least one selected from Mn and Al
- M 2 is Zr, B, W, Mo, Cr, Nb, Mg, Hf, Ta, La, Ti, Sr, Ba , Ce, F, P, S, and Y may be one or more selected from.
- the x means the atomic fraction of nickel among the metal elements in the precursor, and may be 0.6 ⁇ x ⁇ 1, 0.6 ⁇ x ⁇ 0.98, or 0.7 ⁇ x ⁇ 0.95.
- the y denotes the atomic fraction of cobalt among the metal elements in the precursor, and may be 0 ⁇ y ⁇ 0.4, 0.01 ⁇ y ⁇ 0.4, or 0.01 ⁇ y ⁇ 0.3.
- the z means the element fraction of the M 1 element among the metal elements in the precursor, and may be 0 ⁇ z ⁇ 0.4, 0.01 ⁇ z ⁇ 0.4, or 0.01 ⁇ z ⁇ 0.3.
- the w represents the elemental fraction of the M 2 element among the metal elements in the precursor, and may be 0 ⁇ w ⁇ 0.2, 0 ⁇ w ⁇ 0.1, 0 ⁇ w ⁇ 0.05, or 0 ⁇ w ⁇ 0.02.
- the lithium-containing raw material may be, for example, at least one selected from the group consisting of lithium carbonate (Li 2 CO 3 ), lithium hydroxide (LiOH), LiNO 3 , CH 3 COOLi and Li 2 (COO) 2 , , Specifically, it may be lithium carbonate (Li 2 CO 3 ), lithium hydroxide (LiOH), or a combination thereof.
- the cathode active material precursor and the lithium-containing raw material may be mixed in a molar ratio of 1:1 to 1:1.625 or 1:1 to 1:1.15.
- the lithium-containing raw material is mixed below the above range, there is a concern that the capacity of the cathode active material to be produced may decrease, and when the lithium-containing raw material is mixed beyond the above range, unreacted Li remains as a by-product, and the capacity After deterioration and firing, separation of cathode active material particles (causation of cathode active material coalescence) may occur.
- the firing may be performed at a temperature of 700 °C to 1000 °C.
- the sintering temperature is less than 700° C., raw materials remain in the particles due to insufficient reaction, and thus the high-temperature stability of the battery may be deteriorated, and the bulk density and crystallinity of the battery may be deteriorated, resulting in deterioration in structural stability.
- the firing temperature exceeds 1000 ° C., non-uniform growth of particles may occur, and it is difficult to disintegrate the particles, which may cause a decrease in capacity.
- the sintering temperature may be more specifically 700° C. to 980° C.
- the firing may be performed for 5 hours to 35 hours.
- the firing time is less than 5 hours, the reaction time is too short, and it may be difficult to obtain a highly crystalline cathode active material, and when the firing time exceeds 35 hours, the particle size may be excessively increased and production efficiency may be lowered.
- the lithium transition metal oxide may be represented by Formula 1 below.
- M 1 is at least one selected from Mn and Al;
- M 2 is one or more selected from among Zr, B, W, Mo, Cr, Nb, Mg, Hf, Ta, La, Ti, Sr, Ba, Ce, F, P, S, and Y.
- the x1 means the atomic fraction of nickel among metal elements other than lithium in the lithium transition metal oxide, and may be 0.6 ⁇ x1 ⁇ 1, 0.6 ⁇ x1 ⁇ 0.98, or 0.7 ⁇ x1 ⁇ 0.95.
- the y1 denotes an atomic fraction of cobalt among metal elements other than lithium in the lithium transition metal oxide, and may be 0 ⁇ y1 ⁇ 0.4, 0.01 ⁇ y1 ⁇ 0.4, or 0.01 ⁇ y1 ⁇ 0.3.
- the z1 denotes an elemental fraction of element M 1 among metal elements other than lithium in the lithium transition metal oxide, and may be 0 ⁇ z1 ⁇ 0.4, 0.01 ⁇ z1 ⁇ 0.4, or 0.01 ⁇ z1 ⁇ 0.3.
- the w1 means the elemental fraction of the M 2 element among metal elements other than lithium in the lithium transition metal oxide, and may be 0 ⁇ w1 ⁇ 0.2, 0 ⁇ w1 ⁇ 0.1, 0 ⁇ w1 ⁇ 0.05 or 0 ⁇ w1 ⁇ 0.02. there is.
- the method for manufacturing a positive electrode active material according to the present invention includes mixing the lithium transition metal oxide and a washing solution, washing with water, and then drying.
- the present invention includes a phosphorus-based compound in a specific amount and uses a washing solution, which is a basic solution, in the washing process, thereby minimizing surface degradation of the positive electrode active material generated in the washing process and effectively controlling residual lithium. Accordingly, the cathode active material prepared by the method according to the present invention may have excellent thermal stability, and a battery using the cathode active material may have excellent performance.
- the cathode active material prepared by the method according to the present invention may include lithium transition metal oxide; and a coating layer containing phosphorus (P) formed on the lithium transition metal oxide, wherein the phosphorus may be included in a weight of 100 ppm to 1,000 ppm relative to the lithium transition metal oxide.
- the positive electrode active material generated in the washing process can be minimized and residual lithium can be effectively controlled, thereby providing a positive electrode active material with excellent performance.
- the phosphorus compound may include phosphate (PO 4 3- ).
- a coating layer containing phosphorus (P) may be formed on the surface of the lithium transition metal oxide in the washing process.
- the phosphorus-based compound may be at least one selected from (NH 4 ) 2 HPO 4 , Li 3 PO 4 and Na 3 PO 4 in terms of improving the solubility of the washing solution in the solvent.
- the phosphorus-based compound may be (NH 4 ) 2 HPO 4 in terms of improving the removal of residual lithium present on the surface of the lithium transition metal oxide.
- the phosphorus-based compound has a phosphorus content of 100 ppm to 1,000 ppm by weight, specifically, 200 ppm, 250 ppm or more, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, or 1000 ppm or less with respect to the lithium transition metal oxide in the washing solution. It may be included so that the weight of In this case, residual lithium can be effectively controlled, and a coating layer containing phosphorus (P) is formed on the surface of the metal oxide to improve thermal stability.
- P phosphorus
- the thermal stability of the positive electrode active material is improved because a coating layer containing phosphorus is not formed on the lithium transition metal oxide. If the weight is more than 1,000ppm, the coating layer containing phosphorus is formed too thick, and the intercalation / desorption of lithium ions from the surface of the cathode active material is not smooth, resulting in a decrease in performance such as battery efficiency.
- the washing solution may have a pH of 7.00 to 9.00, specifically 7.50, 7.80, 7.85 or more, 8.00, 8.10, 8.50, or 9.00 or less.
- pH is the pH when the temperature is 25°C.
- the pH of the washing solution is within the above range, residual lithium can be easily removed.
- surface deterioration due to a concentration difference between the washing solution and the positive electrode material can be minimized.
- the solvent of the washing solution may be at least one selected from deionized water, distilled water and ethanol.
- the solvent of the washing solution may specifically be deionized water.
- the water washing process may be performed for 5 to 30 minutes.
- the time for performing the washing process is within the above range, residual lithium by-products present on the surface of the lithium transition metal oxide can be easily removed. Accordingly, gelation may not occur when preparing the positive electrode slurry, and gas may not be generated when applied to a battery.
- lithium present in the oxide does not come out, so battery performance may not deteriorate.
- the drying process is a process for removing moisture from the positive electrode active material containing moisture through a water washing process, and may be to remove moisture using a vacuum pump and then dry at 100° C. to 150° C. for 12 hours or more.
- the method for manufacturing a positive electrode active material according to the present invention may further include forming a coating layer by mixing a raw material containing a coating element with the lithium transition metal oxide that has undergone step (B) and heat-treating. Accordingly, a cathode active material having a coating layer formed on the surface of the lithium transition metal oxide can be manufactured.
- Metal elements included in the coating element-containing raw material may be Zr, B, W, Mo, Cr, Nb, Mg, Hf, Ta, La, Ti, Sr, Ba, Ce, F, P, S, and Y. .
- the raw material containing the coating element may be an acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide or oxyhydroxide containing the metal element.
- boric acid H 3 BO 3
- the raw material containing the coating element may be included in a weight of 200 ppm to 2,000 ppm based on the dried lithium transition metal oxide.
- the content of the raw material containing the coating element is within the above range, the capacity of the battery can be improved, and the long-term performance characteristics of the battery can be improved by suppressing the direct reaction between the electrolyte and lithium transition metal oxide.
- the heat treatment may be performed at a temperature of 200 °C to 400 °C.
- the coating layer may be formed while maintaining structural stability of the transition metal oxide.
- the heat treatment may be performed for 1 hour to 10 hours.
- the heat treatment time is within the above range, an appropriate coating layer can be formed and production efficiency can be improved.
- the cathode active material according to the present invention is a lithium transition metal oxide; and a coating layer containing phosphorus (P) formed on the lithium transition metal oxide, wherein the phosphorus is included in a weight of 100 ppm to 1,000 ppm relative to the lithium transition metal oxide.
- the positive electrode active material according to the present invention is prepared according to the above-described positive electrode active material manufacturing method, includes a coating layer containing a specific amount of phosphorus (P), and may have better thermal stability. Accordingly, the electrochemical performance of the secondary battery including the cathode active material according to the present invention may be excellent.
- the lithium transition metal oxide may be represented by Formula 1 below.
- M 1 is at least one selected from Mn and Al;
- M 2 is at least one selected from among Zr, B, W, Mo, Cr, Nb, Mg, Hf, Ta, La, Ti, Sr, Ba, Ce, F, P, S, and Y.
- the x1 means the atomic fraction of nickel among metal elements other than lithium in the lithium transition metal oxide, and may be 0.6 ⁇ x1 ⁇ 1, 0.6 ⁇ x1 ⁇ 0.98, or 0.7 ⁇ x1 ⁇ 0.95.
- the y1 denotes an atomic fraction of cobalt among metal elements other than lithium in the lithium transition metal oxide, and may be 0 ⁇ y1 ⁇ 0.4, 0.01 ⁇ y1 ⁇ 0.4, or 0.01 ⁇ y1 ⁇ 0.3.
- the z1 denotes an elemental fraction of element M 1 among metal elements other than lithium in the lithium transition metal oxide, and may be 0 ⁇ z1 ⁇ 0.4, 0.01 ⁇ z1 ⁇ 0.4, or 0.01 ⁇ z1 ⁇ 0.3.
- the w1 means the elemental fraction of the M 2 element among metal elements other than lithium in the lithium transition metal oxide, and may be 0 ⁇ w1 ⁇ 0.2, 0 ⁇ w1 ⁇ 0.1, 0 ⁇ w1 ⁇ 0.05 or 0 ⁇ w1 ⁇ 0.02. there is.
- the phosphorus in terms of capacity improvement and initial resistance improvement of the secondary battery, is 100 ppm to 1,000 ppm by weight, specifically, 150 ppm, 170 ppm or more, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm relative to the lithium transition metal oxide , It may be included in a weight of 970 ppm or less. In this case, the weight of phosphorus relative to the lithium transition metal oxide may be a value obtained through ICP analysis.
- the thermal stability of the positive electrode active material is not improved, and when the phosphorus is included in a weight of more than 1,000 ppm, the coating layer is formed too thick to form a positive electrode.
- performance such as efficiency of the battery is deteriorated because lithium ions are not smoothly intercalated/deintercalated from the surface of the active material.
- the positive electrode active material has more improved thermal stability, so that the calorific value measured by differential scanning calorimetry (DSC) is 1400 J/g or less, specifically 1200 J/g, 1250 J/g or more, It may be 1350 J/g or less than 1380 J/g.
- DSC differential scanning calorimetry
- the phosphorus may be specifically included in a weight of 200ppm to 900ppm, more specifically, 200ppm to 500ppm compared to the lithium transition metal oxide.
- the positive electrode active material according to the present invention may have a calorific value of 1350 J/g or less as measured by differential scanning calorimetry (DSC). That is, when the amount of phosphorus is within the above range, not only the thermal stability of the cathode active material itself can be further improved, but also the characteristics of the secondary battery including the cathode active material can be further improved.
- the present invention provides a cathode for a lithium secondary battery including the cathode active material.
- the cathode for a secondary battery includes a cathode current collector and a cathode active material layer formed on the cathode current collector, and the cathode active material layer includes the cathode active material according to the present invention.
- the positive current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery, and for example, stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon, nickel, titanium on the surface of aluminum or stainless steel. , those surface-treated with silver, etc. may be used.
- the cathode current collector may have a thickness of typically 3 ⁇ m to 500 ⁇ m, and adhesion of the cathode active material may be increased by forming fine irregularities on the surface of the current collector.
- it may be used in various forms such as films, sheets, foils, nets, porous materials, foams, and non-woven fabrics.
- the positive electrode active material layer may include a conductive material and a binder together with the positive electrode active material.
- the positive electrode 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 positive electrode active material layer.
- excellent capacity characteristics may be exhibited.
- the conductive material is used to impart conductivity to the electrode, and in the battery configured, any material that does not cause chemical change and has electronic conductivity can be used without particular limitation.
- any material that does not cause chemical change and has electronic conductivity can be used without particular limitation.
- Specific examples include graphite such as natural graphite or artificial graphite; carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black, and carbon fiber; metal powders 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, and one of them alone or a mixture of two or more may be used.
- the conductive material may be included in an amount of 1 wt% to 30 wt% based on the total weight of the cathode active material layer.
- the binder serves to improve adhesion between particles of the positive electrode active material and adhesion between the positive electrode active material and the current collector.
- Specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethylcellulose (CMC) ), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, or various copolymers thereof, and the like may be used alone or in a mixture of two or more of them.
- the binder may be included in an amount of 1 wt% to 30 wt% based on the total weight of the catho
- the positive electrode may be manufactured according to a conventional positive electrode manufacturing method except for using the positive electrode active material.
- the composition for forming a cathode active material layer prepared by dissolving or dispersing the above-described cathode active material and, optionally, a binder and a conductive material in a solvent may be coated on a cathode current collector, followed by drying and rolling.
- the types and contents of the positive electrode active material, the binder, and the conductive material are as described above.
- the solvent may be a solvent commonly used in the art, and dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, or water and the like, and one type alone or a mixture of two or more types of these may be used.
- the amount of the solvent used is enough to dissolve or disperse the positive electrode active material, conductive material, and binder in consideration of the coating thickness and manufacturing yield of the slurry, and to have a viscosity capable of exhibiting excellent thickness uniformity during subsequent coating for producing a positive electrode. do.
- the positive electrode may be manufactured by casting the composition for forming the positive electrode active material layer on a separate support and then laminating a film obtained by peeling from the support on a positive electrode current collector.
- the present invention can manufacture an electrochemical device including the anode.
- the electrochemical device may be specifically a battery, a capacitor, and the like, and more specifically, may be a lithium secondary battery.
- the lithium secondary battery specifically includes a positive electrode, a negative electrode positioned opposite to the positive electrode, and a separator and an electrolyte interposed between the positive electrode and the negative electrode, and the positive electrode is the same as described above, so a detailed description is omitted, Hereinafter, only the remaining configurations will be described in detail.
- the lithium secondary battery may optionally 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 the negative electrode current collector.
- the anode current collector is not particularly limited as long as it does not cause chemical change in the battery and has high conductivity.
- it is formed on the surface of copper, stainless steel, aluminum, nickel, titanium, fired carbon, copper or stainless steel.
- a surface treated with carbon, nickel, titanium, silver, or the like, an aluminum-cadmium alloy, or the like may be used.
- the negative electrode current collector may have a thickness of typically 3 ⁇ m to 500 ⁇ m, and like the positive electrode current collector, fine irregularities may be formed on the surface of the current collector to enhance bonding strength of the negative electrode active material.
- it may be used in various forms such as films, sheets, foils, nets, porous materials, foams, and non-woven fabrics.
- the anode active material layer optionally includes a binder and a conductive material together with the anode active material.
- a compound capable of reversible intercalation and deintercalation of lithium may be used as the anode active material.
- Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber, and amorphous carbon; metallic compounds capable of being alloyed with lithium, such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys, or Al alloys; metal oxides capable of doping and undoping lithium, such as SiO ⁇ (0 ⁇ 2), SnO 2 , vanadium oxide, and lithium vanadium oxide; or a composite including the metallic compound and a carbonaceous material, such as a Si-C composite or a Sn-C composite, and any one or a mixture of two or more of these may be used.
- a metal lithium thin film may be used as the anode active material.
- both low crystalline carbon and high crystalline carbon may be used. Soft carbon and hard carbon are typical examples of low crystalline carbon.
- High crystalline carbon includes amorphous, plate-like, scaly, spherical or fibrous natural graphite, artificial graphite, or kish graphite. 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 representative.
- the negative electrode active material may be included in an amount of 80% to 99% by weight based on the total weight of the negative electrode active material layer.
- the binder is a component that assists in bonding between the conductive material, the active material, and the current collector, and may be typically added in an amount of 0.1% to 10% by weight based on the total weight of the negative electrode active material layer.
- binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluorocarbons, roethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, nitrile-butadiene rubber, fluororubber, various copolymers thereof, and the like.
- PVDF polyvinylidene fluoride
- CMC carboxymethylcellulose
- EPDM ethylene-propylene-diene polymer
- sulfonated-EPDM s
- the conductive material is a component for further improving the conductivity of the negative electrode active material, and may be added in an amount of 10% by weight or less, specifically 5% by weight or less, based on the total weight of the negative electrode active material layer.
- the 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 or artificial graphite; carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fibers and metal fibers; metal powders such as carbon fluoride, aluminum, and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives may be used.
- the negative electrode active material layer is prepared by coating a negative electrode composite prepared by dissolving or dispersing a negative electrode active material, and optionally a binder and a conductive material in a solvent on a negative electrode current collector and drying the negative electrode composite, or by drying the negative electrode composite. It can be produced by casting on a support and then laminating a film obtained by peeling from the support on a negative electrode current collector.
- the negative electrode active material layer is formed by applying a negative electrode active material, and optionally a negative electrode composite prepared by dissolving or dispersing a binder and a conductive material in a solvent on a negative electrode current collector and drying the negative electrode composite, or casting the negative electrode composite on a separate support. Then, the film obtained by peeling from the support may be laminated on the negative electrode current collector.
- the separator separates the negative electrode and the positive electrode and provides a passage for lithium ion movement.
- Anything that is normally used as a separator in a lithium secondary battery can be used without particular limitation, especially for the movement of ions in the electrolyte. It is preferable to have low resistance to the electrolyte and excellent ability to absorb the electrolyte.
- a porous polymer film for example, a porous polymer film made of polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, or these
- a laminated structure of two or more layers of may be used.
- conventional porous non-woven fabrics for example, non-woven fabrics made of high-melting 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 selectively used in a single-layer or multi-layer structure.
- the electrolyte used in the present invention includes organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel-type polymer electrolytes, solid inorganic electrolytes, and molten inorganic electrolytes that can be used in the manufacture of lithium secondary batteries, and are limited to these. it is not going to be
- 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 includes ester solvents such as methyl acetate, ethyl acetate, ⁇ -butyrolactone, and ⁇ -caprolactone; ether solvents such as dibutyl ether or tetrahydrofuran; ketone solvents such as cyclohexanone; aromatic hydrocarbon-based solvents such as benzene and fluorobenzene; carbonate-based solvents such as dimethylcarbonate (DMC), diethylcarbonate (DEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), and propylene carbonate (PC); alcohol solvents such as ethyl alcohol and isopropyl alcohol; nitriles such as R-CN (R is a straight-chain, branched or cyclic hydrocarbon group having 2 to 20 carbon atoms and may contain a double
- carbonate-based solvents are preferred, and cyclic carbonates (eg, ethylene carbonate or propylene carbonate, etc.) having high ion conductivity and high dielectric constant capable of increasing the charge and discharge performance of batteries, and low-viscosity linear carbonate-based compounds (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate) is more preferable.
- cyclic carbonate and the chain carbonate are mixed in a volume ratio of about 1:1 to about 1:9, 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 , LiAlO 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 or the like may 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 within the above range, the electrolyte has appropriate conductivity and viscosity, so excellent electrolyte performance can be exhibited, and lithium ions can move effectively.
- the electrolyte may include, for example, haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and triglycerides for the purpose of improving battery life characteristics, suppressing battery capacity decrease, and improving battery discharge capacity.
- haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, and triglycerides
- Ethylphosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphoric acid triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N,N-substituted imida
- One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be further included. In this case, the additive may be included in an amount of 0.1% to 5% by weight based on the total weight of the electrolyte.
- the lithium secondary battery including the cathode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and lifespan characteristics, portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles ( It is useful for electric vehicles such as hybrid electric vehicles (HEVs).
- HEVs hybrid electric vehicles
- a battery module including the lithium secondary battery as a unit cell and a battery pack including the same are provided.
- the battery module or battery pack may include a power tool; electric vehicles, including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Alternatively, it may be used as a power source for one or more medium or large-sized devices among power storage systems.
- electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs);
- PHEVs plug-in hybrid electric vehicles
- the appearance of the lithium secondary battery of the present invention is not particularly limited, but may be a cylindrical shape using a can, a prismatic shape, a pouch shape, or a coin shape.
- the lithium secondary battery according to the present invention can be used not only as a battery cell used as a power source for a small device, but also can be preferably used as a unit cell in a medium-large battery module including a plurality of battery cells.
- NiSO 4 , CoSO 4 and MnSO 4 were mixed in water in an amount such that the molar ratio of nickel:cobalt:manganese was 88:5:7 to prepare a transition metal-containing solution with a concentration of 2.4M.
- a continuous filtration tank reactor (CFTR) equipped with a container containing the transition metal-containing solution and a 350L filtration device (filter) in which a 25wt% NaOH aqueous solution and a 9wt% aqueous NH 4 OH solution are set at 50 ° C. connected to each.
- transition metal-containing solution NaOH aqueous solution, and NH 4 OH aqueous solution were introduced into the reactor to induce formation of nickel cobalt manganese hydroxide particles and particle aggregation, thereby forming a precursor core.
- the transition metal-containing solution was added at a rate of 57.4 mol/hr
- the NH 4 OH aqueous solution was added at a rate of 17 mol/hr
- the NaOH aqueous solution was added at a rate to maintain the pH of the reaction solution at 10.5 to 11.2.
- the reaction proceeded while adjusting the amount of NaOH aqueous solution so that the pH of the reaction solution was 11.3 to 11.5, and nickel cobalt manganese hydrate particles were grown.
- the total reaction time of the precursor core formation time and the particle growth time was 40 hours.
- the grown nickel cobalt manganese hydroxide particles were further reacted for 8 hours to stabilize them.
- the reaction was carried out while continuously discharging the filtrate through a filtering device in the reactor when the reactor became full.
- the precursor and LiOH were mixed at a molar ratio of 1:1.08 and then calcined at 780° C. for 10 hours under an oxygen atmosphere to prepare a Li[Ni 0.88 Co 0.05 Mn 0.07 ]O 2 lithium transition metal oxide.
- a washing solution was prepared by mixing deionized water with (NH 4 ) 2 HPO 4 . At this time, (NH 4 ) 2 HPO 4 was added to the washing solution so that the phosphorus weight was 250 ppm relative to the lithium transition metal oxide, and the washing solution had a pH of 7.87 at 25°C.
- the lithium transition metal oxide and the washing solution were mixed at a weight ratio of 1:1, washed with water for 5 minutes, filtered using a vacuum pump for 2 minutes, and dried in a vacuum oven at 130° C. for 12 hours or longer.
- the dried lithium transition metal oxide was mixed with H 3 BO 3 powder (weight of 1,000 ppm based on the dried lithium transition metal oxide) and heat-treated at 300° C. for 5 hours to form a coating layer containing phosphorus on the lithium transition metal oxide.
- the formed positive electrode active material was prepared.
- a positive electrode active material was prepared in the same manner as in Example 1, except that deionized water was used as a washing solution.
- positive electrode slurries were prepared by mixing each of the positive electrode active materials prepared in Examples 1 to 3 and Comparative Examples 1 to 4, a carbon black conductive material, and a PVdF binder in a weight ratio of 97.5:1.0:1.5 in an NMP solvent.
- the positive electrode slurry was applied to one surface of an aluminum current collector, dried at 130° C., and then rolled to prepare a positive electrode. Meanwhile, a Li metal disk was used as an anode active material.
- An electrode assembly was prepared by interposing a separator between the positive electrode and the Li metal disk negative electrode prepared above, and then placed inside a battery case, and then an electrolyte was injected into the case to prepare a lithium secondary battery half cell. At this time, as the electrolyte, an electrolyte solution in which 1M LiPF 6 was dissolved in an organic solvent of EC/EMC/DEC (3/3/4, vol%) was used.
- the positive electrode active materials prepared in Examples 1 to 3 it was prepared using a water washing solution containing a specific amount of a phosphorus compound, particularly (NH 4 ) 2 HPO 4 , and it was confirmed that the thermal stability was superior to that of Comparative Examples 1 to 4. there is.
- Lithium secondary battery half cells were prepared using the cathode active materials prepared in Examples 1 and 2 and Comparative Examples 1 to 4, and the charge/discharge capacity, initial efficiency, and initial resistance of each lithium secondary battery half cell were evaluated.
- the lithium secondary battery half-cell was charged in CC-CV mode at 25 ° C until it reached 4.3V at 0.1C, and 3.0 at 0.1C.
- charging and discharging are performed by discharging up to V.
- the charge/discharge capacity, initial efficiency, and initial resistance values were obtained, and are shown in Table 3 below.
- the discharge capacity of the lithium secondary battery was measured by repeating the charge and discharge cycles 30 times with a constant current of 0.33C in the range of 45 °C and 3.0 ⁇ 4.3V, and in particular, the ratio of the 30th cycle discharge capacity to the 1st cycle discharge capacity As a capacity retention rate, it is shown in Table 3 below.
- the voltage drop for 60 seconds after the start of discharge in each cycle was measured and divided by the applied current value to confirm the resistance value at high temperature.
- the ratio of the 30th cycle resistance value to the 1st cycle resistance value As the resistance increase rate it is shown in Table 3 below.
- Example 1 227.7 204.7 89.9 14.4 97.7 119.0
- Example 2 227.4 204.4 89.9 14.5 97.6 119.1
- Example 3 226.7 203.5 89.7 14.8 97.5 118.9
- Comparative Example 1 227.9 203.7 89.4 15.6 97.9 129.0
- Comparative Example 2 226.9 204.2 90.0 14.8 97.4 129.9 Comparative Example 3 227.6 203.6 89.5 15.3 97.8 126.0
- Comparative Example 4 226.7 202.3 89.2 15.4 97.4 125.2
- the initial efficiency and capacity retention at high temperature are equivalent to those of the lithium secondary battery including the positive electrode active material of Comparative Examples 1 to 4, and the initial resistance is improved. , it can be confirmed that the long-term performance of the battery is excellent from the remarkably low increase in resistance at high temperature.
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Abstract
Description
리튬 전이금속 산화물에 대한 인의 중량 (ppm) | 비고 | |
실시예 1 | 171 | (NH4)2HPO4를 수세 용액에 리튬 전이금속 산화물에 대하여 인의 함량이 250ppm이 되도록 첨가 |
실시예 2 | 465 | (NH4)2HPO4를 수세 용액에 리튬 전이금속 산화물에 대하여 인의 함량이 500ppm이 되도록 첨가 |
실시예 3 | 961 | (NH4)2HPO4를 수세 용액에 리튬 전이금속 산화물에 대하여 인의 함량이 1,000ppm이 되도록 첨가 |
비교예 2 | 90 | H3PO4를 수세 용액에 리튬 전이금속 산화물에 대하여 인의 함량이 250ppm이 되도록 첨가 |
비교예 3 | 31 | (NH4)2HPO4를 수세 용액에 리튬 전이금속 산화물에 대하여 인의 함량이 50ppm이 되도록 첨가 |
비교예 4 | 1065 | (NH4)2HPO4를 수세 용액에 리튬 전이금속 산화물에 대하여 인의 함량이 1,100ppm이 되도록 첨가 |
발열량 (J/g) | |
실시예 1 | 1282 |
실시예 2 | 1315 |
실시예 3 | 1378 |
비교예 1 | 1474 |
비교예 2 | 1455 |
비교예 3 | 1434 |
비교예 4 | 1393 |
충전 용량 (mAh/g) |
방전 용량 (mAh/g) |
초기 효율 (%) |
초기 저항 (Ω, DCIR) |
용량 유지율 (%, 30사이클) |
저항 증가율 (%, 30사이클) |
|
실시예 1 | 227.7 | 204.7 | 89.9 | 14.4 | 97.7 | 119.0 |
실시예 2 | 227.4 | 204.4 | 89.9 | 14.5 | 97.6 | 119.1 |
실시예 3 | 226.7 | 203.5 | 89.7 | 14.8 | 97.5 | 118.9 |
비교예 1 | 227.9 | 203.7 | 89.4 | 15.6 | 97.9 | 129.0 |
비교예 2 | 226.9 | 204.2 | 90.0 | 14.8 | 97.4 | 129.9 |
비교예 3 | 227.6 | 203.6 | 89.5 | 15.3 | 97.8 | 126.0 |
비교예 4 | 226.7 | 202.3 | 89.2 | 15.4 | 97.4 | 125.2 |
Claims (10)
- (A) 리튬 전이금속 산화물을 준비하는 단계; 및(B) 상기 리튬 전이금속 산화물 및 수세 용액을 혼합하여 수세한 후, 건조하는 단계;를 포함하고,상기 수세 용액은 인계 화합물을 포함하며, 염기성 용액이고,상기 인계 화합물은 상기 수세 용액에 상기 리튬 전이금속 산화물에 대하여 인의 함량이 100ppm 내지 1,000ppm의 중량이 되도록 포함되는 것인 양극 활물질의 제조방법.
- 청구항 1에 있어서,상기 인계 화합물은 인산염(phosphate, PO4 3-)을 포함하는 것인 양극 활물질의 제조방법.
- 청구항 1에 있어서,상기 인계 화합물은 (NH4)2HPO4, Li3PO4 및 Na3PO4 중에서 선택되는 1종 이상인 양극 활물질의 제조방법.
- 청구항 1에 있어서,상기 인계 화합물은 상기 수세 용액에 상기 리튬 전이금속 산화물에 대하여 인의 함량이 200ppm 내지 1,000ppm의 중량이 되도록 포함되는 것인 양극 활물질의 제조방법.
- 청구항 1에 있어서,상기 수세 용액은 pH가 7.00 내지 9.00인 것인 양극 활물질의 제조방법.
- 청구항 1에 있어서,상기 수세 용액의 용매는 탈이온수, 증류수 및 에탄올 중에서 선택되는 1종 이상인 양극 활물질의 제조방법.
- 청구항 1에 있어서,상기 리튬 전이금속 산화물은 하기 화학식 1로 표시되는 것인 양극 활물질의 제조방법:[화학식 1]Li1+aNix1Coy1M1 z1M2 w1O2이때, 0≤a≤0.3, 0.6≤x1<1.0, 0<y1≤0.4, 0<z1≤0.4, 0≤w1≤0.2, x1+y1+z1+w1=1이고,M1은 Mn 및 Al 중에서 선택된 1종 이상이며,M2는 Zr, B, W, Mo, Cr, Nb, Mg, Hf, Ta, La, Ti, Sr, Ba, Ce, F, P, S 및 Y 중에서 선택된 1종 이상이다.
- 청구항 1에 있어서,(C) 상기 (B) 단계를 거친 리튬 전이금속 산화물에 코팅 원소 함유 원료 물질을 혼합하고 열처리하여 코팅층을 형성하는 단계;를 더 포함하는 양극 활물질의 제조방법.
- 리튬 전이금속 산화물; 및상기 리튬 전이금속 산화물 상에 형성된 인(P)을 포함하는 코팅층;을 포함하고,상기 인은 상기 리튬 전이금속 산화물 대비 100ppm 내지 1,000ppm의 중량으로 포함되는 것인양극 활물질.
- 청구항 1에 있어서,상기 양극 활물질은 시차주사열량측정법(DSC)에 의해 측정된 발열량이 1400J/g 이하인 양극 활물질.
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PCT/KR2022/012082 WO2023018277A1 (ko) | 2021-08-13 | 2022-08-12 | 양극 활물질의 제조방법 및 양극 활물질 |
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EP (1) | EP4336588A1 (ko) |
JP (1) | JP2024521042A (ko) |
KR (1) | KR20230025363A (ko) |
CN (1) | CN117397063A (ko) |
WO (1) | WO2023018277A1 (ko) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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KR20150050153A (ko) * | 2013-10-31 | 2015-05-08 | 주식회사 엘지화학 | 리튬 이차전지용 양극 활물질 조성물 및 그 제조방법 |
JP6055761B2 (ja) * | 2011-04-28 | 2016-12-27 | 昭和電工株式会社 | リチウム二次電池用正極活物質の製造方法 |
KR20170084995A (ko) * | 2016-01-13 | 2017-07-21 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지 |
KR20200061889A (ko) * | 2018-11-26 | 2020-06-03 | 에스케이이노베이션 주식회사 | 리튬 이차 전지용 양극 활물질 및 이의 제조방법 |
KR20210063247A (ko) * | 2019-11-22 | 2021-06-01 | 주식회사 엘지화학 | 리튬 이차전지용 양극 활물질의 제조 방법, 상기 제조 방법에 의해 제조된 양극 활물질 |
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2022
- 2022-08-12 CN CN202280038390.4A patent/CN117397063A/zh active Pending
- 2022-08-12 KR KR1020220101069A patent/KR20230025363A/ko unknown
- 2022-08-12 EP EP22856270.8A patent/EP4336588A1/en active Pending
- 2022-08-12 WO PCT/KR2022/012082 patent/WO2023018277A1/ko active Application Filing
- 2022-08-12 JP JP2023568720A patent/JP2024521042A/ja active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6055761B2 (ja) * | 2011-04-28 | 2016-12-27 | 昭和電工株式会社 | リチウム二次電池用正極活物質の製造方法 |
KR20150050153A (ko) * | 2013-10-31 | 2015-05-08 | 주식회사 엘지화학 | 리튬 이차전지용 양극 활물질 조성물 및 그 제조방법 |
KR20170084995A (ko) * | 2016-01-13 | 2017-07-21 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지 |
KR20200061889A (ko) * | 2018-11-26 | 2020-06-03 | 에스케이이노베이션 주식회사 | 리튬 이차 전지용 양극 활물질 및 이의 제조방법 |
KR20210063247A (ko) * | 2019-11-22 | 2021-06-01 | 주식회사 엘지화학 | 리튬 이차전지용 양극 활물질의 제조 방법, 상기 제조 방법에 의해 제조된 양극 활물질 |
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Publication number | Publication date |
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EP4336588A1 (en) | 2024-03-13 |
JP2024521042A (ja) | 2024-05-28 |
CN117397063A (zh) | 2024-01-12 |
KR20230025363A (ko) | 2023-02-21 |
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