WO2017057900A1 - 이차전지용 양극활물질 및 이를 포함하는 이차전지 - Google Patents
이차전지용 양극활물질 및 이를 포함하는 이차전지 Download PDFInfo
- Publication number
- WO2017057900A1 WO2017057900A1 PCT/KR2016/010862 KR2016010862W WO2017057900A1 WO 2017057900 A1 WO2017057900 A1 WO 2017057900A1 KR 2016010862 W KR2016010862 W KR 2016010862W WO 2017057900 A1 WO2017057900 A1 WO 2017057900A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- active material
- positive electrode
- shell
- secondary battery
- core
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 claims abstract description 121
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000002131 composite material Substances 0.000 claims abstract description 67
- 239000013078 crystal Substances 0.000 claims abstract description 48
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 48
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 106
- 239000002184 metal Substances 0.000 claims description 104
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- 150000001869 cobalt compounds Chemical class 0.000 description 1
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- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
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- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
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- 229940099607 manganese chloride Drugs 0.000 description 1
- 239000011564 manganese citrate Substances 0.000 description 1
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- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
-
- 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
-
- 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
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a cathode active material for a secondary battery capable of exhibiting high output characteristics and a secondary battery comprising the same.
- lithium secondary batteries having high energy density and voltage, long cycle life, and low self discharge rate have been commercialized and widely used.
- a lithium secondary battery has a problem in that its life is rapidly decreased as charging and discharging are repeated. In particular, this problem is more serious at high temperatures. This is due to the phenomenon that the electrolyte is decomposed or the active material is deteriorated due to moisture or other effects in the battery, and the internal resistance of the battery is increased.
- LiCoO 2 having a layered structure. LiCoO 2 is most commonly used due to its excellent lifespan characteristics and charge and discharge efficiency. However, LiCoO 2 has a low structural stability and thus is not applicable to high capacity technology of batteries.
- LiNiO 2 LiMnO 2 , LiMn 2 O 4 , LiFePO 4 , Li (Ni p Co q Mn r ) O 2
- LiNiO 2 has the advantage of exhibiting battery characteristics of high discharge capacity, but the synthesis is difficult by a simple solid phase reaction, there is a problem of low thermal stability and low cycle characteristics.
- lithium manganese oxides such as LiMnO 2 or LiMn 2 O 4 have advantages in that they are excellent in thermal safety and inexpensive, but have a small capacity and low temperature characteristics.
- LiMn 2 O 4 but a part merchandising products to low cost, since the Mn + 3 structure modification (Jahn-Teller distortion) due to the not good life property.
- LiFePO 4 has a low price and excellent safety, and a lot of research is being made for hybrid electric vehicles (HEV), but it is difficult to apply to other fields due to low conductivity.
- LiCoO 2 lithium nickel manganese cobalt oxide and Li (Ni p C q Mn r ) O 2 (At this time, P, q, and r are atomic fractions of independent oxide composition elements, respectively, where 0 ⁇ p ⁇ 1, 0 ⁇ q ⁇ 1, 0 ⁇ r ⁇ 1, and 0 ⁇ p + q + r ⁇ 1.
- This material is cheaper than LiCoO 2 and has advantages in that it can be used for high capacity and high voltage, but has a disadvantage in that the rate capability and the service life at high temperature are poor.
- the first technical problem to be solved by the present invention is to provide a cathode active material for a secondary battery and a method for manufacturing the same that can exhibit high output characteristics by controlling the grain size.
- a second technical problem to be solved by the present invention is to provide a secondary battery positive electrode, a lithium secondary battery, a battery module and a battery pack including the positive electrode active material.
- a core A shell surrounding the core; And a buffer layer positioned between the core and the shell, wherein the buffer layer includes a three-dimensional network structure and voids connecting the core and the shell, wherein the three-dimensional network structure in the core, the shell, and the buffer layer are each independently a plurality of layers.
- a cathode active material for a secondary battery including a polycrystalline lithium composite metal oxide of Formula 1 including crystal grains and having an average crystal size of 50 nm to 150 nm.
- M1 is any one or two or more elements selected from the group consisting of Al and Mn
- M2 is any one or two or more elements selected from the group consisting of Zr, Ti, Mg, Ta and Nb
- M3 comprises any one or two or more elements selected from the group consisting of W, Mo and Cr, and 1.0 ⁇ a ⁇ 1.5, 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0.0005 ⁇ z ⁇ 0.03, 0 ⁇ w ⁇ 0.02, 0 ⁇ x + y ⁇ 0.7)
- a nickel raw material, cobalt raw material and M1 raw material (wherein, M1 is prepared by mixing any one or two or more elements selected from the group consisting of Al and Mn) Adding an ammonium cation-containing complex forming agent and a basic compound to the metal-containing solution and coprecipitation at pH 11 to pH 13 to prepare a precursor-containing reaction solution, and the ammonium cation-containing complex forming agent and the basic solution were reacted with the precursor-containing reaction solution. Adding a compound until the pH of the reaction solution is greater than or equal to 8 and less than pH 11 to grow the precursor, and after mixing the grown precursor with a lithium raw material, first firing at 500 ° C. to 700 ° C.
- M3 raw material in which at least one of the processes of mixing (wherein, M3 comprises any one or two or more elements selected from the group consisting of W, Mo and Cr) lithium in the lithium composite metal oxide
- M3 comprises any one or two or more elements selected from the group consisting of W, Mo and Cr
- a method for producing a cathode active material for a secondary battery which is further added in an amount of 0.0005 to 0.03 mole ratio with respect to the total moles of the metal elements except for the above.
- a cathode for a secondary battery a lithium secondary battery, a battery module, and a battery pack including the cathode active material.
- the cathode active material for a secondary battery according to the present invention may exhibit excellent output characteristics, particularly at low temperatures, by controlling grain size.
- FIG. 1 is a schematic cross-sectional view of a cathode active material for a secondary battery according to an embodiment of the present invention.
- Example 2 is a photograph of the precursor prepared in Example 1 observed with a field emission scanning electron microscopy (FE-SEM).
- the size of the secondary battery by controlling the grain size Output characteristics and lifespan characteristics can be improved.
- a cathode active material for a secondary battery includes a core; A shell surrounding the core; And a buffer layer positioned between the core and the shell, the buffer layer including a three-dimensional network structure and voids connecting the core and the shell.
- the three-dimensional network structure in the core, shell and buffer layer each comprises a polycrystalline lithium composite metal oxide of the formula (1) comprising a plurality of crystal grains independently,
- the grains have an average crystal size of 50 nm to 150 nm:
- M1 includes at least one element selected from the group consisting of Al and Mn
- M2 includes any one or two or more elements selected from the group consisting of Zr, Ti, Mg, Ta, and Nb
- M3 includes any one or two or more elements selected from the group consisting of W, Mo, and Cr, and a, x, y, z, and w are each independent atomic fractions of oxide composition elements, 1.0 ⁇ a ⁇ 1.5, 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0.0005 ⁇ z ⁇ 0.03, 0 ⁇ w ⁇ 0.02, 0 ⁇ x + y ⁇ 0.7.
- composition of the lithium composite metal oxide of Chemical Formula 1 is an average composition of the entire cathode active material particles.
- M3 is an element corresponding to group 6 (VIB group) of the periodic table, and serves to suppress particle growth during the firing process during preparation of the active material particles.
- VB group group 6
- M3 may be present at a position where these elements should be present by substituting a part of Ni, Co, or M1, or may react with lithium to form lithium oxide. Accordingly, the size of the crystal grains can be controlled by controlling the content of M3 and the timing of feeding.
- M3 may be any one or two or more elements selected from the group consisting of W, Mo, and Cr, and more specifically, may be at least one element of W and Cr.
- Such M3 may be included in an amount corresponding to z in the lithium composite metal oxide of Chemical Formula 1, that is, 0.0005 ⁇ z ⁇ 0.03.
- z is less than 0.0005 or more than 0.03, it is not easy to implement an active material satisfying the above-described characteristics, and as a result, an effect of improving output and life characteristics may be insignificant.
- the particle structure may be 0.001 ⁇ z ⁇ 0.01 in consideration of the embodied particle structure and the remarkable effect of improving battery characteristics.
- Li may be included in an amount corresponding to a, that is, 1.0 ⁇ a ⁇ 1.5. If a is less than 1.0, the capacity may be lowered. If a is more than 1.5, the particles may be sintered in the firing step, and thus the production of the active material may be difficult. Considering the remarkable effect of improving the capacity characteristics of the positive electrode active material according to the Li content control and the sinterability in the preparation of the active material, the Li may be more specifically included in a content of 1.0 ⁇ a ⁇ 1.15.
- Co may be included in an amount corresponding to x, that is, 0 ⁇ x ⁇ 0.5. If x is 0, the capacity characteristic may be lowered, and if it is more than 0.5, there is a fear of an increase in cost. Considering the remarkable effect of improving the capacity characteristics according to the inclusion of Co, the Co may be included in more specifically 0.10 ⁇ x ⁇ 0.35.
- M1 may be at least one selected from the group consisting of Al and Mn, and more specifically, Al or Mn.
- M1 may be included in an amount corresponding to y, that is, 0 ⁇ y ⁇ 0.5. If y is 0, the improvement effect due to the inclusion of M1 cannot be obtained. If y is greater than 0.5, the output characteristics and capacity characteristics of the battery may be deteriorated. In consideration of the remarkable effect of improving the battery characteristics according to the inclusion of the M1 element, M1 may be included in a content of 0.1 ⁇ y ⁇ 0.3 more specifically.
- the elements of Ni, Co, and M1 in the lithium composite metal oxide or the lithium composite metal oxide of Formula 1 may be replaced by another element, that is, M2, to improve battery characteristics by controlling distribution of metal elements in the active material. It may be partially substituted or doped.
- M2 may be any one or two or more elements selected from the group consisting of Zr, Ti, Mg, Ta, and Nb, and more specifically, Zr or Ti.
- the element of M2 may be included in an amount corresponding to w, that is, 0 ⁇ w ⁇ 0.02 in a range that does not lower the characteristics of the positive electrode active material.
- the lithium composite metal oxide of the formula (1) is a polycrystalline compound containing a plurality of crystal grains, so that the high output characteristics through the control of the content and firing conditions of the M3 element contained in the lithium composite metal oxide during its manufacture
- the crystal grain size is optimized.
- output characteristics can be improved.
- the average crystal size of the polycrystalline crystals is 50 nm to 150 nm, the stability of the crystal structure is further increased, and as a result, the effect of improving the output characteristics is more remarkable.
- the output characteristics are lowered when the average crystal size is out of the above range, and in particular, when the average crystal size is less than 50 nm, there is a risk of deterioration of life characteristics due to the formation of an unstable crystal structure. ) It may cause life characteristic resistance due to occurrence.
- the average crystal size of the primary particles may be more specifically 80nm to 120nm.
- a polycrystal means a crystal formed by gathering two or more crystal particles.
- the average crystal size of the crystal grains can be quantitatively analyzed for the lithium composite metal oxide particles using X-ray diffraction analysis.
- the average crystal size of the primary particles can be quantitatively analyzed by placing the polycrystalline lithium composite metal oxide particles in a holder and analyzing a diffraction grating that emits X-rays to the particles.
- the cathode active material for a lithium secondary battery the core containing the polycrystalline lithium composite metal oxide of Formula 1 and is located surrounding the core, the polycrystalline lithium composite metal oxide of Formula 1 A buffer layer comprising a shell, and positioned between the core and the shell surrounding the core, a void, and a three-dimensional network structure of the polycrystalline lithium composite metal oxide of Formula 1 connecting the core and the shell. It includes more.
- a buffer layer having a three-dimensional network structure connected to the core and the shell is formed between the core and the shell in the particles having a core-shell structure, thereby manufacturing an electrode.
- FIG. 1 is a cross-sectional view schematically showing a cathode active material for a lithium secondary battery according to an embodiment of the present invention. 1 is only an example for describing the present invention and the present invention is not limited thereto.
- a cathode active material 10 for a secondary battery includes a core 1, a shell 2 surrounding the core, and a core between the core and the shell.
- the core 1 includes a polycrystalline lithium composite metal oxide of the formula (1) (hereinafter referred to as 'first lithium composite metal oxide').
- the core 1 may be made of a single particle of the first lithium composite metal oxide, or may be made of secondary particles in which primary particles of the first lithium composite metal oxide are aggregated. At this time, the primary particles may be uniform or non-uniform.
- the shell 2 includes the polycrystalline lithium composite metal oxide (hereinafter referred to as 'second lithium composite metal oxide').
- the second lithium composite metal oxide may be crystal-oriented particles grown radially from the center of the cathode active material to the outside.
- the particles of the second lithium composite metal oxide forming the shell have crystal orientation in a direction in which lithium is easily inserted and detached, thereby realizing higher output characteristics than particles having no crystal orientation in the same composition. .
- the particles of the second lithium composite metal oxide may have various shapes such as polygons, cylinders, fibers, or scales such as hexahedrons. Specifically, it may be fibrous having an aspect ratio of 1.5 or more. If the aspect ratio of the particles of the second lithium composite metal oxide constituting the shell is less than 1.5, uniform grain growth may not be achieved and electrochemical properties may be lowered. In this case, the aspect ratio refers to the ratio of the length in the minor axis direction to the length in the major axis direction of the second lithium composite metal oxide particles.
- the shell 2 may further include a void formed between the particles of the second lithium composite metal oxide.
- a buffer layer 3 including a void 3a and a three-dimensional network structure 3b connecting between the core and the shell is located.
- the void (3a) is formed in the process of converting the active material particles into a hollow structure by controlling the pH of the reactants during the production of the active material, between the core (1) and the shell (2) It forms a space in the buffer function during rolling for electrode production.
- the electrolyte is easily penetrated to the inside of the active material, thereby allowing the reaction with the core, thereby increasing the reaction area of the active material with the electrolyte.
- Such voids 3a may be included in an amount of 30% by volume or less, more specifically, 2% by volume to 30% by volume, based on the total volume of the positive electrode active material.
- the pore 3a When included in the above range, it can exhibit an excellent buffering effect and increase the reaction area with the electrolyte solution without lowering the mechanical strength of the active material.
- the pore 3a may be included in an amount of 5% to 20% by volume based on the total volume of the positive electrode active material.
- the porosity of the buffer layer may be measured by cross-sectional analysis or mercury intrusion of particles using a focused ion beam (FIB).
- the three-dimensional network structure (3b) is formed during the production of the active material particles in the process of converting the active material particles into a hollow structure to form an inner core, is connected between the core and the shell core It serves to support the space between (1) and the shell (2). Accordingly, the three-dimensional network structure 3b includes the polycrystalline lithium composite metal oxide of Formula 1 (hereinafter referred to as a third lithium composite metal oxide) similarly to the core 1 and the shell 2.
- At least one metal element of nickel, M1, and cobalt contained in the polycrystalline lithium composite metal oxide of Formula 1 may increase in the active material particles, or It can be distributed in decreasing concentration gradients.
- the concentration gradient or concentration profile of the metal element in the active material is defined as the depth of the center portion at the surface of the particle, and the Y axis represents the content of the metal element at the particle surface. It means the graph which shows content.
- a positive mean slope of the concentration profile means that the metal element is located in the center portion of the particle relatively more than the surface portion of the particle
- a negative mean slope means that the metal element is located in the surface portion of the particle more than the center portion of the particle. It means that it is located relatively much.
- the concentration gradient and concentration profile of the metal in the active material particles are X-ray photoelectron spectroscopy (XPS), ESCA (Electron Spectroscopy for Chemical Analysis), electron beam microanalyzer (Electron Probe) Micro Analyzer, EPMA), Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP-AES), or Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS)
- XPS X-ray photoelectron spectroscopy
- ESCA Electrodectron Spectroscopy for Chemical Analysis
- electron beam microanalyzer Electro Analyzer
- ICP-AES Inductively Coupled Plasma-Atomic Emission Spectrometer
- ToF-SIMS Time of Flight Secondary Ion Mass Spectrometry
- At least one metal element of nickel, cobalt and M1 may have a concentration gradient in which the concentration of the metal is gradually changed over the active material particles.
- the gradient of concentration gradient of can represent one or more values.
- concentration of the metal is present in a concentration distribution that changes in stages throughout the particle.
- concentration distribution is 0.1 atomic% to 30 atomic%, more specifically 0.1 atomic% to 1 atomic percent, based on the total atomic weight of the metal included in the active material particles, wherein the change in the metal concentration per micrometer in the particles is 20 atomic%, more specifically, it may be a difference of 1 atomic% to 10 atomic%.
- the concentration of nickel contained in the active material may decrease while having a continuous concentration gradient from the center of the active material particles toward the surface of the particles.
- the gradient of the concentration gradient of nickel may be constant from the center of the active material particles to the surface.
- the concentration of M1 contained in the active material may increase while having a continuous concentration gradient from the center of the active material particles toward the surface of the particles.
- the concentration gradient slope of M1 may be constant from the center of the active material particles to the surface.
- M1 may be Mn.
- the concentration of cobalt contained in the active material may increase while having a continuous concentration gradient from the center of the active material particles toward the surface of the particles.
- the concentration gradient slope of the active material may be constant from the center of the active material particles to the surface.
- the content of nickel included in the core may be higher than the content of nickel included in the shell, specifically, the core is a transition metal element gun included in the core
- the nickel may be contained in an amount of 60 mol% or more and less than 100 mol% with respect to the mole, and the shell may include nickel in an amount of 30 mol% or more and less than 65 mol% with respect to the total moles of transition metal elements included in the shell. .
- the content of manganese contained in the core may be less than the content of manganese contained in the shell.
- the content of cobalt contained in the core may be less than the content of cobalt contained in the shell.
- nickel, manganese, and cobalt each independently represent a continuously changing concentration gradient throughout the active material particles, the concentration of nickel from the center of the active material particles The concentration decreases with a continuous concentration gradient in the surface direction, and the cobalt and manganese concentrations may increase independently with a continuous concentration gradient from the center of the active material particles toward the surface.
- nickel, manganese, and cobalt represent a concentration gradient that is continuously and independently changed in the core and the shell, respectively, and the concentration of the nickel is from the center of the core to the core.
- concentrations of cobalt and manganese are each independently from the center of the core to the interface of the core and the buffer layer, and with the buffer layer It can increase with a continuous concentration gradient from the interface of the shell to the shell surface.
- nickel, M1, and cobalt each independently represent a changing concentration gradient throughout the active material particles, and the concentration of nickel decreases with a continuous concentration gradient from the center of the active material particles to the surface direction. And, the concentrations of the cobalt and M1 can be increased each independently having a continuous concentration gradient from the center of the active material particles to the surface direction. As such, the concentration of nickel decreases toward the surface of the active material particles and the concentration of M1 and cobalt increases throughout the active material, thereby improving thermal stability while maintaining the capacity characteristics of the positive electrode active material. have.
- the cathode active material according to an embodiment of the present invention having the structure as described above may be secondary particles in which primary particles are assembled.
- the cathode active material may have an average particle diameter (D 50 ) of 2 ⁇ m to 20 ⁇ m, more specifically 3 ⁇ m to 15 ⁇ m. If the average particle diameter of the positive electrode active material is less than 2 ⁇ m, the stability of the polycrystalline lithium composite metal oxide particles may be lowered, and if it exceeds 20 ⁇ m, the output characteristics of the secondary battery may be lowered. In addition, the positive electrode active material according to the present invention may satisfy the average particle diameter of the secondary particles together with the grain size described above, thereby exhibiting better structural stability and improved output characteristics when the battery is applied.
- the average particle diameter (D 50 ) of the positive electrode active material may be defined as the particle size at 50% of the particle size distribution.
- the average particle diameter (D 50 ) of the positive electrode active material particles is, for example, electrons using a scanning electron microscopy (SEM) or a field emission scanning electron microscopy (FE-SEM). It can be measured by microscopic observation or by laser diffraction method.
- SEM scanning electron microscopy
- FE-SEM field emission scanning electron microscopy
- the particles of the positive electrode active material are dispersed in a dispersion medium, and then introduced into a commercially available laser diffraction particle size measuring apparatus (for example, Microtrac MT 3000) to output ultrasonic waves of about 28 kHz to 60 W. was irradiated with, it can be used to calculate the mean particle size (D 50) of from 50% based on the particle size distribution of the measuring device.
- a commercially available laser diffraction particle size measuring apparatus for example, Microtrac MT 3000
- the ratio of the core radius to the radius of the positive electrode active material is greater than 0 and less than 0.4, more specifically 0.01 to 0.2, even more specifically 0.1 to 0.2, the positive electrode active material to the radius of the positive electrode active material
- the length ratio from the center to the interface of the buffer layer and the shell may be greater than 0 and less than 0.7, more specifically 0.01 to 0.5, even more specifically 0.1 to 0.3.
- the shell region determined according to the following equation (1) is 0.2 to 1, more specifically 0.25 to 0.7, Specifically, it may be 0.5 to 0.6.
- Shell area (radius of anode active material-core radius-buffer layer thickness) / radius of anode active material
- the core, the buffer layer and the shell are formed in the positive electrode active material and the concentration gradients of the metal elements are formed in the respective regions as described above, the distribution of nickel, cobalt and M1 in the active material particles is more optimized and controlled.
- the destruction of the active material by the rolling process during electrode production and maximizing the reactivity with the electrolyte it is possible to further improve the output characteristics and life characteristics of the secondary battery.
- the particle diameter of the core portion can be measured through particle cross-sectional analysis using a focused ion beam (fib).
- the cathode active material according to an embodiment of the present invention may have a BET specific surface area of 0.1 m 2 / g to 1.9m 2 / g.
- the BET specific surface area of the positive electrode active material exceeds 1.9m 2 / g and there is a risk of dispersion decreases, and increase in electrode resistance of the intra-layer active material the positive electrode active material due to the aggregation between the positive electrode active material, and a BET specific surface area of 0.1m 2 / g When less than this, there exists a possibility of the dispersibility fall of a positive electrode active material itself, and a capacity fall.
- the specific surface area of the positive electrode active material is measured by the Brunauer-Emmett-Teller (BET) method, specifically, nitrogen gas at liquid nitrogen temperature (77K) using BELSORP-mino II manufactured by BEL Japan It can calculate from adsorption amount.
- BET Brunauer-Emmett-Teller
- the positive electrode active material according to an embodiment of the present invention may exhibit excellent capacity and charge and discharge characteristics by simultaneously promoting the above average particle diameter and BET specific surface area conditions. More specifically, the cathode active material may have an average particle diameter (D 50 ) of 3 ⁇ m 15 ⁇ m and BET specific surface area of 0.15m 2 / g to 1.5m 2 / g.
- the positive electrode active material according to an embodiment of the present invention may have a tap density of 1.2 g / cc or more, or 1.2 g / cc to 2.5 g / cc.
- the tap density of the positive electrode active material can be measured using a conventional tap density measuring device, and specifically, can be measured using a tap density tester.
- a cathode active material according to an embodiment of the present invention having the structure and physical properties as described above, nickel raw material, cobalt raw material and M1 raw material (wherein M1 is at least one selected from the group consisting of Al and Mn)
- M1 is at least one selected from the group consisting of Al and Mn
- step 2 Adding an ammonium cation-containing complex forming agent and a basic compound to the precursor-containing reaction solution until the pH of the reaction solution is greater than or equal to 8 and less than pH 11 to grow the precursor (step 2), and the grown precursor After mixing with a lithium raw material and performing a first firing at 500 °C to 700 °C and a secondary firing at 700 °C to 900 °C (step 3), the gold M3 raw material during the preparation of the containing solution, and at least one of the process of mixing the grown precursor and the lithium raw material, wherein M3 is any one or two or more selected from the group consisting of W, Mo and Cr It can be produced by a manufacturing method of the (additional elements)).
- each metal in step 1 M2 raw material may be added when mixing the raw material of the element, or M2 raw material may be added when mixing with the lithium raw material in step 2. Accordingly, according to another embodiment of the present invention, a method of manufacturing the cathode active material is provided.
- step 1 in the manufacturing method for the production of the cathode active material preparing a precursor using a nickel raw material, cobalt raw material, M1 raw material and optionally M3 or M2 raw material to be.
- the precursor is a coprecipitation reaction by adding an ammonium cation-containing complex forming agent and a basic compound to a metal-containing solution prepared by mixing nickel raw material, cobalt raw material, M1 raw material, and optionally M3 or M2 raw material.
- a metal-containing solution prepared by mixing nickel raw material, cobalt raw material, M1 raw material, and optionally M3 or M2 raw material.
- the mixing ratio of each raw material may be appropriately determined within a range to satisfy the content condition of each metal element in the final cathode active material.
- the metal-containing solution is an organic solvent (specifically, alcohol, etc.) capable of uniformly mixing nickel raw material, cobalt raw material, M1 containing raw material and optionally M3 or M2 containing raw material with solvent, specifically water, or water, respectively. ) May be added to a mixture of water and water, or a solution containing each metal-containing raw material, specifically, an aqueous solution, may be mixed and then used.
- organic solvent specifically, alcohol, etc.
- metal-containing raw material acetates, nitrates, sulfates, halides, sulfides, hydroxides, oxides or oxyhydroxides and the like can be used, and are not particularly limited as long as they can be dissolved in water.
- cobalt raw material Co (OH) 2 , CoOOH, Co (OCOCH 3 ) 2 ⁇ 4H 2 O, Co (NO 3 ) 2 ⁇ 6H 2 O or Co (SO 4 ) 2 ⁇ 7H 2 O, etc. And any one or a mixture of two or more thereof may be used.
- Ni (OH) 2 , NiO, NiOOH, NiCO 3 ⁇ 2Ni (OH) 2 ⁇ 4H 2 O, NiC 2 O 2 ⁇ 2H 2 O, Ni (NO 3 ) 2 ⁇ 6H 2 O, NiSO 4 , NiSO 4 .6H 2 O, fatty acid nickel salts or nickel halides, and the like, and any one or a mixture of two or more thereof may be used.
- M1 raw material acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide or oxyhydroxide containing M1 element may be used.
- M1 Mn
- manganese oxides include manganese oxides such as Mn 2 O 3 , MnO 2 , and Mn 3 O 4 ;
- Manganese salts such as MnCO 3 , Mn (NO 3 ) 2 , MnSO 4 , manganese acetate, manganese dicarboxylic acid, manganese citrate and fatty acid manganese; Oxy hydroxide, and manganese chloride, and the like, and any one or a mixture of two or more thereof may be used.
- M1 is Al
- an aluminum raw material may include AlSO 4 , AlCl, or AlNO 3 , and any one or a mixture of two or more thereof may be used.
- M2 raw material acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide or oxyhydroxide containing M2 element may be used.
- M 2 titanium oxide may be used.
- the M2 raw material may be used in a range to satisfy the content condition of the M2 element in the final cathode active material.
- M3 raw material acetate, nitrate, sulfate, halide, sulfide, hydroxide, oxide or oxyhydroxide containing M3 element may be used.
- M 3 is W
- tungsten oxide may be used.
- the M3 raw material may be used in a range to satisfy the content condition of the M3 element in the positive electrode active material to be manufactured.
- ammonium cation-containing complexing agent may specifically be NH 4 OH, (NH 4 ) 2 SO 4 , NH 4 NO 3 , NH 4 Cl, CH 3 COONH 4 , or NH 4 CO 3 , and the like. Species alone or mixtures of two or more may be used.
- the ammonium cation-containing complex forming agent may be used in the form of an aqueous solution, wherein a solvent may be a mixture of water or an organic solvent (specifically, alcohol, etc.) that can be mixed with water uniformly.
- the ammonium cation-containing complex forming agent may be added in an amount such that the molar ratio of 0.5 to 1 per mole of the metal salt solution.
- the chelating agent reacts with the metal in a molar ratio of at least 1: 1 to form a complex, but the unreacted complex which does not react with the basic aqueous solution may be converted into an intermediate product, recovered as a chelating agent, and reused.
- the chelating usage can be lowered than usual. As a result, the crystallinity of the positive electrode active material can be increased and stabilized.
- the basic compound may be a hydroxide of an alkali metal or an alkaline earth metal such as NaOH, KOH, or Ca (OH) 2 , or a hydrate thereof, and one or more of these may be used.
- the basic compound may also be used in the form of an aqueous solution, and as the solvent, a mixture of water or an organic solvent (specifically, alcohol, etc.) that can be uniformly mixed with water may be used.
- the coprecipitation reaction may be carried out under the condition that the pH is 11 to 13. If the pH is out of the above range, there is a fear to change the size of the precursor to be prepared or cause particle splitting.
- metal ions may be eluted on the surface of the precursor to form various oxides by side reactions. More specifically, the pH of the mixed solution may be performed at 11 to 12 conditions.
- the ammonium cation-containing complexing agent and the basic compound may be used in a molar ratio of 1:10 to 1: 2 to satisfy the above pH range.
- the pH value means a pH value at the temperature of the liquid 25 °C.
- the coprecipitation reaction may be carried out at a temperature of 40 °C to 70 °C under an inert atmosphere such as nitrogen or argon.
- the stirring process may be selectively performed to increase the reaction rate during the reaction, wherein the stirring speed may be 100 rpm to 2000 rpm.
- the second metal including nickel, cobalt, M1 containing metal salts and optionally M2 containing metal salts at different concentrations from the metal containing solution described above.
- the mixing ratio of the metal containing solution and the second metal containing solution is gradually changed from 100% by volume to 0% by volume to 0% by volume to 100% by volume. It can be carried out by adding a bimetallic containing solution and simultaneously reacting by adding an ammonium cation containing complex former and a basic compound.
- nickel, cobalt, and M1 are independently from the center of the particle to the surface in one coprecipitation reaction process. It is possible to produce composite metal hydroxides having a continuously changing concentration gradient. At this time, the concentration gradient of the metal in the hydroxide and its slope can be easily controlled by the composition and the mixed feed ratio of the metal-containing solution and the second metal-containing solution. It is preferable to lengthen the reaction time and to lower the reaction rate, and to shorten the reaction time and increase the reaction rate in order to make a low density state having a low concentration of a specific metal.
- the speed of the second metal-containing solution added to the metal-containing solution may be carried out continuously increasing in the range of 1% to 30% compared to the initial charge rate.
- the input speed of the metal-containing solution may be 150ml / hr to 210ml / hr
- the input speed of the second metal-containing solution may be 120ml / hr to 180ml / hr
- the initial charge within the input speed range The input rate of the second metal-containing solution can be continuously increased within the range of 1% to 30% of the rate.
- the reaction may be carried out at 40 °C to 70 °C.
- the size of the precursor particles may be adjusted by adjusting the supply amount and the reaction time of the second metal-containing solution to the first metal-containing solution.
- the precursor particles of a composite metal hydroxide are generated as a precursor and are precipitated in a reaction solution.
- the precursor may include a compound of Formula 2 below.
- a drying process may be optionally performed.
- the drying process may be carried out according to a conventional drying method, specifically, may be performed for 15 hours to 30 hours by a method such as heat treatment, hot air injection in the temperature range of 100 °C to 200 °C.
- step 2 is a step of growing the particles of the metal-containing hydroxide prepared in the step 1.
- the particles of the transition metal-containing hydroxide may be added to the reaction solution in which the particles of the metal-containing hydroxide are added until the pH of the reaction solution becomes lower than the pH of the coprecipitation reaction. Can be grown.
- the total mole number of nickel ions, cobalt ions and manganese ions may be 0.5M to 2.5M, or 1M to 2.2M.
- the particle growth step of the metal-containing hydroxide in step 2 may be carried out at a pH lower than the particle generation step of the metal-containing hydroxide in step 1, specifically, lower than the pH in step 1, pH 8 or more And less than pH 11, more specifically in the range of pH 8 to pH 10.5.
- the growth of the nickel-cobalt-manganese composite metal-containing hydroxide particles may be performed by changing the pH of the reactant at a rate of pH 1 to pH 2.5 per hour.
- the desired particle structure can be easily formed by performing the pH change rate as described above at a lower pH than in the coprecipitation reaction.
- ammonium cation-containing complex forming agent and the basic compound when added to the reaction solution in which the particles of the metal-containing hydroxide are formed, they may be added at the same rate, or may be added while continuously reducing the addition rate. If the feed rate is reduced, the feed rate can be reduced at a rate of 20% or more and less than 100%.
- the precipitation rate of the transition metal hydroxide in the particle growth step is faster than that of the lithium transition metal hydroxide in the step 1 can do.
- the density of the vicinity of the outer surface of the particles of the transition metal hydroxide serving as a precursor can be lowered to easily induce the grain growth direction in the subsequent heat treatment process.
- step 2 may be carried out in an inert atmosphere.
- step 2 the step of separating the particles of the grown transition metal hydroxide from the reaction solution and then washing and drying may be optionally further carried out.
- the drying process may be carried out in accordance with a conventional drying method, specifically, may be carried out by a method such as heat treatment, hot air injection in the temperature range of 100 °C to 120 °C.
- the positive electrode active material is prepared by mixing the particles of the metal-containing hydroxide grown in the step 2 with a lithium raw material, and optionally M3 or M2 raw material and then firing It's a step. At this time, M3 and M2 raw materials are the same as described above.
- lithium raw material examples include lithium-containing carbonates (for example, lithium carbonate), hydrates (for example, lithium hydroxide I hydrate (LiOH ⁇ H 2 O), etc.), hydroxides (for example, lithium hydroxide, etc.), nitrates ( For example, lithium nitrate (LiNO 3 ), etc.), chlorides (for example, lithium chloride (LiCl), etc.), and the like may be used alone, or a mixture of two or more thereof may be used.
- the amount of the lithium-containing raw material used may be determined according to the content of lithium and transition metal in the final lithium composite metal oxide, and specifically, the metal element included in the lithium and composite metal hydroxides included in the lithium raw material. (Me) and the molar ratio (molar ratio of lithium / metal element (Me)) can be used in an amount such that 1.0 or more.
- the firing process may be carried out in a multi-stage of primary firing at 250 °C to 500 °C and secondary firing at 700 °C to 900 °C.
- the primary firing is to increase the firing rate during the secondary firing, and then, by performing the secondary firing at a high temperature as compared with the primary firing, the physical properties including the grain size described above can be realized. More specifically, the firing process may be performed in two stages of primary firing at 400 ° C to 500 ° C and secondary firing at 750 ° C to 850 ° C.
- the firing process may be performed in an air atmosphere or an oxygen atmosphere (for example, O 2 ), and more specifically, may be performed in an oxygen atmosphere having an oxygen partial pressure of 20% by volume or more. In addition, the firing process may be performed for 5 hours to 48 hours, or 10 hours to 20 hours under the above conditions.
- O 2 oxygen atmosphere
- the firing process may be performed for 5 hours to 48 hours, or 10 hours to 20 hours under the above conditions.
- a sintering aid may optionally be further added during the firing process.
- the sintering aid can easily grow crystals at low temperatures and minimize the heterogeneous reaction during dry mixing.
- the sintering aid has the effect of making the rounded curved particles by dulling the corners of the lithium composite metal oxide primary particles.
- the lithium oxide-based positive electrode active material including manganese manganese is frequently eluted from the edges of the particles, and the manganese elution reduces the characteristics of the secondary battery, particularly at high temperatures.
- the sintering aid when used, the elution portion of manganese can be reduced by rounding the corners of the primary particles, and as a result, the stability and lifespan characteristics of the secondary battery can be improved.
- the sintering aid is boron compounds such as boric acid, lithium tetraborate, boron oxide and ammonium borate; Cobalt compounds such as cobalt oxide (II), cobalt oxide (III), cobalt oxide (IV), and tricobalt tetraoxide; Vanadium compounds such as vanadium oxide; Lanthanum compounds such as lanthanum oxide; Zirconium compounds such as zirconium boride, calcium zirconium silicate and zirconium oxide; Yttrium compounds such as yttrium oxide; Or gallium compounds such as gallium oxide, and the like, and any one or a mixture of two or more thereof may be used.
- boron compounds such as boric acid, lithium tetraborate, boron oxide and ammonium borate
- Cobalt compounds such as cobalt oxide (II), cobalt oxide (III), cobalt oxide (IV), and tricobalt tetraoxide
- Vanadium compounds such as
- the sintering aid may be used in an amount of 0.2 to 2 parts by weight, more specifically 0.4 to 1.4 parts by weight based on the total weight of the precursor.
- the moisture removing agent may be optionally further added during the firing process.
- the water removing agent may include citric acid, tartaric acid, glycolic acid or maleic acid, and any one or a mixture of two or more thereof may be used.
- the moisture remover may be used in an amount of 0.01 parts by weight to 2 parts by weight based on the total weight of the precursor.
- the particles of the metal-containing hydroxide produced and grown through the above steps 2 and 3 have different crystals inside the particles and outside the particles formed by the subsequent growth of the particles due to differences in process conditions during the manufacturing process, that is, pH. Has the nature. Accordingly, internal crystals made at high pH shrink during the firing process as described above, and crystals made at low pH and temperature grow so that the shrinked crystals form a core and the externally grown crystals form a shell. do.
- the formation of the core and the shell forms voids between the core and the shell, and the crystal located between the core and the shell forms a three-dimensional network structure connecting the inside and the outside of the particles.
- the crystals outside the particles grow radially outward from the center of the particles to have crystal orientation.
- the cathode active material prepared according to the above-described manufacturing method includes a buffer layer including pores between the core and the shell by controlling pH, concentration and rate of the reactants, thereby minimizing destruction of the active material during rolling in the electrode manufacturing process, Maximizing the reactivity with the electrolyte, and the shell forming particles have a crystal structure of an orientation that facilitates insertion and removal of lithium ions can improve the resistance and life characteristics of the secondary battery.
- the positive electrode active material can control the distribution of the transition metal throughout the active material particles, thereby exhibiting high capacity, long life and thermal stability when the battery is applied, and can minimize performance deterioration at high voltage.
- the positive electrode active material manufactured by the above process can exhibit high output characteristics, particularly excellent output characteristics at low temperatures, by controlling the grain size as described above.
- the distribution of the transition metal in the cathode active material can be additionally controlled, as a result of which the thermal stability is improved, thereby minimizing performance deterioration at high voltage.
- a cathode including the cathode active material, and a lithium secondary battery.
- the positive electrode is formed on the positive electrode current collector and the positive electrode current collector, and includes a positive electrode active material layer containing the positive electrode active material.
- the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
- carbon, nickel, titanium on a surface of aluminum or stainless steel Surface treated with silver, silver or the like can be used.
- the positive electrode current collector may have a thickness of typically 3 ⁇ m to 500 ⁇ m, and may form fine irregularities on the surface of the current collector to increase adhesion of the positive electrode active material.
- it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, or a nonwoven body.
- the cathode active material layer may further include at least one of a conductive material and a binder, together with the cathode active material described above.
- the conductive material is used to impart conductivity to the electrode.
- the conductive material may be used without particular limitation as long as it has electronic conductivity without causing chemical change. Specific examples thereof include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black and carbon fiber; Metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Or conductive polymers such as polyphenylene derivatives, and the like, or a mixture of two or more kinds thereof may be used.
- the conductive material may be included in an amount of 1 wt% to 30 wt% with respect to the total weight of the positive electrode active material layer.
- the binder serves to improve adhesion between the cathode active material particles and adhesion between the cathode active material and the current collector.
- specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC).
- the binder may be included in an amount of 1% by weight to 30% by weight based on the total weight of the positive electrode active material layer.
- the positive electrode may be manufactured according to a conventional positive electrode manufacturing method except for using the positive electrode active material described above.
- a composition for forming a positive electrode active material layer prepared by dissolving or dispersing at least one of a binder and a conductive material in a solvent, if necessary, may be prepared by drying and rolling. Can be.
- the type and content of the cathode active material, the binder, and the conductive material are as described above.
- the solvent may be a solvent generally used in the art, and may include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone or acetone. Water, and the like, one of these alone or a mixture of two or more thereof may be used.
- the amount of the solvent is sufficient to dissolve or disperse the positive electrode active material, the conductive material, and the binder in consideration of the coating thickness of the slurry and the production yield, and to have a viscosity that can exhibit excellent thickness uniformity during application for the production of the positive electrode. Do.
- the positive electrode may be prepared by casting the composition for forming the positive electrode active material layer on a separate support, and then laminating the film obtained by peeling from the support onto a positive electrode current collector.
- an electrochemical device including the anode is provided.
- the electrochemical device may be specifically a battery, a capacitor, or the like, and more specifically, a lithium secondary battery.
- the lithium secondary battery specifically includes a positive electrode, a negative electrode positioned to face the positive electrode, a separator and an electrolyte interposed between the positive electrode and the negative electrode, and the positive electrode is as described above.
- the lithium secondary battery may further include a battery container for accommodating the electrode assembly of the positive electrode, the negative electrode, and the separator, and a sealing member for 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 negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
- the negative electrode current collector may be formed on a surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper, or stainless steel. Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy and the like can be used.
- the negative electrode current collector may have a thickness of 3 ⁇ m to 500 ⁇ m, and like the positive electrode current collector, fine concavities and convexities may be formed on the surface of the current collector to enhance the bonding force of the negative electrode active material.
- it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
- the negative electrode active material layer optionally includes a binder and a conductive material together with the negative electrode active material.
- the negative electrode active material layer is coated with a negative electrode active material, and optionally a composition for forming a negative electrode including a binder and a conductive material on a negative electrode current collector and dried, or casting the negative electrode forming composition on a separate support It may be produced by laminating a film obtained by peeling from this support onto a negative electrode current collector.
- a compound capable of reversible intercalation and deintercalation of lithium may be used.
- Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fibers, and amorphous carbon;
- Metallic compounds capable of alloying with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys or Al alloys;
- Metal oxides capable of doping and undoping lithium such as SiO x (0 ⁇ x ⁇ 2), SnO 2 , vanadium oxide, lithium vanadium oxide;
- a composite including the metallic compound and the carbonaceous material such as a Si-C composite or a Sn-C composite, and any one or a mixture of two or more thereof may be used.
- a metal lithium thin film may be used as the anode active material.
- the carbon material both low crystalline carbon and high crystalline carbon can be used. Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is amorphous, plate, scaly, spherical or fibrous natural graphite or artificial graphite, Kish graphite (Kish) graphite, pyrolytic carbon, mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar pitch High-temperature calcined carbon such as derived cokes is typical.
- the binder and the conductive material may be the same as described above in the positive electrode.
- the separator is to separate the negative electrode and the positive electrode and to provide a passage for the movement of lithium ions, if it is usually used as a separator in a lithium secondary battery can be used without particular limitation, in particular to the ion movement of the electrolyte It is desirable to have a low resistance against the electrolyte and excellent electrolytic solution-moisture capability.
- a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer or the like Laminate structures of two or more layers may be used.
- a porous nonwoven fabrics such as nonwoven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers and the like may be used.
- a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be optionally used as a single layer or a multilayer structure.
- examples of the electrolyte used in the present invention include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like, which can be used in manufacturing a lithium secondary battery. It doesn't happen.
- the electrolyte may include an organic solvent and a lithium salt.
- the organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
- the organic solvent may be an ester solvent such as methyl acetate, ethyl acetate, ⁇ -butyrolactone or ⁇ -caprolactone; Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethylcarbonate (DMC), diethylcarbonate (DEC), methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate, Carbonate solvents such as PC); Alcohol solvents such as ethyl alcohol and isopropyl alcohol; Nitriles such as R-CN (R is a C2 to C20 linear, branched or cyclic hydrocarbon group, which may include a
- carbonate-based solvents are preferable, and cyclic carbonates having high ionic conductivity and high dielectric constant (for example, ethylene carbonate or propylene carbonate) that can improve the charge and discharge performance of a battery, and low viscosity linear carbonate compounds (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate and the like is more preferable.
- the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of about 1: 1 to about 1: 9, so that the performance of the electrolyte may be excellent.
- the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
- the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 .
- LiCl, LiI, or LiB (C 2 O 4 ) 2 and the like can be used.
- the concentration of the lithium salt is preferably used within the range of 0.1M to 2.0M. When the concentration of the lithium salt is included in the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can move effectively.
- the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, tri, etc. for the purpose of improving battery life characteristics, suppressing battery capacity reduction, and improving battery discharge capacity.
- haloalkylene carbonate-based compounds such as difluoroethylene carbonate, pyridine, tri, etc.
- Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate 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 included. In this case, the additive may be included in an amount of 0.1% by weight to 5% by weight based on the total weight of the electrolyte.
- the lithium secondary battery including the cathode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention rate
- portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles ( It is useful for electric vehicle fields such as hybrid electric vehicle (HEV).
- HEV hybrid electric vehicle
- 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 the battery pack is a power tool (Power Tool); Electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Or it can be used as a power source for any one or more of the system for power storage.
- Power Tool Electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Or it can be used as a power source for any one or more of the system for power storage.
- sodium tungstate dehydrate as a raw material of nickel sulfate, cobalt sulfate, manganese sulfate and tungsten was added to the molar ratio of the metal element contained in each compound in water.
- the resultant nickel manganese cobalt-based composite metal hydroxide particles were mixed with lithium hydroxide as a lithium raw material and a lithium (Li): composite metal (Me) in a molar ratio of 1: 1.07, followed by oxygen atmosphere (oxygen partial pressure 20 %), The primary heat treatment at 500 °C 10 hours, and secondary heat treatment at 820 °C 10 hours to prepare a positive electrode active material.
- sodium tungstate dehydrate as a raw material of nickel sulfate, cobalt sulfate, manganese sulfate and tungsten was added to the molar ratio of the metal element contained in each compound in water.
- a metal salt solution of 2M concentration was prepared by mixing at a molar ratio of 60: 20: 20: 0.25.
- the vessel containing the metal salt solution was connected to enter the reactor, and further prepared by 4M NaOH solution and 7% NH 4 OH aqueous solution was connected to each reactor.
- the NaOH aqueous solution and the NH 4 OH aqueous solution were added to lower the pH at a rate of pH 2 per hour, thereby changing the pH to 9.5 and inducing the growth of hydroxide particles. Since the reaction was maintained for 24 hours to grow nickel manganese cobalt-based composite metal hydroxide.
- the resulting nickel manganese cobalt-based composite metal hydroxide particles were mixed with lithium hydroxide and lithium (Li): composite metal (Me) in a molar ratio of 1: 1.07 as a lithium raw material, followed by oxygen atmosphere (oxygen partial pressure 20%). ), The first heat treatment at 500 °C for 10 hours, the second heat treatment at 820 °C for 10 hours to prepare a positive electrode active material.
- sodium tungstate dehydrate as a raw material of nickel sulfate, cobalt sulfate, manganese sulfate and tungsten was added to the molar ratio of the metal element contained in each compound in water.
- a metal salt solution of 2M concentration was prepared by mixing at a molar ratio of 60: 20: 20: 0.25.
- the vessel containing the metal salt solution was connected to enter the reactor, and further prepared by 4M NaOH solution and 7% NH 4 OH aqueous solution was connected to each reactor.
- the NaOH aqueous solution and the NH 4 OH aqueous solution were added to lower the pH at a rate of pH 2 per hour, thereby changing the pH to 9.5 and inducing the growth of hydroxide particles. Since the reaction was maintained for 24 hours to grow nickel manganese cobalt-based composite metal hydroxide.
- the cathode active material was prepared by annealing for 10 hours at 500 ° C. for 10 hours and at 820 ° C. for 10 hours under an oxygen atmosphere (20% oxygen partial pressure).
- nickel sulfate, cobalt sulfate, and manganese sulfate were mixed in water at a molar ratio of 60:20:20 based on the molar ratio of the metal elements included in each compound in water at a 2M concentration.
- the metal salt solution of was prepared.
- the vessel containing the metal salt solution was connected to enter the reactor, and prepared with 4M NaOH solution and 7% aqueous NH 4 OH solution was connected to the reactor.
- the NaOH aqueous solution and the NH 4 OH aqueous solution were added to lower the pH at a rate of pH 2 per hour, thereby changing the pH to 9.5 and inducing the growth of hydroxide particles. Since the reaction was maintained for 24 hours to grow nickel manganese cobalt-based composite metal hydroxide.
- the resulting nickel manganese cobalt-based composite metal hydroxide particles were mixed with lithium hydroxide and lithium (Li): composite metal (Me) in a molar ratio of 1: 1.07 as a lithium raw material, followed by oxygen atmosphere (oxygen partial pressure 20%). ), The first heat treatment at 500 °C for 10 hours, the second heat treatment at 820 °C for 10 hours to prepare a positive electrode active material.
- nickel sulfate, cobalt sulfate, and manganese sulfate were mixed in water at a molar ratio of 80:10:10 based on the molar ratio of metal elements included in each compound in water at a concentration of 2M.
- the vessel containing the first metal salt solution was connected to enter the reactor, and the vessel containing the second metal salt solution was connected to enter the first metal salt container.
- 4M NaOH solution and 7% NH 4 OH aqueous solution were prepared and connected to the reactor, respectively.
- the pH was lowered at a rate of pH 2 per hour to change the pH to 9.5, and the second metal salt solution was introduced at 150 ml / hr into the container of the first metal salt to induce the growth of hydroxide particles and to generate a concentration gradient inside the particles. It was induced to. Since the reaction was maintained for 24 hours to grow nickel manganese cobalt-based composite metal hydroxide.
- the resultant nickel manganese cobalt-based composite metal hydroxide particles were mixed with a lithium hydroxide and lithium (Li): composite metal (Me) in a molar ratio of 1: 1.07 as a lithium raw material, followed by oxygen atmosphere (oxygen partial pressure 20%). Under, 10 hours of primary heat treatment at 500 °C, 10 hours of secondary heat treatment at 820 °C to prepare a positive electrode active material.
- a lithium secondary battery was manufactured using the cathode active materials prepared in Examples 1 and 2, Comparative Example 1, and Reference Example, respectively.
- the positive electrode active material, the carbon black conductive material, and the PVdF binder prepared in Examples 1 to 2, Comparative Example 1, and Reference Example were 95: 2.5: 2.5 in a weight ratio of N-methylpyrrolidone solvent.
- the mixture was mixed at a ratio to prepare a composition for forming a positive electrode (viscosity: 5000 mPa ⁇ s), which was applied to an aluminum current collector, dried at 130 ° C., and then rolled to prepare a positive electrode.
- a negative electrode active material a natural graphite, a carbon black conductive material, and a PVdF binder are mixed in an N-methylpyrrolidone solvent in a weight ratio of 85: 10: 5 to prepare a composition for forming a negative electrode, which is applied to a copper current collector. To prepare a negative electrode.
- An electrode assembly was manufactured between the positive electrode and the negative electrode prepared as described above through a separator of porous polyethylene, the electrode assembly was placed in a case, and an electrolyte solution was injected into the case to prepare a lithium secondary battery.
- the particles of the nickel manganese cobalt-based composite metal hydroxide prepared as a precursor of the positive electrode active material according to Example 1 were observed by field emission scanning electron microscopy (FE-SEM), and the results of the core and shell Semi-diameter (corresponding to the thickness of the shell) and volume were calculated respectively. The results are shown in FIG. 2 and Table 1 below.
- Example 1 the cathode active material prepared in Example 1 was processed using ion milling, and the cross-sectional structure of the cathode active material was observed using FE-SEM. The results are shown in FIG.
- the total particle diameter of the positive electrode active material was 4.3 ⁇ m.
- the thickness (radius) of the core portion was 0.4 ⁇ m
- the thickness of the worm was 0.6 ⁇ m
- the thickness of the shell was 1.15 ⁇ m.
- the porosity of the buffer layer in the positive electrode active material was about 10% by volume.
- the BET specific surface area was calculated from the nitrogen gas adsorption amount under liquid nitrogen temperature (77K) using BELSORP-mino II manufactured by BEL Japan, and tap density was measured using a tap density tester.
- the BET specific surface area of the cathode active material prepared in Example 1 was 0.92 m 2 / g, and the tap density was 1.75 g / m 3 .
- the crystal size of the polycrystalline lithium composite metal oxide particles of Examples 1 to 2, Comparative Example 1 and Reference Example was measured by XRD crystal analysis.
- the polycrystalline lithium composite metal oxide particles of Examples 1 to 2, Comparative Example 1 and Reference Example were put in about 5 g of the holder, respectively, and the X-rays were irradiated on the particles to analyze the diffraction grating. peak) or the half-width of three or more peaks to determine grain size and content of nickel (Ni) intercalated into the lithium site.
- Table 2 The results are shown in Table 2 below.
- Example 1 (W doping & farm tools ship) 2.868 14.220 101.26 4.959 106 4.769 1.1
- Example 2 (W doping) 2.867 14.216 101.19 4.959 108 4.772 1.0 Comparative Example 1 (bare) 2.866 14.210 101.1 4.959 178 4.777 1.1 Reference example (farm tool ship) 2.867 14.212 101.14 4.958 157 4.774 0.6
- the positive electrode active materials of Examples 1 and 2 in which the grain size of the polycrystalline lithium composite metal oxide constituting the active material by W doping, showed nearly equivalent grain sizes and nickel content inserted in the lithium site.
- the positive electrode active materials of Comparative Example 1 and Reference Example in which the crystal grain size was not controlled, showed a large grain size of 150 nm or more, and the positive electrode active material of Reference Example was made of nickel (Ni) embedded in a lower lithium site than Example 1 Content is indicated.
- the positive electrode active material prepared in Example 1 was subjected to component analysis using EPMA. The results are shown in FIG. 3 and Table 3.
- the lithium secondary battery was charged / discharged 800 times under conditions of 1C / 2C at a temperature of 25 ° C. within a range of 2.8V to 4.15V driving voltage.
- cycle capacity retention which is the ratio of the discharge capacity at the 800th cycle with respect to the resistance at room temperature (25 ° C) and low temperature (-30 ° C) and the initial capacity after 800 charge / discharge cycles at room temperature Were respectively measured and shown in Table 4 below.
- Example 1 1.18 1.02 94.5
- Example 2 1.23 1.11 92.8 Comparative Example 1 1.45 1.59 92.5 Reference Example 1.34 1.25 95.4
- a buffer layer having a three-dimensional network structure and voids is formed between the core and the shell, and metal elements of nickel, manganese, and cobalt are distributed in concentration gradients throughout the active material particles, respectively, and the active material
- the lithium secondary battery including the active material has a positive electrode active material of Comparative Example 1 that does not have a core-shell structure, no concentration gradient of metal elements is formed, and the grain size of the lithium composite metal oxide constituting the active material is not controlled.
- the positive electrode active material according to the present invention exhibits an excellent output characteristics and life characteristics improvement effect.
- the lithium secondary battery including the positive electrode active material of Example 1 includes a core-shell structure and a buffer layer, and the metal elements in the active material particles have a concentration gradient, but the grain size of the lithium composite metal oxide constituting the active material is distributed.
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Abstract
Description
반직경(㎛) | 부피(㎛3) | |
코어 | 0.94 | 3.5 |
쉘 | 1.085 | 31.3 |
전체 | 2.025 | 34.8 |
a-axis(Å) | c-axis(Å) | 단위격자 셀 부피(Å8) | c/a | 결정립 크기(nm) | 밀도(g/cc) | Ni occ. @ Li site (몰%) | |
실시예 1(W도핑&농도구배) | 2.868 | 14.220 | 101.26 | 4.959 | 106 | 4.769 | 1.1 |
실시예 2(W도핑) | 2.867 | 14.216 | 101.19 | 4.959 | 108 | 4.772 | 1.0 |
비교예 1(bare) | 2.866 | 14.210 | 101.1 | 4.959 | 178 | 4.777 | 1.1 |
참고예(농도구배) | 2.867 | 14.212 | 101.14 | 4.958 | 157 | 4.774 | 0.6 |
Scan | Ni(mol%) | Co(mol%) | Mn(mol%) | |
코어 | 01 | 68 | 18 | 14 |
완충층 | 02 | 65 | 20 | 15 |
쉘 | 03 | 62 | 21 | 16 |
04 | 60 | 22 | 16 | |
05 | 58 | 24 | 19 | |
전체 | 60 | 23 | 17 |
상온(25℃) 저항(mohm) | 저온(-30℃)에서의 전압 강하(V) | 상온(25℃)에서의 800회 사이클 용량유지율 (%) | |
실시예 1 | 1.18 | 1.02 | 94.5 |
실시예 2 | 1.23 | 1.11 | 92.8 |
비교예 1 | 1.45 | 1.59 | 92.5 |
참고예 | 1.34 | 1.25 | 95.4 |
Claims (20)
- 코어;상기 코어를 둘러싸며 위치하는 쉘; 및상기 코어와 쉘 사이에 위치하며, 상기 코어와 쉘을 연결하는 3차원 망목구조체 및 공극을 포함하는 완충층을 포함하고,상기 코어, 쉘 및 완충층에서의 3차원 망목구조체는 각각 독립적으로 복수 개의 결정립을 포함하는 하기 화학식 1의 다결정 리튬 복합금속 산화물을 포함하며,상기 결정립은 평균 결정 크기가 50nm 내지 150nm인 것인 이차전지용 양극활물질.[화학식 1]LiaNi1 -x- yCoxM1yM3zM2wO2(상기 화학식 1에서, M1은 Al 및 Mn으로 이루어진 군에서 선택되는 적어도 어느 하나의 원소를 포함하고, M2는 Zr, Ti, Mg, Ta 및 Nb로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상의 원소를 포함하며, 그리고 M3은 W, Mo 및 Cr로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상의 원소를 포함하고, 1.0≤a≤1.5, 0<x≤0.5, 0<y≤0.5, 0.0005≤z≤0.03, 0≤w≤0.02, 0<x+y≤0.7이다)
- 제1항에 있어서,상기 니켈, 코발트 및 M1 중 적어도 어느 하나의 금속원소는, 상기 활물질 입자 내에서 변화하는 농도구배를 나타내는 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 코어 내에 포함되는 니켈의 함량이 쉘 내에 포함되는 니켈의 함량 보다 많은 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 코어 내에 포함되는 M1의 함량이 쉘 내에 포함되는 M1의 함량 보다 적은 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 코어 내에 포함되는 코발트의 함량이 쉘 내에 포함되는 코발트의 함량 보다 적은 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 코어 내에 포함되는 니켈의 함량이 쉘 내에 포함되는 니켈의 함량 보다 많으며,상기 코어는 코어 내 포함되는 전이 금속원소 총 몰에 대하여 60몰% 이상 100몰% 미만의 함량으로 니켈을 포함하고,상기 쉘은 쉘 내 포함되는 전이 금속원소 총 몰에 대하여 30몰% 이상 65몰% 미만의 함량으로 니켈을 포함하는 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 니켈, 코발트 및 M1은 활물질 입자 전체에 걸쳐 각각 독립적으로 변화하는 농도구배로 분포하고,상기 니켈은 활물질 입자의 중심에서부터 표면 방향으로 감소하는 농도구배로 분포하며, 그리고상기 코발트 및 M1은 각각 독립적으로 활물질 입자의 중심에서부터 표면 방향으로 증가하는 농도구배로 분포하는 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 쉘은 양극활물질의 중심에서부터 표면 방향으로 방사형으로 성장된 결정배향성의 다결정 리튬 복합금속 산화물의 입자를 포함하는 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 양극활물질의 반지름에 대한 코어 반지름의 비가 0초과 0.4미만이고, 상기 양극활물질의 반지름에 대한, 양극활물질 중심에서 완충층과 쉘의 계면까지의 길이의 비가 0초과 0.7 미만인 것인 이차전지용 양극활물질.
- 제1항에 있어서,하기 수학식 1에 따라 결정되는 양극활물질의 반지름에 대한 쉘 두께의 비인 쉘 영역이 0.2 내지 1인 것인 이차전지용 양극활물질.[수학식 1]쉘 영역=(양극활물질의 반지름-코어 반지름-완충층 두께)/양극활물질의 반지름
- 제1항에 있어서,상기 M1이 망간(Mn) 또는 알루미늄(Al)인 것인 이차전지용 양극활물질.
- 제1항에 있어서,평균 입자 직경(D50)이 2㎛ 내지 20㎛, BET 비표면적이 0.1m2/g 내지 1.9m2/g 이며, 1.2g/cc 내지 2.5 g/cc의 탭밀도를 갖는 것인 이차전지용 양극활물질.
- 니켈 원료물질, 코발트 원료물질 및 M1 원료물질(이때, M1은 Al 및 Mn으로 이루어진 군에서 선택되는 적어도 어느 하나의 원소를 포함함)을 혼합하여 제조한 금속 함유 용액에, 암모늄 양이온 함유 착물 형성제 및 염기성 화합물을 첨가하여 pH 11 내지 pH 13에서 공침반응시켜, 전구체 포함 반응용액을 준비하는 단계,상기 전구체 포함 반응용액에 암모늄 양이온 함유 착물 형성제와 염기성 화합물을 상기 반응용액의 pH가 8 이상 pH 11 미만이 될 때까지 첨가하여 상기 전구체를 성장시키는 단계; 및상기 성장된 전구체를 리튬 원료물질과 혼합한 후 500℃ 내지 700℃에서의 1차 소성 및 700℃ 내지 900℃에서의 2차 소성을 수행하는 단계를 포함하며,상기 금속 함유 용액의 제조시, 또는 상기 성장된 전구체와 리튬 원료물질과의 혼합시에 M3 원료물질(이때, M3은 W, Mo 및 Cr로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상의 원소를 포함함)을 최종 제조되는 리튬 복합금속 산화물에서의 리튬을 제외한 금속원소의 총 몰에 대하여 0.0005 내지 0.03몰비로 더 첨가하는, 제1항에 따른 이차전지용 양극활물질의 제조방법.
- 제13항에 있어서,상기 전구체의 성장 단계는 반응물의 pH를 시간당 pH 1 내지 pH 2.5의 속도로 변화시키며 수행되는 것인 이차전지용 양극활물질의 제조방법.
- 제13항에 있어서,상기 리튬 원료물질은 리튬 원료물질내 포함되는 리튬과 상기 전구체 내 포함되는 금속원소(Me)와의 몰비(리튬/금속원소(Me)의 몰비)가 1.0 이상이 되도록 사용되는 것인 이차전지용 양극활물질의 제조방법.
- 제13항에 있어서,상기 전구체 포함 반응용액을 준비 단계시, 상기 금속 함유 용액과는 서로 다른 농도로 니켈 원료물질, 코발트 원료물질 및 M1 원료물질을 포함하는 제2 금속 함유 용액을 더 첨가하는 이차전지용 양극활물질의 제조방법.
- 제13항에 있어서,상기 1차 및 2차 소성이 각각 독립적으로 공기 또는 산소 분위기하에서 수행되는 것인 이차전지용 양극활물질의 제조방법.
- 제13에 있어서,상기 1차 및 2차 소성이 각각 독립적으로 산소 분압 20% 이하의 분위기하에서 수행되는 것인 이차전지용 양극활물질의 제조방법.
- 제1항에 따른 양극활물질을 포함하는 이차전지용 양극.
- 제19항에 따른 양극을 포함하는 리튬 이차전지.
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EP3249723B1 (en) | 2018-12-05 |
CN107251282A (zh) | 2017-10-13 |
PL3249723T3 (pl) | 2019-09-30 |
CN107251282B (zh) | 2021-03-12 |
KR20170038485A (ko) | 2017-04-07 |
EP3249723A1 (en) | 2017-11-29 |
KR101913897B1 (ko) | 2018-12-28 |
EP3249723A4 (en) | 2018-05-02 |
US10862156B2 (en) | 2020-12-08 |
US20180048015A1 (en) | 2018-02-15 |
JP6562576B2 (ja) | 2019-08-21 |
JP2018521456A (ja) | 2018-08-02 |
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