WO2016204563A1 - 이차전지용 양극활물질, 이의 제조방법 및 이를 포함하는 이차전지 - Google Patents
이차전지용 양극활물질, 이의 제조방법 및 이를 포함하는 이차전지 Download PDFInfo
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- 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
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
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- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a cathode active material for a secondary battery, a manufacturing method thereof, and a secondary battery including the same.
- lithium secondary batteries having high energy density and voltage, long cycle life, and low self discharge rate have been commercialized and widely used.
- lithium cobalt-based oxides that are easily synthesized and have excellent electrochemical performance including lifespan characteristics are mainly used.
- portable devices such as mobile phones and tablet PCs become smaller and smaller, high-capacity and energy-efficient batteries are also required.
- the packing density of the active material must be increased or the voltage must be increased.
- the active material of such a large particle has a relatively low surface area, the active area in contact with the electrolyte is also narrow. This narrow active area acts kinetically (kinetic) adversely, resulting in a relatively low rate characteristics and initial capacity.
- the first problem to be solved by the present invention is to solve the above problems, to provide a positive electrode active material for secondary batteries having a high output and long life characteristics and a method of manufacturing the same.
- Another object of the present invention is to provide a positive electrode, a lithium secondary battery, a battery module, and a battery pack including the positive electrode active material.
- a third problem to be solved by the present invention is to provide a precursor useful for the preparation of the positive electrode active material and a method of manufacturing the same.
- a cathode active material for a secondary battery the core; A shell surrounding the core; And a buffer layer positioned between the core and the shell, wherein the buffer layer comprises a three-dimensional network structure and voids connecting the core and the shell, wherein the three-dimensional network structure in the core, shell, and buffer layer are each independently lithium nickel manganese.
- a cathode active material for a battery is provided.
- the nickel transition material at a different concentration from the first transition metal-containing solution containing the nickel raw material, cobalt raw material and manganese raw material, and the first transition metal containing solution Preparing a second transition metal-containing solution comprising a cobalt raw material and a manganese raw material; The second transition to the first transition metal-containing solution so that the mixing ratio of the first transition metal-containing solution and the second transition metal-containing solution gradually changes from 100% by volume to 0% by volume to 100% by volume
- a secondary battery positive electrode including the positive electrode active material.
- a lithium secondary battery including the positive electrode is provided.
- the nickel transition material at a different concentration from the first transition metal-containing solution containing the nickel raw material, cobalt raw material and manganese raw material, and the first transition metal containing solution Preparing a second transition metal-containing solution comprising a cobalt raw material and a manganese raw material; The second transition to the first transition metal-containing solution so that the mixing ratio of the first transition metal-containing solution and the second transition metal-containing solution gradually changes from 100% by volume to 0% by volume to 100% by volume
- a precursor of a cathode active material for a secondary battery includes a core and a shell surrounding the core, wherein the core and the shell each independently include a nickel manganese cobalt-based composite metal hydroxide.
- the metal element of at least one of nickel, manganese, and cobalt exhibits a concentration gradient gradually changing in any one of the core, the shell, and the precursor as a whole, and the nickel manganese cobalt-based composite included in the shell
- the metal hydroxide is provided with a precursor of the positive electrode active material for a secondary battery, which has a radial crystal orientation in the direction of the surface from the center of the precursor particles.
- a buffer layer of a lithium composite metal oxide having a mesh structure connected to the core and the shell is further formed between the core and the shell in the particles having a core-shell structure, and nickel and cobalt in the active material particles.
- the crystal structure of the orientation to minimize the destruction of the active material by the rolling process in the electrode manufacturing, to maximize the reactivity with the electrolyte, and to facilitate the insertion and detachment of lithium ions particles of the shell It can improve the output characteristics and life characteristics of the secondary battery.
- the positive electrode active material according to the present invention is a battery in which high capacity, high life and thermal stability are required, such as a battery for an automobile or a power tool, in particular, a battery in a battery where performance degradation at high voltage is required, such as a battery for an automobile. It is useful as an active material.
- 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).
- a cathode active material for a secondary battery according to an embodiment of the present invention
- a buffer layer comprising 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 independently comprises a lithium nickel manganese cobalt-based composite metal oxide
- the metal element of at least one of the nickel, manganese, and cobalt exhibits a concentration gradient that gradually changes in any one of the core, the shell, and the positive electrode active material.
- a buffer layer of a three-dimensional network structure connected to the core and the shell is further formed between the core and the shell in the particles having a core-shell structure, and an active material.
- FIG. 1 is a cross-sectional structural view schematically showing a cathode active material for a 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 is a lithium nickel manganese cobalt-based composite metal as a compound capable of reversible intercalation and deintercalation of lithium (lithiated intercalation compound).
- Oxide hereinafter, simply 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 is a lithium nickel manganese cobalt-based composite metal oxide as a compound capable of reversible intercalation and deintercalation of lithium (lithiated intercalation compound). (Hereinafter, simply 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 surface thereof.
- 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 forming a buffer layer having a three-dimensional network structure between the core and the shell in the active material particles by controlling the pH of the reactants in the preparation of the active material, Between the core 1 and the shell 2, a space is formed in the mesh structure to buffer 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 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 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 of particles using a focused ion beam (FIB) or mercury intrusion.
- the three-dimensional network structure (3b) is formed in the process of generating an inner core in the manufacture of the active material, is connected between the core and the shell between the core (1) and the shell (2) To support the space.
- the three-dimensional network structure 3b is a lithium nickel manganese as a compound capable of reversible intercalation and deintercalation of lithium, like the core 1 and the shell 2 (lithiated intercalation compound).
- Cobalt-based composite metal oxides hereinafter, simply referred to as 'third lithium composite metal oxide').
- the first to third lithium composite metal oxides in the core, the shell, and the buffer layer may each independently include a compound of Formula 1 below:
- M1 is any one or two or more elements selected from the group consisting of W, Mo and Cr
- M2 is any one selected from the group consisting of Al, Zr, Ti, Mg, Ta and Nb
- Or includes two or more elements, wherein 1.0 ⁇ a ⁇ 1.5, 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.03, 0 ⁇ w ⁇ 0.02, 0 ⁇ x + y ⁇ 1)
- composition of the compound of Formula 1 is the average composition of each of the first to third lithium composite metal oxides in the core, shell or buffer layer.
- 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.
- Ni may be included in an amount corresponding to 1-x-y, where 0 ⁇ x + y ⁇ 1. More specifically, in Chemical Formula 1, the content of Ni may be 0.3 ⁇ 1-x-y ⁇ 1. If 1-x-y is less than 0.3, the capacity characteristic may be lowered, and if it is more than 1, there is a fear of low temperature stability. In consideration of the excellent capacity characteristics and stability improvement effect of the Ni inclusion, it may be more specifically 0.3 ⁇ 1-x-y ⁇ 0.8.
- Co may be included in an amount corresponding to x, that is, 0 ⁇ x ⁇ 0.5.
- the content of Co in the lithium composite metal oxide of Chemical Formula 1 exceeds 0.5, there is a fear of increased cost.
- the Co may be included in more specifically 0.10 ⁇ x ⁇ 0.35.
- Mn can improve the structural stability of the active material, and as a result can improve the stability of the battery.
- the Mn may be included in an amount corresponding to y and in an amount of 0 ⁇ y ⁇ 0.5.
- y in the lithium composite metal oxide of Formula 1 exceeds 0.5, there is a concern that the output characteristics and capacity characteristics of the battery may be deteriorated.
- Mn may be included in an amount of 0.10 ⁇ y ⁇ 0.30 more specifically.
- M1 is any one or two or more elements selected from the group consisting of W, Mo, and Cr, and serves to suppress particle growth during the firing process during preparation of the active material particles.
- M1 may be present at a position where these elements should be present by substituting a part of Ni, Co, or Mn, or may react with lithium to form lithium oxide. Accordingly, by controlling the size of the crystal grains by adjusting the content of M1 and the timing of feeding, it is possible to further improve the output and life characteristics of the battery.
- M1 may be included in an amount of z, that is, 0 ⁇ z ⁇ 0.03.
- the crystal structure When the content of M1 exceeds 0.03, the crystal structure may be distorted or disintegrated, and the battery capacity may be reduced by preventing the movement of lithium ions. More specifically, considering the embodying the particle structure according to the M1 content control and the remarkable effect of improving the battery characteristics, it may be 0.005 ⁇ z ⁇ 0.01.
- elements of Ni, Co, and Mn in the lithium composite metal oxide of Formula 1 may be partially substituted or doped by another element, that is, M2, in order to improve battery characteristics by controlling distribution of metal elements in the active material.
- M2 may be any one or two or more elements specifically selected from the group consisting of Al, Zr, Ti, Mg, Ta, and Nb.
- Al an average oxidation number of the active material may be maintained to improve battery life characteristics.
- 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 positive electrode active material according to the embodiment of the present invention including the first to third lithium composite metal oxides having the above-mentioned composition has, on average, 1.0 ⁇ a ⁇ 1.5 and 0 ⁇ x ⁇ 0.5 in Chemical Formula 1 in the entire active material. , 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.03, 0 ⁇ w ⁇ 0.02, 0 ⁇ x + y ⁇ 0.5, more specifically 1.0 ⁇ a ⁇ 1.15, 0.10 ⁇ x ⁇ 0.35, 0.10 ⁇ y ⁇ Ni excess of compound 0.30, 0 ⁇ z ⁇ 0.03, 0 ⁇ w ⁇ 0.02, 0 ⁇ x + y ⁇ 0.4.
- the metal element of at least one of nickel, manganese, and cobalt included in the cathode active material 10 may exhibit a concentration gradient gradually changing in any one of the core, shell, and active material particles.
- nickel, cobalt and manganese contained in the positive electrode active material may increase or decrease while showing a concentration gradient gradually changing from the center of the positive electrode active material particles to the particle surface, or in the core and the cell, respectively.
- the concentration gradient slope of the metal element may be constant, that is, the slope value is one.
- the 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 cathode active material 20 atomic%, more specifically, it may be a difference of 1 atomic% to 10 atomic%.
- the concentration gradient structure and concentration of the metal in the positive electrode active material particles may be determined by using an Electron Probe Micro Analyzer (EPMA), Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP). -AES) or Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS), and more specifically, using EPMA from the center of the cathode active material to the surface. While moving, the atomic ratio of each metal can be measured.
- EPMA Electron Probe Micro Analyzer
- ICP Inductively Coupled Plasma-Atomic Emission Spectrometer
- -AES Inductively Coupled Plasma-Atomic Emission Spectrometer
- TOF-SIMS Time of Flight Secondary Ion Mass Spectrometry
- At least one metal element of nickel, manganese, and cobalt shows a concentration gradient that gradually changes throughout the active material particles, within the active material particles
- the gradient of the concentration gradient of the metal element of may represent one or more values.
- At least one of the metal elements of nickel, manganese, and cobalt has a concentration gradient gradually changing independently in the core and the shell, respectively,
- the gradients of concentration gradients of the metal elements in the shell may be the same or different from each other.
- the concentration of nickel contained in the positive electrode active material decreases with a gradual concentration gradient from the center of the active material particles toward the surface of the particles;
- each of the core and the shell may be independently reduced with a gradual 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 cathode active material particles to the surface, or in the core and the shell, respectively.
- the concentration of manganese contained in the positive electrode active material increases with a gradual concentration gradient from the center of the active material particles toward the surface of the particles;
- each of the core and the shell may be independently increased with a gradual concentration gradient from the center of the active material particles toward the surface of the particles.
- the concentration gradient of manganese may be constant from the center of the cathode active material particles to the surface, or in the core and the shell, respectively.
- the concentration of cobalt contained in the positive electrode active material increases with a gradual concentration gradient from the center of the active material particles toward the surface of the particles;
- each of the core and the shell may be independently increased with a gradual concentration gradient from the center of the active material particles toward the surface of the particles.
- the concentration gradient of the cobalt may be constant from the center of the cathode active material particles to the surface, or in the core and the shell, respectively.
- the content of nickel included in the core may be higher than the content of nickel included in the shell, and specifically, the core may include a metal element (lithium) included in the core.
- Nickel in an amount of at least 60 mol% and less than 100 mol% with respect to the total mole, and the shell is at least 30 mol% and less than 60 mol% with respect to the total moles of metal elements (excluding lithium) included in the shell. Nickel may be included.
- 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 gradually 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 gradual concentration gradient in the surface direction, and the cobalt and manganese concentrations may increase independently with a gradual concentration gradient from the center of the active material particles toward the surface.
- nickel, manganese, and cobalt each independently represent a gradually changing concentration gradient in the core and the shell, the concentration of nickel is the core and the core from the center of the core. Gradually decreasing from the interface of the buffer layer and from the interface of the buffer layer and the shell to the shell surface, and the cobalt and manganese concentrations are independently from the center of the core to the interface of the core and the buffer layer, and the buffer layer and the shell It can increase with a gradual concentration gradient from the interface of to the shell surface.
- the positive electrode active material having the above structure may have an average particle diameter (D 50 ) of 2 ⁇ m to 20 ⁇ m in consideration of the specific surface area and the positive electrode mixture density. If the average particle diameter of the positive electrode active material is less than 2 ⁇ m, there is a fear that the dispersibility in the active material layer is lowered due to aggregation between the positive electrode active materials. If the average particle diameter exceeds 20 ⁇ m, the mechanical strength and the specific surface area of the positive electrode active material may be reduced. In addition, considering the rate characteristic and initial capacity characteristics improvement effect due to the specific structure may have an average particle diameter (D 50 ) of 3 ⁇ m 15 ⁇ m.
- 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 according to an embodiment of the present invention may be measured using, for example, a laser diffraction method.
- the average particle diameter (D 50 ) of the positive electrode active material is about 28 kHz by dispersing the particles of the positive electrode active material in the dispersion medium, and then introduced into a commercially available laser diffraction particle size measuring apparatus (for example, Microtrac MT 3000). after a review of the output 60 W, it is possible to calculate the mean particle size (D 50) of from 50% based on the particle size distribution of the measuring device.
- the ratio of the core radius to the radius of the positive electrode active material is more 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 manganese in the active material particles is more optimized and controlled.
- the destruction of the positive electrode 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 positive electrode active material of the structure according to the embodiment of the present invention, the first transition metal containing solution containing a nickel raw material, cobalt raw material and manganese raw material, and the first transition metal containing solution at different concentrations Preparing a solution containing a second transition metal including a nickel raw material, a cobalt raw material, and a manganese raw material; (Step 1); The second transition to the first transition metal-containing solution so that the mixing ratio of the first transition metal-containing solution and the second transition metal-containing solution gradually changes from 100% by volume to 0% by volume to 100% by volume
- Step 2 And adding an ammonium cation-containing complex forming agent and a basic compound to the reaction solution until the pH of the reaction solution becomes higher than pH 8 and lower than pH 11 to grow the particles of the nickel manganese cobalt-based composite metal hydroxide (step) 3); And it may be prepared by a manufacturing method comprising a step (step 4) of mixing the grown nickel manganese cobalt-based composite metal hydroxide particles with a lithium-containing raw material.
- a method of manufacturing the cathode active material is provided.
- step 1 includes a first transition metal-containing solution including a nickel raw material, a cobalt raw material, and a manganese raw material, and the first transition.
- a second transition metal-containing solution including a nickel raw material, a cobalt raw material and a manganese raw material is prepared at a different concentration from the metal-containing solution.
- the second transition metal-containing solution may be prepared by the same method as the first transition metal-containing solution, except that the second transition metal-containing solution includes nickel, cobalt, and manganese at different concentrations from the first transition metal-containing solution.
- the first transition metal-containing solution and the second transition metal-containing solution are nickel raw material, cobalt raw material, manganese raw material, and optionally other raw materials of the metal (M1 or M2), wherein M1 is One, two or more elements selected from the group consisting of W, Mo, and Cr, and M2 is one or two or more elements selected from the group consisting of Al, Zr, Ti, Mg, Ta, and Nb), a solvent,
- it may be prepared by adding water or an organic solvent (specifically, alcohol, etc.) that can be mixed with water uniformly and water, or a solution containing each metal-containing raw material, specifically, an aqueous solution. It can also be used after mixing.
- metal-containing raw material of nickel, cobalt and manganese respective metal element-containing acetates, nitrates, sulfates, halides, sulfides, hydroxides, oxides, or oxyhydroxides can be used, and particularly limited so long as they can be dissolved in water. It doesn't work.
- 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.
- manganese raw material 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.
- the final precursor or active material further comprises M1 or M2 (wherein M1 is any one or two or more elements selected from the group consisting of W, Mo and Cr, M2 is Al, Zr, Ti, Mg , Ta, or Nb), any one or two or more elements selected from the group consisting of Ta, Nb, M1 or M2 containing raw material may be optionally further added in the preparation of the first and second transition metal-containing solution in step 1 .
- M1 is any one or two or more elements selected from the group consisting of W, Mo and Cr
- M2 is Al, Zr, Ti, Mg , Ta, or Nb
- any one or two or more elements selected from the group consisting of Ta, Nb, M1 or M2 containing raw material may be optionally further added in the preparation of the first and second transition metal-containing solution in step 1 .
- M1 or M2-containing raw material examples include acetates, nitrates, sulfates, halides, sulfides, hydroxides, oxides, or oxyhydroxides containing M1 or M2 elements. Can be used. For example, when M1 is W, tungsten oxide or the like may be used.
- the M1 and M2-containing raw materials may be used in a range to satisfy the content conditions of the M1 and M2 elements in the final precursor.
- step 2 the mixing ratio of the first transition metal-containing solution and the second transition metal-containing solution is 100% by volume: 0% by volume to 0% by volume: 100
- the second transition metal-containing solution was added to the first transition metal-containing solution so as to gradually change to volume%, and an ammonium cation-containing complex former and a basic compound were added to coprecipitate at pH 11 to pH 13 to obtain nickel.
- one coprecipitation reaction process includes nickel manganese cobalt-based composite metal hydroxide
- the nickel, cobalt and manganese may each independently prepare a precursor exhibiting a concentration gradient gradually changing from the center of the particle to the surface.
- the concentration gradient of the metal in the precursor and its slope can be easily controlled by the composition and the mixed feed ratio of the first transition metal-containing solution and the second transition metal-containing solution, the high density of the specific metal
- the rate of the second transition metal-containing solution added to the first transition metal-containing solution may be performed gradually increasing in the range of 1% to 30% compared to the initial charge rate.
- the input speed of the first transition metal-containing solution may be 150ml / hr to 210ml / hr
- the input speed of the second transition metal containing solution may be 120ml / hr to 180ml / hr
- the input speed range In the range of 1% to 30% of the initial charge rate within the input rate of the second transition metal-containing solution may be gradually increased.
- the reaction may be carried out at 40 °C to 70 °C.
- the size of the precursor and the cathode active material particles may be controlled by adjusting the supply amount and the reaction time of the second transition metal-containing solution to the first transition metal-containing solution. Specifically, it may be desirable to appropriately adjust the supply amount and the reaction time of the second transition metal-containing solution to have the cathode active material particle size as described above.
- the ammonium cation-containing complex forming agent is specifically NH 4 OH, (NH 4 ) 2 SO 4 , NH 4 NO 3 , NH 4 Cl, CH 3 COONH 4 , or NH 4 CO 3 , or the like.
- 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 mixture of the first and second transition metal-containing 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 for forming the particles of the transition metal-containing hydroxide may be carried out under the condition that the pH of the aqueous solution containing the raw material of the mixed transition metal is pH 11 to pH 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 aqueous solution containing the raw material of the transition metal may be performed under the condition of pH 11 to pH 12.
- 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 the measured 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 rate may be 100rpm to 2000rpm.
- a drying process may be optionally carried out, wherein the drying process may be carried out at 110 °C to 400 °C 15 hours to 30 hours.
- step 3 is a step of growing the particles of the nickel manganese cobalt-based composite metal hydroxide prepared in step 2.
- 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 nickel manganese cobalt-based composite metal hydroxide in the step 3 may be carried out at a lower pH than the particle generation step of the nickel manganese cobalt-based composite metal hydroxide in step 1, specifically, in step 2 It can be carried out in the range of pH 8 or more and less than pH 11, more specifically pH 8 to pH 10.5, lower than the pH of.
- the growth step of the nickel manganese cobalt-based composite metal hydroxide particles, the pH of the reactants at a rate of pH 1 to pH 2.5 per hour through the input rate control of the materials, specifically, the ammonium cation-containing complex forming agent and the basic compound It can be done in varying ways. As such, 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 nickel manganese cobalt-based composite metal hydroxide are formed, they may be added at the same rate, or gradually reduced with the addition rate. Can be. 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 nickel manganese cobalt-based composite metal hydroxide in the particle growth step was determined in the nickel manganese cobalt-based composite in step 2. It can be faster than the precipitation rate of the metal hydroxide. As a result, the density of the vicinity of the outer surface of the particles of the nickel manganese cobalt-based composite metal hydroxide serving as a precursor can be lowered to easily induce the grain growth direction during the subsequent heat treatment process.
- the crystals of the inside of the precursor particles and the outside of the particles formed by the subsequent growth of particles through the control of the above conditions have different properties. Accordingly, during the preparation of the cathode active material using the precursor, the internal crystals made when the pH is high during the heat treatment process after mixing with the lithium raw material shrinks, and the crystals made at the low pH and temperature grow, thereby shrinking the crystals. Silver cores are formed, and outwardly grown crystals form shells, and the formation of such cores and shells forms voids between the cores and the shells, while crystals located between the cores and the shells are characterized by The three-dimensional network structure connecting the outside will be formed.
- step 3 may be carried out in an inert atmosphere.
- the process of separating the particles of the grown nickel manganese cobalt-based composite metal hydroxide from the reaction solution and optionally washing and drying may be further performed.
- 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.
- a heat treatment process for the particles of the grown nickel manganese cobalt-based composite metal hydroxide may be selectively performed.
- the heat treatment process for the particles of the nickel manganese cobalt-based composite metal hydroxide may be performed in an air atmosphere or an oxidation atmosphere (for example, O 2, etc.), and more specifically, may be performed under an oxidation atmosphere.
- the heat treatment process may be performed at 250 °C to 1000 °C. 5 hours to 48 hours, or 10 hours to 20 hours at the above temperature conditions.
- the heat treatment process may be carried out in two or three stages of multi-stage to maintain the concentration gradient and grain orientation. Specifically, it may be carried out by a method of maintaining 5 to 15 hours at 250 ° C to 450 ° C, 5 to 15 hours at 450 ° C to 600 ° C, and 5 to 15 hours at 700 ° C to 900 ° C.
- a moisture removing agent may be optionally further added to the nickel manganese cobalt-based composite metal hydroxide.
- 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 mol to 0.2 mol based on 1 mol of nickel manganese cobalt-based composite metal hydroxide.
- the crystallization structure of the core-shell in the particles of the nickel manganese cobalt-based composite metal hydroxide produced and grown through the steps 2 and 3 by the above heat treatment process and the concentration gradient of the metal element are fixed.
- the crystals outside the particles grow radially from the center of the particles to the outside, i.e., the surface direction, to further fix the crystal orientation.
- the core As a result of the above manufacturing process, the core; And a shell surrounding the core, wherein the core and the shell each independently include a lithium nickel manganese cobalt-based composite metal oxide, and at least one metal element of the nickel, manganese, and cobalt is the core.
- Precursors are prepared that are useful for the preparation of positive electrode active materials that exhibit a gradually changing concentration gradient within any of the regions of the shell and the precursor.
- a cathode active material precursor prepared by the manufacturing method is provided.
- the precursor may include nickel manganese cobalt-based composite metal hydroxide of the formula (2).
- M1 is any one or two or more elements selected from the group consisting of W, Mo and Cr
- M2 is any one selected from the group consisting of Al, Zr, Ti, Mg, Ta and Nb
- two or more elements 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.03, 0 ⁇ w ⁇ 0.02, 0 ⁇ x + y ⁇ 1, and more specifically 0 ⁇ x ⁇ 0.5 , 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.03, 0 ⁇ w ⁇ 0.02, 0 ⁇ x + y ⁇ 0.7 and more specifically 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0.002 ⁇ z ⁇ 0.03 , 0 ⁇ w ⁇ 0.02, 0 ⁇ x + y ⁇ 0.4)
- composition of the nickel manganese cobalt-based composite metal hydroxide of Chemical Formula 2 is an average composition of the entire precursor.
- the precursor includes a core and a shell surrounding the core, wherein the core and the shell each independently include the nickel-manganese-cobalt-based composite metal oxide of Formula 1, wherein the nickel and manganese And at least one metal element of cobalt indicates a concentration gradient that gradually changes in any one of the core, shell, and precursor particles as a whole, and the nickel manganese cobalt-based composite metal hydroxide included in the shell is a precursor particle. Radial crystal orientation from the center of the surface to the surface direction.
- the precursor may be further positioned between the core and the shell according to the conditions during the heat treatment process, and may further include a buffer layer including a three-dimensional network structure and voids connecting the core and the shell.
- nickel, cobalt, and manganese contained in the precursor may increase or decrease from the center of the precursor particles to the particle surface, or gradually showing a concentration gradient in the core and the cell, respectively.
- the concentration gradient slope of the metal element may be constant.
- the concentration of the metal gradually shows a concentration gradient" in the precursor means that the concentration of the metal is present in a concentration distribution that gradually changes throughout the precursor particles.
- the concentration distribution is 0.1 atomic% to 30 atomic%, more specifically 0.1 atomic% to 20 atomic percent, based on the total atomic weight of the metal included in the precursor, the change in the metal concentration per micrometer in the particles, respectively Atomic%, more specifically, may be a difference of 1 atomic% to 10 atomic%.
- the concentration gradient structure and concentration of the metal in the precursor particles may be determined by using an Electron Probe Micro Analyzer (EPMA), Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP-). AES) or Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS), and more specifically, using EPMA to move from the center of the precursor to the surface.
- EPMA Electron Probe Micro Analyzer
- ICP- Inductively Coupled Plasma-Atomic Emission Spectrometer
- TOF-SIMS Time of Flight Secondary Ion Mass Spectrometry
- step 4 the particles of the nickel manganese cobalt-based composite metal hydroxide grown in the step 3 is mixed with a raw material containing lithium and heat-treated to interpose the core- It is a step of preparing a cathode active material having a shell formed structure.
- lithium-containing raw material examples include lithium-containing carbonates (for example, lithium carbonate), hydrates (for example, lithium hydroxide I hydrate (LiOH ⁇ H 2 O), and the like), hydroxides (for example, lithium hydroxide, etc.) , Nitrates (e.g., lithium nitrate (LiNO 3 ), etc.), chlorides (e.g., lithium chloride (LiCl), etc.), and the like.
- the amount of the lithium-containing raw material may be determined according to the content of lithium and transition metal in the final lithium composite metal oxide.
- a sintering agent may be optionally further added.
- the sintering agent is specifically a compound containing ammonium ions such as NH 4 F, NH 4 NO 3 , or (NH 4 ) 2 SO 4 ; Metal oxides such as B 2 O 3 or Bi 2 O 3 ; Or a metal halide such as NiCl 2 or CaCl 2, and any one or a mixture of two or more thereof may be used.
- the sintering agent may be used in an amount of 0.01 mol to 0.2 mol with respect to 1 mol of the precursor.
- the effect of improving the sintering characteristics of the precursor may be insignificant, and when the content of the sintering agent is too high, exceeding 0.2 mole, the performance of the cathode active material is reduced and filled due to the excess sintering agent. There is a fear that the initial capacity of the battery may decrease during discharge progression.
- a moisture removing agent may be optionally further added.
- 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 to 0.2 mole based on 1 mole of the precursor.
- the heat treatment process for the mixture of the particles of the nickel manganese cobalt-based composite metal hydroxide and the raw material containing lithium can be performed in an air atmosphere or an oxidizing atmosphere (for example, O 2 ), and more specifically, under an oxidizing atmosphere. Can be performed.
- the heat treatment process may be performed at 250 °C to 1000 °C. 5 hours to 48 hours, or 10 hours to 20 hours at the above temperature conditions.
- the heat treatment process may be performed in two or three stages by adding a low-temperature firing process to maintain the concentration gradient and grain orientation. Specifically, it may be carried out by a method of maintaining 5 to 15 hours at 250 ° C to 450 ° C, 5 to 15 hours at 450 ° C to 600 ° C, and 5 to 15 hours at 700 ° C to 900 ° C.
- the particles of the nickel manganese cobalt-based composite metal hydroxide produced and grown through the above steps 2 and 3 may be formed inside the particles and outside the particles formed by the subsequent growth of particles due to differences in process conditions, ie, pH, during the manufacturing process.
- Crystals have different properties. That is, the internal crystals made when the pH is high shrinks during the heat treatment process as described above, and the crystals made at low pH and temperature grow. As a result, the shrunken crystals form a core, and the outgrown crystals form a shell, and the formation of such cores and shells forms voids between the cores and the shells, while crystals located between the cores and the shells. Is to form a three-dimensional network structure connecting the inside and the outside of the particles. In addition, the crystals outside the particles grow radially outward from the center of the particles to have crystal orientation.
- the positive electrode active material prepared according to the above-described manufacturing method includes a buffer layer containing pores between the core and the shell by controlling the pH, concentration and rate of the reactants, so that there is no fear of destroying the active material during rolling in the electrode manufacturing process, Reactivity with the electrolyte is maximized, and the particles forming the shell have a crystal structure of an orientation that facilitates insertion and removal of lithium ions, thereby improving resistance and lifespan 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.
- a cathode and a lithium secondary battery including the cathode active material are provided.
- 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 change in the battery.
- carbon, nickel, titanium on the surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or 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, a nonwoven body.
- the cathode active material layer may include 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, thermal 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 typically be included in an amount of 1% to 30% by weight based on 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.
- the positive electrode active material and optionally, a composition for forming a positive electrode active material layer including a binder and a conductive material may be prepared by applying a positive electrode current collector, followed by drying and rolling.
- 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 or a capacitor, and more specifically, may be 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 similarly to the positive electrode current collector, fine concavities and convexities may be formed on the surface of the current collector to enhance the bonding force of the negative electrode active material.
- it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
- 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; Dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate, Carbonate solvents such as PC); Alcohol solvents such as ethyl alcohol and isopropyl alcohol; Nitriles such as R-CN (R is a C2 to C20 linear, branched or cyclic hydrocarbon group, which may include
- 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.
- cyclic carbonate and the chain carbonate are mixed and used in a volume ratio of about 1: 1 to 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 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 .
- LiCl, LiI, or LiB (C 2 O 4 ) 2 and the like can be used.
- the concentration of the lithium salt is preferably used within the range of 0.1M to 2.0M. When the concentration of the lithium salt is included in the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can move effectively.
- the electrolyte includes, in addition to the electrolyte components, haloalkylene carbonate-based compounds such as difluoroethylene carbonate for the purpose of improving the life characteristics of the battery, suppressing the reduction of the battery capacity, and improving the discharge capacity of the battery; Or pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N
- One or more additives such as -substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol or aluminum trichloride may be included. In this case, the additive may be included in an amount of 0.1% by weight to 5% by weight based on the total weight of the electrolyte.
- the 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.
- the precursor according to an embodiment of the present invention the first transition metal containing solution containing a nickel raw material, cobalt raw material and manganese raw material, and the first transition metal containing solution at different concentrations
- a second transition metal-containing solution including a nickel raw material, a cobalt raw material, and a manganese raw material (step 2-1); The second transition to the first transition metal-containing solution so that the mixing ratio of the first transition metal-containing solution and the second transition metal-containing solution gradually changes from 100% by volume to 0% by volume to 100% by volume
- Step 2-2 Adding an ammonium cation-containing complex forming agent and a basic compound to the reaction solution until the pH of the reaction solution is above pH 8 and below pH 11 to grow particles of the nickel manganese cobalt-based composite metal hydroxide (step 2 It can be prepared by a manufacturing method comprising -3).
- steps 2-1 to 2-3 may be performed by the same method as steps 1 to 3 in the method for preparing the positive electrode active material, and thus detailed description thereof will be omitted.
- the core As a result of the above manufacturing process, the core; And a shell surrounding the core, wherein the core and the shell each independently include a nickel manganese cobalt-based composite metal hydroxide, and at least one metal element of the nickel, manganese, and cobalt includes the core,
- Precursors useful for the preparation of the positive electrode active material described above are prepared, which exhibit a gradually changing concentration gradient within the region of either the shell and the precursor as a whole.
- the precursor may include nickel manganese cobalt-based composite metal hydroxide of the formula (2).
- M1 is any one or two or more elements selected from the group consisting of W, Mo and Cr
- M2 is any one selected from the group consisting of Al, Zr, Ti, Mg, Ta and Nb
- two or more elements 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.03, 0 ⁇ w ⁇ 0.02, 0 ⁇ x + y ⁇ 1, and more specifically 0 ⁇ x ⁇ 0.5 , 0 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.03, 0 ⁇ w ⁇ 0.02, 0 ⁇ x + y ⁇ 0.7 and more specifically 0 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.5, 0.002 ⁇ z ⁇ 0.03 , 0 ⁇ w ⁇ 0.02, 0 ⁇ x + y ⁇ 0.4)
- the precursor includes a core and a shell positioned surrounding the core, wherein the core and the shell each independently include the nickel manganese cobalt-based composite metal hydroxide of Formula 2, and the nickel, manganese, and cobalt At least one of the metal elements, the concentration gradient gradually changes in the region of any one of the core, shell and precursor, the nickel manganese cobalt-based composite metal hydroxide contained in the shell is at the center of the precursor particles It has radial crystal orientation in the surface direction.
- the precursor may be further positioned between the core and the shell according to the conditions during the heat treatment process, and may further include a buffer layer including a three-dimensional network structure and voids connecting the core and the shell.
- nickel, cobalt, and manganese contained in the precursor may increase or decrease from the center of the precursor particles to the particle surface, or gradually showing a concentration gradient in the core and the cell, respectively.
- the concentration gradient slope of the metal element may be constant.
- at least one metal element of nickel, manganese and cobalt shows a concentration gradient that gradually changes throughout the precursor particles,
- the gradient of concentration gradient of the metal element in the precursor particles may exhibit one or more values.
- At least one of the metal elements of nickel, manganese, and cobalt has a concentration gradient which gradually changes independently in the core and the shell, respectively, and the concentration gradient of the metal elements in the core and the shell.
- the slopes may be the same or different from each other.
- the concentration of nickel contained in the precursor gradually decreases with a concentration gradient from the center of the precursor particles toward the surface of the particles;
- each may gradually decrease while having a concentration gradient from the center of the precursor particles to the surface of the particles.
- the gradient of the concentration gradient of nickel may be constant from the center to the surface of the precursor particles, or in the core and the shell, respectively.
- the concentration of manganese contained in the precursor is gradually increased with a concentration gradient from the center of the precursor particles to the surface of the particles;
- the concentration may gradually increase in the core and the shell, each having a concentration gradient from the center of the precursor particle to the surface of the particle.
- the concentration gradient of manganese may be constant from the center to the surface of the precursor particles, or in the core and the shell, respectively.
- the concentration of cobalt in the precursor is gradually increased while having a concentration gradient from the center of the precursor particles toward the surface of the particles;
- the concentration may gradually increase in the core and the shell, each having a concentration gradient from the center of the precursor particle to the surface of the particle.
- the concentration gradient slope of the precursor may be constant from the center to the surface of the precursor particles, or in the core and the shell, respectively.
- the content of nickel included in the core may be higher than the content of nickel included in the shell, and specifically, the total moles of metal elements included in the core under the core and nickel content in the shell.
- the nickel may be included in an amount of at least 70 mol% and less than 100 mol%, and the shell may include nickel in an amount of 30 mol% or more and less than 75 mol% based on the total moles of 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 gradually changing concentration gradient throughout the precursor particles, and the concentration of the nickel is gradually increasing while having a concentration gradient from the center of the precursor particles to the surface direction. And the concentrations of cobalt and manganese may gradually increase, each independently having a concentration gradient from the center of the precursor particles toward the surface.
- the capacity characteristics of the positive electrode active material in the preparation of the positive electrode active material include a combined concentration gradient in which the concentration of nickel decreases and the concentration of manganese and cobalt increases toward the surface side of the precursor particles in part or in whole. It can improve thermal stability while maintaining
- the precursor may have an average particle diameter (D 50 ) of 3 ⁇ m to 20 ⁇ m in consideration of the specific surface area of the positive electrode active material and the positive electrode mixture density. If the average particle diameter (D 50 ) of the precursor is less than 3 ⁇ m, coagulation between precursors may occur. If the average particle diameter (D 50 ) is more than 20 ⁇ m, there is a fear that the mechanical strength and specific surface area of the precursor may be reduced. In addition, considering the effect of improving the rate characteristics and initial capacity characteristics of the positive electrode active material due to its specific structure may have an average particle diameter (D 50 ) of 3 ⁇ m to 15 ⁇ m.
- the average particle diameter (D 50 ) of the precursor may be defined as the particle size at 50% of the particle size distribution.
- the average particle diameter (D 50 ) of the precursor particles may be measured using, for example, a laser diffraction method, more specifically, after dispersing the precursor particles in a dispersion medium, commercially available laser diffraction particle sizes Introduced into a measuring device (e.g., Microtrac MT 3000), an ultrasonic wave of about 28 kHz can be irradiated with an output of 60 W, and the average particle diameter (D 50 ) at 50% of the particle size distribution in the measuring device can be calculated. have.
- the core may be secondary particles in which primary particles of nickel manganese cobalt-based composite metal hydroxides are aggregated.
- the ratio of the core radius to the radius of the precursor particles is greater than 0 and less than 0.5, more specifically greater than 0 and less than 0.4, even more specifically 0.01 to 0.2, or 0.1 to 0.2.
- the shell region determined according to the following equation (2) is 0.2 to 1, more specifically 0.25 to 0.7, more specifically May be 0.5 to 0.6.
- Shell area (curve radius-core radius) / curve radius
- the core and the shell in the precursor are formed at the above-mentioned ratio, and the concentration gradient of the metal element is formed in each region, the distribution of nickel, cobalt and manganese in the active material particles is more optimized and controlled, thereby producing the electrode.
- the distribution of nickel, cobalt and manganese in the active material particles is more optimized and controlled, thereby producing the electrode.
- 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 precursor prepared by the manufacturing method according to an embodiment of the present invention has improved mechanical strength by controlling the distribution of intraparticle nickel, cobalt and manganese in particles having a core-shell structure, Destruction of the active material by the rolling process during electrode production can be minimized. Further, due to the difference in density between the core and the shell, the buffer layer of the three-dimensional network structure connected to the core and the shell is further formed during the heat treatment for the preparation of the positive electrode active material, so that the unique structure including the three-dimensional network structure and the voids in the buffer layer. Reactivity between the active material and the electrolyte can be maximized, and the shell-forming particles can improve the output characteristics and lifespan characteristics of the secondary battery by having a crystal structure with an orientation that facilitates insertion and removal of lithium ions. .
- nickel sulfate, cobalt sulfate and manganese sulfate were mixed in water in an amount such that the molar ratio of nickel: cobalt: manganese was 40:30:30 in water at a 2M concentration.
- a metal containing solution was prepared.
- the vessel containing the first transition metal containing solution was connected to enter the reactor, and the vessel containing the second transition metal containing solution was connected to enter the first transition metal containing solution container.
- 4M NaOH solution and 7% NH 4 OH aqueous solution were prepared and connected to the reactor, respectively.
- the first transition metal-containing solution 180 ml / hr of the first transition metal-containing solution, 180 ml / hr of NaOH aqueous solution, and NH 4 OH aqueous solution were added at a rate of 10 ml / hr to react for 30 minutes to form a seed of nickel manganese cobalt-based composite metal hydroxide. . Afterwards, the amount of NH 4 OH and NaOH is gradually decreased, and the pH is lowered at a rate of pH 2 per hour to change the pH to 9.5. At the same time, the second transition metal-containing solution is 150ml into the container of the first transition metal-containing solution.
- nickel cobalt manganese-based composite metal hydroxide particles were added to induce the growth of nickel cobalt manganese-based composite metal hydroxide particles and at the same time induced a concentration gradient inside the 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-containing hydroxide particles were separated and washed with water and dried in an oven at 120 °C to prepare a precursor.
- the precursor prepared above was mixed with lithium hydroxide as a lithium raw material at a molar ratio of 1: 1.07, and then heat-treated at 300 ° C. for 10 hours, at 500 ° C. for 10 hours, and at 820 ° C. for 10 hours to prepare a cathode active material.
- nickel sulfate, cobalt sulfate, manganese sulfate and magnesium sulfate were mixed in water so that the molar ratio of nickel: cobalt: manganese: magnesium was 40: 30: 30: 0.02 to 2M.
- the second transition metal containing solution was prepared.
- the vessel containing the first transition metal containing solution was connected to enter the reactor, and the vessel containing the second transition metal containing solution was connected to enter the vessel of the first transition metal containing solution.
- 4M NaOH solution and 7% NH 4 OH aqueous solution were prepared and connected to the reactor, respectively.
- the resulting nickel manganese cobalt-based composite metal hydroxide particles were separated and washed with water and dried in an oven at 120 °C to prepare a precursor.
- the precursor particles prepared above were mixed with lithium hydroxide as a lithium raw material in a molar ratio of 1: 1.07, and then heat-treated at 300 ° C. for 10 hours, at 500 ° C. for 10 hours, and at 820 ° C. for 10 hours to prepare respective cathode active materials. .
- Heat treatment at 500 ° C. for 10 hours and 10 hours at 820 ° C. includes a tungsten-doped lithium composite metal oxide, and a cathode active material in which nickel, cobalt, and manganese in the lithium composite metal oxide has a concentration gradient is prepared.
- the lithium transition metal oxide constituting the cathode active material is LiNi 0 . 6 Mn 0 . 2 Co 0 .
- Nickel sulfate, cobalt sulfate, and manganese sulfate were each added in water so as to have a composition of 2 O 2 , thereby preparing a transition metal-containing solution.
- the total concentration of the transition metal-containing solution in the aqueous solution was connected to enter the reactor to be 2M.
- 4M NaOH solution and 7% aqueous NH 4 OH solution were prepared and connected to the reactor, respectively.
- the resulting nickel manganese cobalt composite metal hydroxide particles were separated and washed with water and dried in an oven at 120 ° C.
- the nickel manganese cobalt composite metal hydroxide particles prepared above were mixed with lithium hydroxide as a lithium raw material at a molar ratio of 1: 1.07, and then heat-treated at 850 ° C. for 15 hours to prepare a cathode active material.
- a lithium secondary battery was manufactured using the cathode active materials prepared in Examples 1 to 3 and Reference Example 1, respectively.
- the cathode active material, the carbon black conductive material and the PVdF binder prepared in Examples 1 to 3 and Reference Example 1 were mixed in a ratio of 95: 2.5: 2.5 by weight in an N-methylpyrrolidone solvent to form a cathode.
- the composition (viscosity: 5000 mPa * s) was produced, this was apply
- 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.
- Example 1 The precursor prepared in Example 1 was observed by field emission scanning electron microscopy (FE-SEM), and the diameters and volumes of the core and the shell, and the volume ratio in the precursor were calculated from the results. The results are shown in FIG. 2 and Table 1 below. The values in Table 1 below are mean values.
- 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 porosity of the buffer layer 3 in the positive electrode active material was about 10% by volume relative to the total thickness of the positive electrode active material.
- Example 2 the precursor prepared in Example 1 was subjected to component analysis using EPMA, and the results are shown in Table 2 below.
- the concentration of Ni decreases from the center of the precursor particles to the surface, and the concentration of Co and Mn is included as an increasing concentration gradient.
- the positive electrode active material prepared in Example 1 was subjected to component analysis using EPMA. The results are shown in Table 3 below.
- the coin cell (using a cathode of Li metal) prepared using the cathode active materials prepared in Examples 1 and 1 was charged at 25 ° C. until a constant current (CC) of 4.25V was reached at 4.25V, and then 4.25V.
- the battery was charged at a constant voltage (CV) of and charged for the first time until the charging current became 0.05 mAh. Thereafter, it was left for 20 minutes and then discharged until it became 3.0V with a constant current of 0.1C.
- Discharge capacity of the 1st cycle was measured using the said charge and discharge as 1 cycle. Then, the charge and discharge capacity, charge and discharge efficiency and rate characteristics were evaluated by varying the discharge conditions at 2C. The results are shown in Table 4 below.
- the lithium secondary battery including the positive electrode active material of Example 1 showed the same level of effect in terms of charge and discharge efficiency and rate characteristics compared to the lithium secondary battery containing the positive electrode active material of Reference Example 1, but in terms of capacity characteristics Showed a more improved effect.
- the battery characteristics of the lithium secondary battery including the cathode active material in Example 1 and Reference Example 1 were evaluated in the following manner.
- the lithium secondary battery was charged / discharged under a condition of 1C / 2C within a range of 2.8 to 4.15V driving voltage at a temperature of 25 ° C. At this time, 800 cycles of charge / discharge were performed under the above conditions, with one charge and one discharge as one cycle.
- 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 cycles of charge and discharge at room temperature.
- Example 1 1.25 1.15 95.4 Reference Example 1 1.48 1.42 93.7
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Abstract
Description
길이(㎛) | 부피(㎛3) | 전구체내 내 부피 비율 (부피%) | |
코어 | 0.94 (코어 반지름) | 3.5 | 10.0 |
쉘 | 1.085 (쉘 두께) | 31.3 | 90.0 |
전체 | 2.025 (전구체 반지름) | 34.8 | 100 |
Scan | Ni(mol%) | Co(mol%) | Mn(mol%) | |
코어 | 01 | 75 | 14 | 11 |
02 | 75 | 14 | 11 | |
쉘 | 03 | 71 | 17 | 14 |
04 | 59 | 20 | 17 | |
05 | 56 | 23 | 21 | |
전체 | 61 | 22 | 17 |
Scan | Ni(mol%) | Co(mol%) | Mn(mol%) | |
코어 | 01 | 68 | 18 | 4 |
완충층 | 02 | 65 | 20 | 8 |
쉘 | 03 | 62 | 21 | 12 |
04 | 60 | 22 | 16 | |
05 | 58 | 24 | 19 | |
전체 | 60 | 23 | 17 |
제1충방전 | 2C rate | ||||
충전용량(mAh/g) | 방전용량(mAh/g) | 충방전 효율(%) | 용량(mAh/g) | 2.0C/0.1C (%) | |
실시예1 | 196.3 | 180.9 | 92.1 | 162.8 | 89.9 |
참고예1 | 193.4 | 178.0 | 92.1 | 159.3 | 89.8 |
상온(25℃) 저항(mohm) | 저온(-30℃) 저항(V) | 상온(25℃)에서의 800 사이클 용량유지율 (%) | |
실시예1 | 1.25 | 1.15 | 95.4 |
참고예1 | 1.48 | 1.42 | 93.7 |
Claims (29)
- 이차전지용 양극활물질로서,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 리튬 니켈망간코발트계 복합금속 산화물을 포함하고,상기 니켈, 망간 및 코발트 중 적어도 어느 하나의 금속원소는, 상기 코어, 쉘 및 양극활물질 전체 중 어느 하나의 영역 내에서 점진적으로 변화하는 농도구배를 나타내는 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 니켈, 망간 및 코발트 중 적어도 어느 하나의 금속원소는 코어 및 쉘 내에서 각각 독립적으로 점진적으로 변화하는 농도구배를 나타내고,상기 코어 및 쉘 내에서의 금속원소의 농도구배 기울기 값이 서로 다른 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 니켈, 망간 및 코발트 중 적어도 어느 하나의 금속원소는 코어 및 쉘 내에서 각각 독립적으로 점진적으로 변화하는 농도구배를 나타내고,상기 코어 및 쉘 내에서의 금속원소의 농도구배 기울기 값이 서로 동일한 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 망간의 함량이 쉘 내에 포함되는 망간의 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 코어는 코어 내 포함되는 금속 원소(단, 리튬 제외) 총 몰에 대하여 60몰% 이상 100몰% 미만의 함량으로 니켈을 포함하고,상기 쉘은 쉘 내 포함되는 금속 원소(단, 리튬 제외) 총 몰에 대하여 30몰% 이상 60몰% 미만의 함량으로 니켈을 포함하는 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 니켈, 망간 및 코발트는 양극활물질 입자 전체에 걸쳐 각각 독립적으로 점진적으로 변화하는 농도구배를 나타내고,상기 니켈의 농도는 양극활물질 입자의 중심에서부터 표면 방향으로 점진적인 농도구배를 가지면서 감소하고, 그리고상기 코발트 및 망간의 농도는 각각 독립적으로 양극활물질 입자의 중심에서부터 표면 방향으로 점진적인 농도구배를 가지면서 증가하는 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 니켈, 망간 및 코발트는 코어 및 쉘 내에서 각각 독립적으로 점진적으로 변화하는 농도구배를 나타내고,상기 니켈의 농도는 코어의 중심에서부터 코어와 완충층의 계면까지, 그리고 완충층과 쉘의 계면에서부터 쉘 표면까지 점진적인 농도구배를 가지면서 감소하고, 그리고상기 코발트 및 망간의 농도는 각각 독립적으로 코어의 중심에서부터 코어와 완충층의 계면까지, 그리고 완충층과 쉘의 계면에서부터 쉘 표면까지 점진적인 농도구배를 가지면서 증가하는 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 코어는 리튬 니켈망간코발트계 복합금속 산화물의 1차 입자가 응집된 2차 입자인 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 완충층내 공극율은 양극활물질 총 부피에 대하여 30부피% 이하인 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 쉘은 양극활물질의 중심에서 표면 방향으로 방사형으로 성장된 결정배향성의 리튬 니켈망간코발트계 복합금속 산화물의 입자를 포함하는 것인 이차전지용 양극활물질.
- 제1항에 있어서,상기 코어, 쉘 및 완충층에 있어서의 리튬 니켈망간코발트계 복합금속 산화물은 각각 독립적으로 하기 화학식 1의 화합물을 포함하는 것인 이차전지용 양극활물질.[화학식 1]LiaNi1-x-yCoxMnyM1zM2wO2(상기 화학식 1에서, M1은 W, Mo 및 Cr로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상의 원소를 포함하고, M2는 Al, Zr, Ti, Mg, Ta 및 Nb로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상의 원소를 포함하며, 1.0≤a≤1.5, 0<x≤0.5, 0<y≤0.5, 0≤z≤0.03, 0≤w≤0.02, 0<x+y<1이다)
- 제1항에 있어서,상기 양극활물질의 반지름에 대한 코어 반지름의 비가 0 초과 0.4 미만이고, 상기 양극활물질의 반지름에 대한, 양극활물질 중심에서 완충층과 쉘의 계면까지의 길이의 비가 0 초과 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,3㎛ 내지 20㎛의 평균 입자 직경을 갖는 것인 이차전지용 양극활물질.
- 니켈 원료물질, 코발트 원료물질 및 망간 원료물질을 포함하는 제1전이금속 함유 용액, 및 상기 제1전이금속 함유 용액과는 서로 다른 농도로 니켈 원료물질, 코발트 원료물질 및 망간 원료물질을 포함하는 제2전이금속 함유 용액을 준비하는 단계;상기 제1전이금속 함유 용액과 상기 제2전이금속 함유 용액의 혼합 비율이 100부피%:0부피%에서 0부피%:100부피%까지 점진적으로 변화되도록 상기 제1전이금속 함유 용액에 상기 제2전이금속 함유 용액을 첨가하는 동시에, 암모늄 양이온 함유 착물 형성제와 염기성 화합물을 첨가하여 pH 11 내지 pH 13에서 공침반응시켜, 니켈망간코발트계 복합금속 수산화물의 입자가 생성된 반응용액을 준비하는 단계;상기 반응용액에 암모늄 양이온 함유 착물 형성제와 염기성 화합물을 상기 반응용액의 pH가 8 이상 pH 11 미만이 될 때까지 첨가하여 상기 니켈망간코발트계 복합금속 수산화물의 입자를 성장시키는 단계; 그리고상기 성장된 니켈망간코발트계 복합금속 함유 수산화물의 입자를 리튬 함유 원료물질과 혼합한 후 열처리하는 단계를 포함하는, 제1항에 따른 이차전지용 양극활물질의 제조방법.
- 제17항에 있어서,니켈망간코발트계 복합금속 함유 수산화물의 입자가 생성된 반응용액의 준비 단계는 40℃ 내지 70℃에서 수행되는 것인 이차전지용 양극활물질의 제조방법.
- 제17항에 있어서,상기 암모늄 양이온 함유 착물 형성제는 NH4OH, (NH4)2SO4, NH4NO3, NH4Cl, CH3COONH4, 및 NH4CO3로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상의 혼합물을 포함하는 것인 이차전지용 양극활물질의 제조방법.
- 제17항에 있어서,상기 염기성 화합물은 알칼리 금속의 수화물, 알칼리 금속의 수산화물, 알칼리 토금속의 수화물 및 알칼리 토금속의 수산화물로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상의 혼합물을 포함하는 것인 이차전지용 양극활물질의 제조방법.
- 제17항에 있어서,상기 니켈망간코발트계 복합금속 함유 수산화물의 입자의 성장 단계는 반응물의 pH를 시간당 pH 1 내지 pH 2.5의 속도로 변화시키며 수행되는 것인 이차전지용 양극활물질의 제조방법.
- 제17항에 있어서,상기 열처리가 250℃ 내지 1000℃의 온도에서 실시되는 것인 이차전지용 양극활물질의 제조방법.
- 제17항에 있어서,상기 열처리가 250℃ 내지 450℃에서 5 내지 15시간 동안의 제1열처리, 450℃ 내지 600℃에서 5 내지 15시간 동안의 제2열처리, 그리고 700℃ 내지 900℃에서 5 내지 15시간 동안의 제3열처리를 포함하는 다단계 열처리 방법에 의해 수행되는 것인 이차전지용 양극활물질의 제조방법.
- 제1항에 따른 양극활물질을 포함하는 이차전지용 양극.
- 제24항에 따른 양극을 포함하는 리튬 이차전지.
- 니켈 원료물질, 코발트 원료물질 및 망간 원료물질을 포함하는 제1전이금속 함유 용액, 및 상기 제1전이금속 함유 용액과는 서로 다른 농도로 니켈 원료물질, 코발트 원료물질 및 망간 원료물질을 포함하는 제2전이금속 함유 용액을 준비하는 단계;상기 제1전이금속 함유 용액과 상기 제2전이금속 함유 용액의 혼합 비율이 100부피%:0부피%에서 0부피%:100부피%까지 점진적으로 변화되도록 상기 제1전이금속 함유 용액에 상기 제2전이금속 함유 용액을 첨가하는 동시에, 암모늄 양이온 함유 착물 형성제와 염기성 화합물을 첨가하여 pH 11 내지 pH 13에서 공침반응시켜, 니켈망간코발트계 복합금속 수산화물의 입자가 생성된 반응용액을 준비하는 단계; 및상기 반응용액에 암모늄 양이온 함유 착물 형성제와 염기성 화합물을 상기 반응용액의 pH가 pH 8 이상, pH 11 미만이 될 때까지 첨가하여 상기 니켈망간코발트계 복합금속 수산화물의 입자를 성장시키는 단계를 포함하는, 제1항에 따른 이차전지용 양극활물질의 전구체를 제조하는 방법.
- 이차전지용 양극활물질의 전구체로서,코어, 및 상기 코어를 둘러싸며 위치하는 쉘을 포함하며,상기 코어 및 쉘은 각각 독립적으로 니켈망간코발트계 복합금속 수산화물을 포함하고,상기 니켈, 망간 및 코발트 중 적어도 어느 하나의 금속원소는, 상기 코어, 쉘 및 전구체 전체 중 어느 하나의 영역 내에서 점진적으로 변화하는 농도구배를 나타내며,상기 쉘 내 포함되는 니켈망간코발트계 복합금속 수산화물은 전구체 입자의 중심에서 표면 방향으로의 방사형의 결정배향성을 갖는 것인 이차전지용 양극활물질의 전구체.
- 제27항에 있어서,상기 니켈망간코발트계 복합금속 수산화물은 하기 화학식 2의 화합물을 포함하는 것인 이차전지용 양극활물질의 전구체.[화학식 2]Ni1-x-yCoxMnyM1zM2wOH(상기 화학식 2에서, M1은 W, Mo 및 Cr로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상의 원소를 포함하고, M2는 Al, Zr, Ti, Mg, Ta 및 Nb로 이루어진 군에서 선택되는 어느 하나 또는 둘 이상의 원소를 포함하며, 0<x≤0.5, 0<y≤0.5, 0≤z≤0.03, 0≤w≤0.02, 0<x+y<1이다)
- 제28항에 있어서,상기 니켈, 망간 및 코발트는 전구체 입자 전체에 걸쳐 각각 독립적으로 변화하는 농도구배를 나타내고,상기 니켈의 농도는 전구체 입자의 중심에서부터 표면 방향으로 농도구배를 가지면서 감소하고, 그리고상기 코발트 및 망간의 농도는 각각 독립적으로 전구체 입자의 중심에서부터 표면 방향으로 농도구배를 가지면서 증가하는 것인 이차전지용 양극활물질의 전구체.
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