Positive electrode active material for lithium secondary battery and lithium secondary battery including the same

Abstract

The present embodiment relates to a positive electrode active material for a lithium secondary battery and a lithium secondary battery including the same. [Solution] According to one embodiment, a positive electrode active material for a lithium secondary battery includes a metal oxide in the form of a single particle and a coating layer located on the surface of the metal oxide, and the coating layer may have a plurality of stripe shapes including protrusions based on a longitudinal cross section.

Description

[Technical Field]

[0001] The present embodiment relates to a positive electrode active material for a lithium secondary battery and a lithium secondary battery including the same. [Background technology]

[0002] Recently, driven by the explosive demand for electric vehicles and the demand for increased driving distance, the development of secondary batteries having high capacity and high energy density to meet these demands has been actively pursued worldwide.

[0003] To meet these requirements, a technology using high-nickel NCM (nickel cobalt manganese) cathode material with a high Ni content has been proposed. At the same time, to improve the density of the electrodes, which are the components of the cell, the material must be constructed in a bimodal form, with a certain ratio of large and small particles blended together.

[0004] However, in the case of cathode materials that are composed of secondary particles formed by agglomeration of primary particles ranging in size from several tens of nanometers to several micrometers, the specific surface area of ​​the powder is large, resulting in a large area in contact with the electrolyte, which increases the possibility of gas generation and reduces the lifespan.

[0005] To solve this problem, methods have been proposed to increase the size of primary particles using sintering agents or fluxes, but this method has the problem of reducing the electrochemical performance of the positive electrode active material due to the formation of rocksalt structures on the particle surface.

[0006] Therefore, there is a need to develop a positive electrode active material that has excellent electrochemical performance while increasing the size of the primary particles. Summary of the Invention [Problem to be solved by the invention]

[0007] In accordance with the present invention, a positive electrode active material having a single particle form and excellent electrochemical performance, and a lithium secondary battery including the same, are provided. [Means for solving the problem]

[0008] According to one embodiment, a positive electrode active material for a lithium secondary battery includes a metal oxide in the form of a single particle and a coating layer disposed on a surface of the metal oxide, and the coating layer may have a plurality of stripes including protrusions in a longitudinal cross section.

[0009] A lithium secondary battery according to an embodiment may include the positive electrode, a negative electrode, and an electrolyte. [Effects of the Invention]

[0010] The positive electrode active material for a lithium secondary battery according to an embodiment has a single particle form, and the surface structure is modified so that a coating layer having a stripe shape is located on the surface, thereby realizing a lithium secondary battery with excellent electrochemical performance. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a SEM image of the positive electrode active material prepared in Example 4, measured at a magnification of 20,000 times. [Figure 2] FIG. 2 is a SEM image of the positive electrode active material prepared according to Comparative Example 3, measured at a magnification of 20,000 times. [Figure 3] FIG. 3 is a SEM image of the positive electrode active material prepared in Example 4, measured at a magnification of 120,000 times. [Figure 4] FIG. 4 is an SEM image of a vertical cross section obtained by processing a cross section of the cathode active material prepared in Example 4 in the longitudinal direction (direction B in FIG. 4) using a focused ion beam (FIB) and then measuring the cross section at a magnification of 60,000 times. [Figure 5]FIG. 5 is a diagram schematically illustrating the distance and height between the stripe-shaped protrusions in Area A and Area B in FIG. [Figure 6] FIG. 6 is a SEM image of the positive electrode active material prepared in Example 8, measured at 5,000 times magnification. [Figure 7] FIG. 7 shows the results of measuring the HPPC resistance values ​​of the positive electrode active materials prepared in Example 4 and Comparative Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0012] Terms such as "first," "second," and "third" are used to describe various parts, components, regions, layers, and / or sections, but are not limited thereto. These terms are used only to distinguish one part, component, region, layer, or section from another part, component, region, layer, or section. Therefore, a first part, component, region, layer, or section described below may be referred to as a second part, component, region, layer, or section without departing from the scope of the present invention.

[0013] The terminology used herein is merely for the purpose of referring to particular embodiments and is not intended to limit the present invention. As used herein, the singular forms "a," "an," and "the" include the plural forms unless the context clearly dictates otherwise. As used in the specification, the term "comprising" embodies certain properties, regions, integers, steps, operations, elements, and / or components, and does not exclude the presence or addition of other properties, regions, integers, steps, operations, elements, and / or components.

[0014] When a part is referred to as being "on" another part, it may be directly on top of the other part, or there may be other parts between them. In contrast, when a part is referred to as being "directly on top" of another part, there are no other parts between them.

[0015] Unless otherwise defined, all terms, including technical and scientific terms, used herein have the same meaning as commonly understood by a person of ordinary skill in the art to which the present invention pertains. Terms defined in commonly used dictionaries are additionally interpreted to have a meaning consistent with the relevant technical literature and the presently disclosed content, and are not interpreted in an ideal or very formal sense unless otherwise defined.

[0016] "Positive electrode active material for lithium secondary batteries" As described above, when the size of the primary particles is increased, a rocksalt structure is formed on the surface, resulting in a decrease in the electrochemical performance of the positive electrode active material. However, in this embodiment, this problem is solved by realizing a positive electrode active material having a modified surface structure in which a coating layer having a striped pattern including protrusions is located on the surface of a single-particle metal oxide formed by increasing the size of the primary particles.

[0017] That is, a positive electrode active material for a lithium secondary battery according to an embodiment may include a metal oxide in the form of a single particle and a coating layer disposed on a surface of the metal oxide, and the coating layer may have a plurality of stripes including protrusions on a longitudinal cross section.

[0018] In this case, the average length in the short side direction of the stripe-shaped protrusions included in the coating layer may be 110 nm or more, more specifically, in the range of 110 nm to 250 nm.

[0019] The average length in the long side direction of the stripes contained in the coating layer may be 650 nm or more, more specifically, in the range of 680 nm to 1500 nm.

[0020] When the distance between the protrusions and the average height of the protrusions included in the stripe shape formed on the coating layer satisfy the above ranges, the electrochemical performance of a lithium secondary battery using the positive electrode active material according to the present embodiment can be significantly improved.

[0021] The average distance between the stripe-shaped protrusions included in the coating layer may be in the range of 10 nm to 60 nm or 18 nm to 45 nm, and the average height of the protrusions may be in the range of 18 nm to 75 nm or 25 nm to 65 nm.

[0022] The stripe shape may satisfy the following formula 1: (Formula 1)4

[0023] In formula 1, A is the length of the short side of the stripe-shaped protrusion, and B is the length of the long side of the stripe-shaped protrusion.

[0024] Specifically, formula 1 may be in the range of 5 to 10. When the width and longitudinal length of the stripe-shaped protrusions satisfy the ranges of formula 1, a positive electrode active material can be provided that has excellent room-temperature resistance and high-temperature life characteristics, while also exhibiting a significantly reduced rate of increase in high-temperature resistance.

[0025] The stripe shape may satisfy the following formula 2: (Formula 2)0.1 <D / C<8

[0026] In formula 2, C is the distance between the protrusions forming the stripe shape, and D is the height of the protrusions forming the stripe shape.

[0027] Specifically, formula 2 may be in the range of 0.5 to 5 or 0.7 to 4. When the ratio of the distance between the stripe-shaped protrusions and the height of the protrusions satisfies the range of formula 2, a positive electrode active material can be provided that has excellent room-temperature resistance and high-temperature life characteristics, while also exhibiting a significantly reduced rate of increase in high-temperature resistance.

[0028] ​Meanwhile, the positive electrode active material may have a Li / Ni cation mixing ratio of 1.5% or less, more specifically, 1.1 to 1.4%. If the Li / Ni cation mixing ratio is too high, the Li layer may easily collapse, which may significantly reduce the battery's lifespan. If the Li / Ni cation mixing ratio is too low, the irreversible sites in the bulk portion of the positive electrode active material may increase, reducing the mobility of lithium ions and degrading the resistance and output characteristics. Therefore, when the Li / Ni cation mixing ratio satisfies the above range, a positive electrode active material with low resistance and improved lifespan can be realized, which is advantageous.

[0029] In this specification, the Li / Ni cation mixing ratio means the amount of Ni substituted for the Li site.

[0030] In this embodiment, the coating layer may contain at least one of Co, Al, W, V, Ti, Nb, Ce, B, and P. In this case, the content of the element contained in the coating layer may be in the range of 0.5 mol % to 3.5 mol % based on the entire coating layer. Since the coating layer contains at least one of these elements in the above range, the surface structure of the positive electrode active material of this embodiment can be modified.

[0031] The metal oxide may contain nickel, cobalt, and manganese, and the content of nickel in the entire metal oxide may be greater than the sum of the contents of cobalt and manganese.

[0032] More specifically, the nickel content in the metal oxide particles may be 0.8 mol or more per mol of the nickel, cobalt, and manganese, and more specifically, the nickel content may be in the range of 0.8 to 0.99, 0.85 to 0.99, or 0.88 to 0.99.

[0033] When the nickel content in the lithium metal oxide is 0.8 moles or more, as in this embodiment, a cathode active material with high output characteristics can be realized. The cathode active material of this embodiment having such a composition has a high energy density per volume, which can improve the capacity of the battery to which it is applied, making it highly suitable for use in electric vehicles.

[0034] The metal oxide further comprises a doping element, which may comprise at least one of Al, Zr, Nb, Mo, W, Ti, Ce, Mg, B, P, V, Sr, and B.

[0035] The content of the doping element may be in the range of 0.0005 mol to 0.04 mol or 0.001 mol to 0.03 mol, where the sum of the nickel, cobalt, manganese and the doping element is 1 mol. Here, the doping element refers to the doping amount of the doping element contained in the final cathode active material.

[0036] In order to ensure a long life and various electrochemical performances of a positive electrode active material, it is important to select a doping element. In the present embodiment, various doping elements are used as described above to improve the characteristics of the positive electrode active material.

[0037] In this embodiment, the doping elements may include Zr and Al.

[0038] Zr ions occupy the Li site, acting as a kind of pillar, mitigating the contraction of the lithium ion path during the charge and discharge process and stabilizing the layered structure. This phenomenon reduces cation mixing, increases the lithium diffusion coefficient, and can extend the cycle life.

[0039] Furthermore, Al ions migrate to tetragonal lattice sites, preventing the layered structure from deteriorating into a spinel structure, which is relatively difficult for lithium ions to move through.

[0040] The Zr content may be in the range of 0.001 mol to 0.01 mol, more specifically, 0.0016 mol to 0.005 mol, based on 1 mol of the total of the nickel, cobalt, manganese and doping element. When the Zr doping amount satisfies the above range, it is possible to reduce the rate of increase in high-temperature resistance and ensure excellent life characteristics.

[0041] The Al content may be 0.001 mol to 0.04 mol, more specifically, 0.004 mol to 0.028 mol, 0.0045 mol to 0.027 mol, or 0.0055 mol to 0.025 mol, based on 1 mol of the total of the nickel, cobalt, manganese, and doping element. When the Al doping amount satisfies the above range, high-temperature life and thermal stability can be further improved.

[0042] Next, the average crystal grain size of the metal oxide may be 200 nm or more.

[0043] When the average crystal grain size is within this range, it can be defined as a single particle. Furthermore, when the average crystal grain size is within this range, crystallization has progressed well, which can reduce residual lithium on the surface of the positive electrode active material and further improve the life characteristics of the lithium secondary battery.

[0044] In this specification, the average crystal grain size is defined as being measured by the following method.

[0045] 1. Sample structure analysis using Rigaku smart lab equipment 2. 45kV, 200mA (9kW) applied to the Cu anode to generate X-rays 3. The optical system has an incident slit of 1 / 2 deg and a receiving slit of 8.0mm. 4. Scan from 10 to 80°, step 0.02°, 10° / min. 5. Calculate crystal size using SmartLab Studio II v4.2.82.0S / W 6. Calculations are performed using WPPF (Whole powder pattern fitting) in software. 7. Use Layered structure for WPPF progression and set Profile fitting to FP method 8. Receiving optic is set to Graphite (002) and Soller slit 3.8 9. Set Shape to Spherical, Strain to 0, Fix, Refine and calculate crystal size

[0046] The average particle size (D50) of the positive electrode active material may be 2.5 μm or more, more specifically, in the range of 3.0 μm to 5.0 μm. In this embodiment, a single-particle positive electrode active material having such an average particle size can be produced without the need for an expensive crushing device or multiple crushing processes. That is, even when using a conventional crushing device, a single-particle positive electrode active material having a uniform particle size distribution with very little fine or large powder can be produced. Therefore, when the average particle size of the positive electrode active material of this embodiment satisfies the above range, a lithium secondary battery with excellent electrochemical properties can be realized.

[0047] Meanwhile, the positive electrode active material of the present embodiment may further include a positive electrode active material containing a metal oxide in the form of secondary particles formed by aggregation of primary particles.

[0048] That is, the cathode active material may include a cathode active material containing the metal oxide in the form of single particles, and a cathode active material containing the metal oxide in the form of secondary particles, the average particle size (D50) of which is larger than the average particle size (D50) of the cathode active material containing the metal oxide in the form of single particles. When the cathode active material containing the metal oxide in the form of single particles and the cathode active material containing the metal oxide in the form of secondary particles are mixed and used in a bimodal manner as described above, the density of the electrode mixture can be advantageously increased.

[0049] In this bimodal cathode active material, the mixing ratio of the cathode active material containing a metal oxide in single particle form and the cathode active material containing a metal oxide in secondary particle form may be in the range of 30:70 to 10:90 or 25:75 to 15:85 by weight (single particle:secondary particle). When the cathode active materials containing metal oxides in single particle and secondary particle forms are mixed and used in such a weight ratio, the density of the electrode mixture can be increased.

[0050] In this case, the positive electrode active materials including the metal oxide in the form of single particles and the metal oxide in the form of secondary particles may have the same composition or different compositions. Specifically, both the positive electrode active materials including the metal oxide in the form of single particles and the metal oxide in the form of secondary particles may include nickel, cobalt, manganese, and a doping element.

[0051] For example, the positive electrode active material containing the metal oxide in the form of secondary particles may contain nickel, cobalt, and manganese, and the content of the nickel in the entire metal oxide in the form of secondary particles may be greater than the sum of the contents of the cobalt and manganese.

[0052] More specifically, the content of nickel in the metal oxide particles in the form of secondary particles may be 0.8 mol or more based on 1 mol of the nickel, cobalt, and manganese, and more specifically, the content of nickel may be in the range of 0.8 to 0.99, 0.85 to 0.99, or 0.88 to 0.99.

[0053] The metal oxide in secondary particle form further comprises a doping element, and the doping element may comprise at least one of Al, Zr, Nb, Mo, W, Ti, Ce, Mg, B, P, V, Sr, and B.

[0054] The specific description and content of the doping element are the same as those of the positive electrode active material containing the single particle metal oxide described above, and therefore will not be repeated here.

[0055] In addition, in this embodiment, the average particle size (D50) of the cathode active material containing the metal oxide in the form of secondary particles may be in the range of 10 μm to 20 μm, or 12 μm to 17 μm. When the average particle size of the cathode active material containing the metal oxide in the form of secondary particles satisfies this range, large particles and small particles can be appropriately distributed in the bimodal cathode active material, thereby improving the energy density of the lithium secondary battery.

[0056] "Lithium secondary battery" In yet another embodiment of the present invention, there is provided a lithium secondary battery including a positive electrode including the positive electrode active material according to the embodiment of the present invention described above, a negative electrode, and an electrolyte disposed between the positive electrode and the negative electrode.

[0057] Specifically, the positive electrode includes a current collector and a positive electrode active material layer formed on the current collector, and the characteristics of the positive electrode active material constituting the positive electrode active material layer are the same as those described above. Therefore, a detailed description of the positive electrode active material will be omitted.

[0058] The current collector may be, for example, stainless steel, aluminum, nickel, titanium, baked carbon, or aluminum or stainless steel whose surface has been treated with carbon, nickel, titanium, silver, or the like.

[0059] Meanwhile, the positive electrode active material layer may include a binder and a conductive material.

[0060] The binder serves to firmly adhere the positive electrode active material particles to each other and to the current collector.

[0061] The conductive material is used to impart electrical conductivity to the electrode, and any material can be used as long as it is electron-conductive without causing chemical changes in the battery that is constructed.

[0062] The positive electrode is fabricated by mixing an active material, a conductive material, and a binder in a solvent to prepare an active material composition, and then coating the composition on a current collector. Since this electrode fabrication method is well known in the art, a detailed description thereof will be omitted. Examples of the solvent include, but are not limited to, N-methylpyrrolidone.

[0063] The negative electrode includes a current collector and a negative electrode active material layer formed on the current collector, and the negative electrode active material layer includes a negative electrode active material.

[0064] The negative electrode active material includes a material capable of reversibly intercalating / deintercalating lithium ions, lithium metal, a lithium metal alloy, a material capable of doping and dedoping lithium, or a transition metal oxide.

[0065] The material capable of reversibly intercalating / deintercalating lithium ions is a carbon material, and any carbon-based negative electrode active material commonly used in lithium ion secondary batteries may be used, and representative examples thereof include crystalline carbon, amorphous carbon, or a combination of these.

[0066] The lithium metal alloy can be an alloy of lithium and a metal selected from the group consisting of Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn.

[0067] Examples of the substance capable of doping and undoping lithium include Si, SiO x (0 < x < 2), Si-Y alloy (where Y is an element selected from the group consisting of an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, and a combination thereof, and is not Si), Sn, SnO2, Sn-Y (where Y is an element selected from the group consisting of an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, and a combination thereof, and is not Sn), and the like.

[0068] Examples of the transition metal oxide include vanadium oxide, lithium vanadium oxide, and the like.

[0069] The negative electrode active material layer also contains a binder and may selectively further contain a conductive material.

[0070] Examples of the binder include polyvinyl alcohol, carboxymethyl cellulose / styrene-butadiene rubber, hydroxypropylene cellulose, diacetylene cellulose, polyvinyl chloride, polyvinyl pyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, etc., but are not limited thereto. The binder can be mixed at 1 wt% to 30 wt% based on the total amount of the composition for forming the negative electrode active material layer.

[0071] The conductive material is not particularly limited as long as it is conductive and does not induce chemical changes in the battery, and specific examples include graphite such as natural graphite and artificial graphite; carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fiber and metal fiber; metal powders such as carbon fluoride, aluminum, and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives. The conductive material can be mixed in an amount of 0.1 wt % to 30 wt % with respect to the total amount of the composition for forming the negative electrode active material layer.

[0072] The current collector may be selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and combinations thereof.

[0073] The negative electrode is fabricated by mixing an active material, a conductive material, and a binder in a solvent to prepare an active material composition, and then coating the composition on a current collector. Since this electrode fabrication method is well known in the art, a detailed description thereof will be omitted. Examples of the solvent include, but are not limited to, N-methylpyrrolidone.

[0074] Examples of the electrolyte include, but are not limited to, organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel polymer electrolytes, solid inorganic electrolytes, and molten inorganic electrolytes that can be used in manufacturing lithium secondary batteries.

[0075] Specifically, the organic liquid electrolyte includes a non-aqueous organic solvent and a lithium salt.

[0076] The non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.

[0077] The lithium salt is a substance that dissolves in an organic solvent and acts as a source of lithium ions in the battery, enabling basic operation of a lithium secondary battery, and facilitating the movement of lithium ions between the positive electrode and the negative electrode.

[0078] Depending on the type of lithium secondary battery, a separator may be present between the positive electrode and the negative electrode. Such a separator can be made of polyethylene, polypropylene, polyvinylidene fluoride, or a multilayer film of two or more of these layers. Of course, mixed multilayer films such as a polyethylene / polypropylene two-layer separator, a polyethylene / polypropylene / polyethylene three-layer separator, or a polypropylene / polyethylene / polypropylene three-layer separator can also be used.

[0079] Lithium secondary batteries are classified into lithium ion batteries, lithium ion polymer batteries, and lithium polymer batteries depending on the type of separator and electrolyte used, and may be classified into cylindrical, prismatic, coin, pouch, etc. depending on the shape, and into bulk and thin film types depending on the size. The structure and manufacturing method of these batteries are widely known in the field, so detailed description will be omitted. [Example]

[0080] The following detailed description of the present invention is provided by way of example only and does not limit the scope of the present invention, which is defined solely by the scope of the claims that follow.

[0081] "Example 1 - Positive electrode active material in single particle form, heat treated at 600°C for 6 hours" (1) Preparation of precursor The precursor was prepared by a conventional coprecipitation method.

[0082] Specifically, NiSO4·6H2O was used as the nickel source material, CoSO4·7H2O was used as the cobalt source material, and MnSO4·H2O was used as the manganese source material. These raw materials were dissolved in distilled water to produce metal salt aqueous solutions.

[0083] After preparing the coprecipitation reactor, N2 was purged to prevent oxidation of metal ions during the coprecipitation reaction, and the reactor temperature was maintained at 50°C.

[0084] NH4(OH) was added as a chelating agent to the co-precipitation reactor, and NaOH was used to adjust the pH. The precipitate obtained by the co-precipitation process was filtered, washed with distilled water, and dried in an oven at 100°C for 24 hours to prepare a cathode active material precursor.

[0085] The composition of the produced precursor was (Ni 0.98 Co 0.01 Mn 0.01 )(OH)2, and the average particle size (D50) was approximately 4 μm.

[0086] (2) Manufacturing of positive electrode active material 684 g of the precursor prepared in (1) was weighed with 315 g of LiOH·H2O, 2.94 g of Al(OH)3, and 1.47 g of ZrO2, and then uniformly mixed and fired at 830-890°C for 24 hours in a box-type firing furnace with an oxygen inflow of 1,000 mL / min to synthesize a metal oxide cathode material. The mixture was then crushed using a jet mill to prepare a cathode active material containing single particle metal oxide.

[0087] Approximately 1.927 g of Co(OH)2 was mixed with 100 g of the single particle metal oxide, and the mixture was heat-treated at 600°C for 6 hours in an oxygen atmosphere to prepare a cathode active material having a coating layer formed thereon.

[0088] "Examples 2 to 7" A positive electrode active material having a coating layer formed thereon was prepared in the same manner as in Example 1, except that the heat treatment conditions during the formation of the coating layer were adjusted as shown in Table 1 below.

[0089] [Table 1]

[0090] "Example 8 (1) Preparation of precursor" The composition is (Ni 0.92 Co 0.04 Mn 0.04 A precursor was produced in the same manner as in Example 1, except that the average particle size (D50) was about 14.5 μm.

[0091] (2) Manufacturing of large particle size positive electrode active material To 684 g of the precursor prepared in (1), 325 g of LiOH·H2O, 11.4 g of Al(OH)3, and 3.2 g of ZrO2 were weighed, mixed uniformly, and fired at 830-890°C for 24 hours in a box-type firing furnace with an oxygen inflow rate of 1,000 mL / min to synthesize a metal oxide cathode material.

[0092] Thereafter, the powder was crushed using an ACM (Air Classifying Mill), washed with water to remove residual lithium on the surface, and then dried for 12 hours.

[0093] Next, a mixture of 100 g of dried cathode material and about 0.35 g of boric acid (H3BO3) was mixed and heat-treated at 250°C to 300°C for 5 hours in an air atmosphere.

[0094] (3) Manufacturing of bimodal cathode active material The positive electrode active material prepared in (2) and the positive electrode active material prepared in Example 4 were mixed in a weight ratio of 8:2 to prepare a bimodal positive electrode active material.

[0095] Comparative Example 1 (1) Preparation of precursor A precursor was produced in the same manner as in Example 1.

[0096] (2) Manufacturing of positive electrode active material 684 g of the precursor prepared in (1) was weighed with 315 g of LiOH·H2O, 2.94 g of Al(OH)3, and 1.47 g of ZrO2, and then uniformly mixed and fired at 830-890°C for 24 hours in a box-type firing furnace with an oxygen inflow of 1,000 mL / min to synthesize a metal oxide cathode material. The mixture was then crushed using a jet mill to prepare a cathode active material containing single particle metal oxide.

[0097] "Comparative Example 2" The cathode active material prepared according to Comparative Example 1 was additionally heat-treated at 660° C. for 6 hours to prepare a cathode active material according to Comparative Example 2.

[0098] "Comparative Example 3 - Co coating layer formed by wet method" A positive electrode active material was produced in the same manner as in Comparative Example 1.

[0099] Next, 0.03 grams (g) of LiNO3 and 11.74 g of Co(NO3)2·6H2O were dissolved in 100 g of H2O heated to 60°C, and 100 g of the cathode material of Comparative Example 1 was added. The resulting slurry was stirred for 30 minutes and then spray-dried to obtain a powder. The powder was placed in an alumina crucible and heated to approximately 450°C at a rate of approximately 5°C per minute. The temperature was maintained at approximately 450°C for approximately 1 hour, and then the temperature was increased by approximately 2°C per minute to approximately 700°C and maintained for approximately 2 hours. The sample was then cooled to room temperature to produce the cathode active material of Comparative Example 2.

[0100] "Experimental Example 1: Electrochemical Performance Evaluation" (1) Manufacturing of coin-type half cells For the positive electrode active materials prepared in Examples 1 to 8 and Comparative Examples 1 and 2, coin-type half cells were prepared as follows to evaluate the physical properties and electrochemical properties.

[0101] Specifically, the positive electrode active material, polyvinylidene fluoride binder (product name: KF1120), and carbon black conductive material were mixed in a weight ratio of 96.5:1.5:2, and this mixture was added to N-methyl-2-pyrrolidone solvent so that the solid content was approximately 30 wt % to produce a positive electrode active material slurry.

[0102] The slurry was coated on an aluminum foil (thickness: 15 μm) as a positive electrode current collector using a doctor blade, dried, and then rolled to prepare a positive electrode. The loading amount of the positive electrode was about 15 mg / cm. 2 The electrode thickness is approximately 65 μm and the rolling density is approximately 3.4 g / cm 3 That was all.

[0103] A 2032 coin-type half-cell was fabricated using the cathode, lithium metal anode (300 μm thick, MTI), electrolyte, and polypropylene separator in a conventional manner. The electrolyte was a mixed solution of 1M LiPF6 dissolved in a mixed solvent of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate (EMC) (mixing ratio EC:DMC:EMC = 3:4:3 vol%). After fabrication, the half-cell was aged at room temperature for 10 hours.

[0104] (2) Measurement of residual lithium and particle size Residual lithium was measured using a METTLER TOLEDO T50 model, and particle size was measured using a microtrac S3500 model.

[0105] (3) Capacity evaluation The coin-type half cell prepared according to the experimental preparation was aged at room temperature (25° C.) for 10 hours, and then a charge / discharge test was carried out.

[0106] The capacity evaluation was performed with 200mAh / g as the reference capacity, and the charge / discharge conditions were CC / CV 2.5 to 4.25V with a 1 / 20C cut-off. The initial capacity was measured with a 0.2C charge / 0.2C discharge.

[0107] (4) Measurement of life characteristics The lifespan characteristics were measured 50 times at high temperature (45°C) under the conditions of 0.5C charge / 1.0C discharge.

[0108] (5) Measurement of resistance characteristics The room temperature initial resistance (DC-IR (Direct current internal resistance)) was calculated by charging the battery at 0.2C and discharging it at 0.2C once at 25°C under constant current-constant voltage conditions of 2.5V to 4.25V with a 1 / 20C cutoff, and measuring the voltage 60 seconds after applying the discharge current at 4.25V, 100% charge.

[0109] The resistance increase rate was measured by comparing the resistance measured initially at high temperature (45°C) (initial resistance at room temperature) with the resistance measured after 30 cycles in the same manner as the initial resistance measurement, and the increase rate was converted into a percentage (%).

[0110] "Experimental Example 2: X-ray diffraction evaluation" -Sample structure analysis using Rigaku smart lab equipment - 45kV, 200mA (9kW) applied to the Cu anode to generate X-rays -The device optics is set to incident slit 1 / 2 deg and receiving slit 8.0mm. -XRD measurement is performed at a scan speed of 10 to 80°, a step speed of 0.02°, and a scanning speed of 10° / min.

[0111] "Experimental Example 3: Method for measuring the cation mixing ratio" 1. Sample structure analysis using Rigaku smart lab equipment 2. 45kV, 200mA (9kW) applied to the Cu anode to generate X-rays 3. The optical system has an incident slit of 1 / 2 deg and a receiving slit of 8.0mm. 4. Scan from 10 to 80°, step 0.02°, 10° / min. 5. Calculate crystal size using SmartLab Studio II v4.2.82.0S / W 6. Calculations are performed using WPPF (Whole powder pattern fitting) in software. 7. Use Layered structure for WPPF progression and set Profile fitting to FP method 8. Receiving optic is set to Graphite (002) and Soller slit 3.8 9. Set Shape to Spherical, Strain to 0, Fix, Refine and calculate crystal size 10.In the Crystal structure tab, use the Occupancy of Ni1 as the Cation mixing value.

[0112] [Table 2]

[0113] Referring to Table 2, it can be seen that Examples 1 to 8, which employ positive electrode active materials containing single-particle metal oxides with a Co coating layer, exhibit superior electrochemical performance, such as increased discharge capacity and improved lifespan, compared to Comparative Examples 1 and 2, which do not employ a Co coating layer. In particular, the positive electrode active material of Example 4, which was prepared using a heat treatment temperature of 660°C in the coating layer formation process, exhibited the best 0.2C discharge capacity, lifespan, and high-temperature resistance increase rate characteristics.

[0114] "Experimental Example 4: Analysis of the structure of the positive electrode active material" FIG. 1 is an SEM image of the cathode active material prepared in Example 4, magnified 20,000 times, and FIG. 2 is an SEM image of the cathode active material prepared in Comparative Example 3, magnified 20,000 times.

[0115] The positive electrode active material prepared according to the example had a wave-like shape on the surface of the single particle, as can be seen from Figure 1. In this case, the electrochemical performance was the best.

[0116] Also, referring to FIG. 2, it can be seen that when the Co coating layer is formed using a wet method, the surface does not include a stripe-shaped pattern.

[0117] Next, FIG. 3 is a SEM image of the positive electrode active material prepared in Example 4, measured at a magnification of 120,000 times.

[0118] In addition, the distances between and heights of nine stripe-shaped protrusions formed on the coating layer of the positive electrode active material formed in Example 4 were measured and are shown in Table 3 below.

[0119] [Table 3]

[0120] 3, it can be seen that the coating layer on the surface of the cathode active material prepared in Example 4 includes a plurality of stripes. Also, it can be seen from Table 4 that the length (A) of the protrusions forming the stripes in the longitudinal direction and the length (B) of the stripes in the width direction satisfy the range of Equation 1.

[0121] FIG. 4 is an SEM image of a vertical cross section of a cathode active material prepared in Example 4, which was processed in the longitudinal direction (direction B in FIG. 3) using a focused ion beam (FIB), and then measured at a magnification of 60,000 times. FIG. 5 is a schematic diagram illustrating the distance and height between the stripe-shaped protrusions of Area A and Area B in FIG. 4.

[0122] In addition, for the samples shown in Table 4, an image as shown in FIG. 4 was taken, and then the distance between the protrusions (C) and the height of the protrusions (D) in the regions corresponding to Area A and Area B were measured and shown in Table 4 below.

[0123] [Table 4]

[0124] Referring to Table 4, the distance between protrusions (C) in Area A ranges from 20.98 nm to 62.94 nm, and the height of the protrusions (D) ranges from 45.56 nm to 63.45 nm. The distance between protrusions (C) in Area B ranges from 24.68 nm to 42.12 nm, and the height of the protrusions (D) ranges from 24.20 nm to 32.89 nm. In other words, it can be seen that the average distance between the stripe-shaped protrusions formed on the coating layer of the cathode active material according to one embodiment is 20 nm or more, and the average height is 22 nm or more.

[0125] It can also be confirmed that the distance (C) between the stripe-shaped protrusions and the height (D) of the stripe-shaped protrusions satisfy the range of Equation 2.

[0126] Next, Figure 6 is an SEM image of the cathode active material prepared in Example 8, measured at 5,000 times magnification. That is, it is related to the cathode active material prepared in a bimodal form.

[0127] Referring to FIG. 6, it can be seen that large grain sizes of polycrystals and small grain sizes of single grains are uniformly mixed.

[0128] "Experimental Example 5: HPPC Evaluation" The positive electrode active materials prepared in Example 4 and Comparative Example 3 were used to measure the HPPC resistance in the following manner, and the results are shown in FIG.

[0129] <Cell Preparation> 1. Fabrication of 2032 coin cells (electrode density: 3.5 g / cc) 2. Coin cell is rested for 10 hours in a 25°C chamber (Purpose: Electrolyte impregnation and synchronization of chamber and cell temperatures)

[0130] <HPPC pattern of the cell> 1. Activation and capacity confirmation of the cell Charge: CC / CV {CC: 0.2C} {CV: 0.005C} Discharge: CC {CC: 0.2C} (Reference capacity: 200 mAh / g) (Cut off Voltage: 2.5V - 4.25V) 2. C-rate calculation based on the obtained capacity (Capacity: approximately 4.5 mAh) (0.2C current: approximately 0.9 mA) 3. Full charge at 0.2C and 4.25V with the calculated C-rate (SOC 100% state) 4. (1) Discharge at 0.2C for 30 min (Purpose: SOC - 10%) (2) Discharge at 1C for 10 s (Purpose: Resistance measurement at target SOC) (3) Charge at 0.2C for 50 s (Purpose: Compensation for the SOC (capacity) lost during 1C, 10 s discharge) 5. Repeat the above "4." nine times (SOC ~ 10%)

[0131] <HPPC value calculation> Calculation of HPPC values for each SOC (90 - 10%) (Initial voltage of (2) - Final voltage of (2)) / ((2)'s 1C current) = (10sΩ for each SOC)

[0132] Referring to Fig. 7, it can be confirmed that the HPPC resistance value of the positive electrode active material manufactured by Example 4 in which Co is dry-coated to form a coating layer is lower than that of the positive electrode active material manufactured by Comparative Example 3 in which Co is wet-coated.

[0133] HPPC resistance is the resistance value measured according to the SOC of a battery, and the lower the HPPC resistance, the less energy loss there is, leading to improved battery output. As can be seen from Figure 7, the positive electrode active material of this example exhibits low HPPC resistance, which indicates excellent charging speed and output, confirming its suitability for use in batteries for electric vehicles.

[0134] The positive electrode active material according to an embodiment has a single particle form, and has a surface structure modified so that a coating layer having a stripe shape is located on the surface, thereby providing a positive electrode active material with improved discharge capacity, room temperature resistance, high temperature life, and high temperature resistance characteristics.

[0135] The present invention is not limited to the above-described embodiments, and can be manufactured in various different forms, and those skilled in the art will understand that the present invention can be embodied in other specific forms without changing the technical spirit or essential characteristics of the present invention. Therefore, it should be understood that the above-described embodiments are illustrative in all respects and not limiting.

Claims

1. a metal oxide in single particle form; a coating layer located on the surface of the metal oxide; Including, The coating layer has a plurality of stripes including protrusions on the basis of a cross section in the width direction.

2. 2. The positive electrode active material for a lithium secondary battery according to claim 1, wherein the average length of the protrusions in the short side direction is 110 nm or more.

3. 2. The positive electrode active material for a lithium secondary battery according to claim 1, wherein the average length of the protrusions in the long side direction is 650 nm or more.

4. 2. The positive electrode active material for a lithium secondary battery according to claim 1, wherein an average distance between the protrusions is in the range of 10 nm to 60 nm.

5. 2. The positive electrode active material for a lithium secondary battery according to claim 1, wherein the average height of the protrusions is in the range of 18 nm to 75 nm.

6. The positive electrode active material for a lithium secondary battery according to claim 1 , wherein the stripe shape satisfies the following formula 1: (Formula 1) 4<B / A<11 (In formula 1, A is the length of the stripe-shaped protrusion in the short side direction, and B is the length of the stripe-shaped protrusion in the long side direction.)

7. The positive electrode active material for a lithium secondary battery according to claim 1 , wherein the stripe shape satisfies the following formula 2: (Formula 2) 0.1<D / C<8 (In Equation 2, C is the distance between the protrusions forming the stripe shape, and D is the height of the protrusions forming the stripe shape.)

8. The positive electrode active material for a lithium secondary battery according to claim 1 , wherein the positive electrode active material has a Li / Ni cation mixing ratio of 1.5% or less.

9. 2. The positive electrode active material for a lithium secondary battery according to claim 1, wherein the coating layer contains at least one of Co, Al, W, V, Ti, Nb, Ce, B, and P.

10. The content of the element contained in the coating layer is The positive electrode active material for a lithium secondary battery according to claim 9, wherein the content is in the range of 0.5 mol % to 3.5 mol % based on the entire coating layer.

11. the metal oxide comprises nickel, cobalt, and manganese; 2. The positive electrode active material for a lithium secondary battery according to claim 1, wherein the content of said nickel in the entire metal oxide is greater than the total content of said cobalt and manganese.

12. The metal oxide further comprises a doping element; 12. The positive electrode active material for a lithium secondary battery according to claim 11, wherein the doping element comprises at least one of Al, Zr, Nb, Mo, W, Ti, Ce, Mg, B, P, V, Sr, and B.

13. 2. The positive electrode active material for a lithium secondary battery according to claim 1, wherein the metal oxide has a crystal grain size of 200 nm or more.

14. The positive electrode active material for a lithium secondary battery according to claim 1 , further comprising a positive electrode active material containing a metal oxide in the form of secondary particles formed by aggregation of primary particles.

15. 15. The positive electrode active material for a lithium secondary battery according to claim 14, wherein the average particle size (D50) of the positive electrode active material containing the metal oxide in the form of secondary particles is larger than the average particle size (D50) of the positive electrode active material containing the metal oxide in the form of single particles.

16. the metal oxide in secondary particle form comprises nickel, cobalt, and manganese; The positive electrode active material for a lithium secondary battery according to claim 14 , wherein the content of the nickel in the entire metal oxide in the form of secondary particles is greater than the total content of the cobalt and manganese.

17. The metal oxide in the form of secondary particles further comprises a doping element; 17. The positive electrode active material for a lithium secondary battery according to claim 16, wherein the doping element comprises at least one of Al, Zr, Nb, Mo, W, Ti, Ce, Mg, B, P, V, Sr, and B.

18. The positive electrode active material for a lithium secondary battery according to claim 14 , wherein the positive electrode active material containing the metal oxide in the form of single particles and the metal oxide in the form of secondary particles has the same or different composition.

19. A positive electrode comprising the positive electrode active material according to any one of claims 1 to 18; a negative electrode; Electrolytes, A lithium secondary battery comprising:

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