CN106410131B - Positive electrode active material for lithium secondary battery, method for producing same, and lithium secondary battery - Google Patents

Positive electrode active material for lithium secondary battery, method for producing same, and lithium secondary battery Download PDF

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CN106410131B
CN106410131B CN201610617321.5A CN201610617321A CN106410131B CN 106410131 B CN106410131 B CN 106410131B CN 201610617321 A CN201610617321 A CN 201610617321A CN 106410131 B CN106410131 B CN 106410131B
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lithium
positive electrode
active material
electrode active
secondary battery
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CN106410131A (en
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权镐真
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a positive electrode active material for a lithium secondary battery, a method for preparing the same, and a lithium secondary battery, wherein the positive electrode active material for the lithium secondary battery comprises: a lithium-containing compound; and a surface treatment layer formed on the lithium-containing compound, wherein the surface treatment layer contains a material selected from the group consisting of Al (OH)3And a compound containing B and a compound containing Si.

Description

Positive electrode active material for lithium secondary battery, method for producing same, and lithium secondary battery
Technical Field
The present invention relates to a positive electrode active material for a lithium secondary battery, a method for preparing the same, and a lithium secondary battery comprising the same.
Background
In the fields of IT, electric vehicles, and energy storage devices, lithium secondary batteries are currently the most attracting attention as energy devices. In 1990, since sony corporation first realized commercialization of lithium secondary batteries, it has been remarkably developed in the past 25 years. The initial application field was limited to the field of mobile devices such as notebook computers, but the application range is now expanded to large-scale energy storage devices as well as electric vehicles. Particularly, with the emphasis on environmental protection and efficiency, the applicable field of lithium secondary batteries is expanding to the electric vehicle field and the energy storage device field as new industrial fields, and the applicable field thereof is rapidly expanding.
However, as the application field of lithium secondary batteries expands to the fields of electric vehicles and energy storage devices, the demand for improving the performance of lithium secondary batteries is continuously increasing, and in this field, IT is necessary to achieve high capacity and life characteristics and also to achieve extremely high thermal stability, reliability, and price.
Over the past 25 years, the positive electrode active materials of lithium secondary batteries have been greatly developed, and in order to increase the capacity, lithium-cobalt compounds (L iCoO) have been used2) Start to continueDeveloped to lithium-nickel-cobalt-manganese based compounds (L iNi)xCoyMnzO2X: y: z ═ 1: 1: 1, 4: 3: 3, 5: 2: 3, 6: 2: 2, 8: 1: 1), and further, a lithium-nickel-cobalt-aluminum compound (L iNi) as an ultra-high capacity positive electrode was continuously developedxCoyAlzO2X is equal to 80, 83, 85, 88), and the application range is continuously expanded, generally, in order to strengthen the overall structure, one or more transition metals are coated on the core layer of the positive electrode active material to form a core layer having a stable overall structure, and surface treatment is performed in order to further improve the life characteristics, thermal stability, reliability, and the like1-x-yM'xM"yO2The core layer having a stabilized overall structure is used by coating with a metal such as M ═ Mg or M ═ Ti. In this manner, the lithium-cobalt compound having a stabilized overall structure is subjected to a surface treatment for the purpose of improving the life characteristics, thermal stability, reliability, and the like. The development of the coating technique is applicable not only to lithium-cobalt compounds but also to lithium-manganese compounds, lithium-nickel-cobalt-aluminum compounds, and the like.
In the case of the second method, the development direction for developing a high-capacity lithium secondary battery is directed to use the same kind of positive electrode active material, and since a general positive electrode active material has a layered structure except for a lithium-manganese-based compound, if a charging voltage is increased, the discharge capacity is increased, for example, if a charging voltage is increased, the discharge capacity is increased, and the discharge capacity is increased, if a charging voltage is increased, the discharge capacity is increased, and the lithium secondary battery has a higher charge-discharge capacity, namely, a higher discharge-discharge capacity, namely, a higher charge-discharge capacity, namely, a higher discharge-voltage, namely, a higher discharge-voltage, namely, a discharge-voltage, higher discharge-voltage, and a charge-discharge-voltage-discharge-voltage-stability, namely, if a charge-voltage-stability is increased, and a lithium-stability is higher, namely, higher, namely, and a charge-stability is compared to a higher.
Disclosure of Invention
An object of the present invention is to provide a positive electrode active material for a lithium secondary battery, the positive electrode active material including: a lithium-containing compound; and a surface treatment layer formed on the lithium-containing compound, wherein the surface treatment layer contains a material selected from the group consisting of Al (OH)3And a compound containing B and a compound containing Si.
However, the technical problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood from the following description by those skilled in the art to which the present invention pertains.
The present invention provides a positive electrode active material for a lithium secondary battery, the positive electrode active material for the lithium secondary battery comprising: a lithium-containing compound; and a surface treatment layer formed on the lithium-containing compound, wherein the surface treatment layer contains a material selected from the group consisting of Al (OH)3And a compound containing B and a compound containing Si.
The lithium-containing compound may include one or more compounds selected from the group consisting of a lithium-nickel-cobalt-manganese-based compound, a lithium-nickel-cobalt-aluminum-based compound, and a lithium-cobalt-based compound.
The lithium-containing compound may be a lithium-nickel-cobalt-manganese-based compound represented by the following chemical formula 1:
chemical formula 1
LixNi1-y-z-aCoyMnzMaA2
In the formula, x is more than or equal to 0.95 and less than or equal to 1.1, y is more than or equal to 0.05 and less than or equal to 0.2, z is more than or equal to 0.05 and less than or equal to 0.3, and a is more than or equal to 0.04, wherein M is more than or equal to one selected from the group consisting of Mg, Ti, Al and Zr, and A is selected from the group consisting of O, F, S and P.
The surface treatment layer may contain Al (OH)3B-containing compounds and Si-containing compounds, or may comprise Al (OH)3And a B-containing compound, or may comprise Al (OH)3And a Si-containing compound, or may comprise a B-containing compound and a Si-containing compound.
The surface treatment layer contains Al (OH)3In the case of the B-containing compound and the Si-containing compound, the amount of the compound is adjusted to 100 parts by weight of Al (OH)3It may contain 20 to 100 parts by weight of the B-containing compound and 30 to 100 parts by weight of the Si-containing compound.
In the particle distribution of the positive electrode active material, when the 50% cumulative mass particle size distribution diameter is D50, D50 may be 5 μm to 7 μm.
As an example of the present invention, the present invention provides a method for preparing a positive electrode active material for a lithium secondary battery, the method comprising: step a, preparing a lithium-containing compound; step b, preparing a composition comprising a metal selected from the group consisting of Al (OH)3A surface treatment solution of two or more solutions selected from the group consisting of a solution, a solution containing a compound B and a solution containing a compound Si; and a step c of adding the lithium-containing compound prepared in the step a to the surface treatment solution prepared in the step b, followed by mixing and drying.
In the above step b, Al (OH)3The solution, the solution containing the B compound, or the solution containing the Si compound may be prepared by using water or 95% or less ethanol as a solvent.
In the above stepsIn step b, Al (OH)3The concentration of each solute in the solution, the B-containing compound solution, or the Si-containing compound solution may be 1ppm to 1000 ppm.
In the above step c, the weight ratio of the surface treatment solution and the lithium-containing compound may be 0.5: 1 to 1: 3.
in the above step c, the mixing and the drying may be performed simultaneously.
In the above step c, the mixing and drying may be performed at a temperature of 50 to 150 ℃ for 1 to 10 hours.
The present invention may further include a step d of performing additional heat treatment at a temperature higher than the drying temperature in the step c.
The additional heat treatment may be performed at a temperature of 100 to 700 ℃ for 1 to 10 hours.
As another example of the present invention, the present invention provides a lithium secondary battery comprising the above-described positive electrode active material.
The positive electrode active material for a lithium secondary battery according to the present invention is characterized by comprising: a lithium-containing compound; and a surface treatment layer formed on the lithium-containing compound, wherein the surface treatment layer contains a material selected from the group consisting of Al (OH)3And a compound selected from the group consisting of a B-containing compound and a Si-containing compound, wherein the lithium-containing compound is surface-treated with a plurality of compounds, whereby the lithium secondary battery has the effects of improving high-temperature and normal-temperature life characteristics, thermal stability and expansion characteristics under high-voltage conditions.
Drawings
Fig. 1 is a graph showing thermal characteristics of a B-containing compound.
Fig. 2 is a photograph showing an apparatus that can simultaneously perform mixing and drying in the method for preparing a positive electrode active material of the present invention.
Fig. 3 is a scanning electron micrograph showing the positive electrode active material of the present invention.
Fig. 4 is a graph for analyzing the X-ray diffraction crystal structure of the positive electrode active material of the present invention.
Fig. 5a to 5e are graphs showing the normal temperature life characteristics of a button cell and a fuel cell including the positive electrode active material of the present invention.
Fig. 6a to 6f are graphs showing high-temperature life characteristics of a button cell and a fuel cell including the positive electrode active material of the present invention.
Fig. 7 is a graph showing the capacity retention rate of coin cells containing the positive electrode active material of the present invention as a function of C-rate.
Fig. 8 is a graph showing thermal stability of a coin cell including the positive electrode active material of the present invention.
Fig. 9 is a graph showing the expansion characteristics of a fuel cell including the positive electrode active material of the present invention.
Fig. 10 is a graph comparing high-temperature life characteristics of coin cells including the positive electrode active material of the present invention according to whether a specific element is applied to a lithium-containing compound.
Fig. 11 is a graph comparing high output characteristics of C-rate variation of a fuel cell including the collection active material of the present invention according to the amount of a specific element applied to a lithium-containing compound.
Detailed Description
At present, lithium secondary batteries are applied not only to the IT field but also to the electric vehicles, energy storage devices, and the like, and the application field of lithium secondary batteries is rapidly expanding. In this case, IT is sufficient that the battery life is about 300 times in the lithium secondary battery for IT, but the battery life needs to be about 1000 to 2000 times at a high temperature in the lithium secondary battery for electric vehicles, and the service life needs to be about 10 years in the lithium secondary battery for energy storage devices.
The present inventors have studied a surface treatment technique of a positive electrode active material for improving the life and reliability characteristics of a lithium secondary battery in order to apply the lithium secondary battery to the IT field, the electric vehicle field, and the energy storage field, and have confirmed that the life characteristics of the lithium secondary battery can be improved when a lithium-containing compound is surface-treated with a plurality of compounds, particularly under high-voltage and high-temperature conditions, thereby completing the present invention.
The present invention will be described in detail below.
The present invention provides a positive electrode active material for a lithium secondary battery, comprising: a lithium-containing compound; and a surface treatment layer formed on the lithium-containing compound, wherein the surface treatment layer contains a material selected from the group consisting of Al (OH)3And a compound containing B and a compound containing Si.
The lithium-containing compound may include one or more compounds selected from the group consisting of a lithium-nickel-cobalt-manganese compound, a lithium-nickel-cobalt-aluminum compound, and a lithium-cobalt compound, corresponding to the core layer of the positive electrode active material layer. Since the lithium-containing compound has a layered structure, increasing the charge voltage increases the discharge capacity, which leads to a problem of reducing the life characteristics of the secondary battery, and thus, a technique for improving the problem is required. In particular, the lithium-containing compound is preferably a lithium-nickel-cobalt-manganese-based compound having a nickel content of 30 to 90% or a lithium-nickel-cobalt-aluminum-based compound having a nickel content of 80 to 88%, but is not limited thereto. In this case, the higher the nickel content, the lower the thermal stability, and therefore, a surface treatment technique for improving the above problem is required.
Specifically, the lithium-containing compound may be a lithium-nickel-cobalt-manganese-based compound represented by the following chemical formula 1:
chemical formula 1
LixNi1-y-z-aCoyMnzMaA2
In the formula, x is more than or equal to 0.95 and less than or equal to 1.1, y is more than or equal to 0.05 and less than or equal to 0.2, z is more than or equal to 0.05 and less than or equal to 0.3, and a is more than or equal to 0.04, wherein M is more than or equal to one selected from the group consisting of Mg, Ti, Al and Zr, and A is selected from the group consisting of O, F, S and P.
Specifically, the M is added based on coating, and in the case of coating the lithium-containing compound with M, the lithium secondary battery has an effect of improving high-temperature life characteristics under high-voltage conditions.
At this time, in the case of applying M alone, it is preferable that M be 0.001. ltoreq. a.ltoreq.0.02, and in the case of composite application of M, it is preferable that M be 0.001. ltoreq. a.ltoreq.0.04, but it is not limited thereto. By adjusting the amount of M applied to the lithium-containing compound as described above, the lithium secondary battery can ensure High output characteristics at a High C-rate.
The surface treatment layer may contain Al (OH)3B-containing compounds and Si-containing compounds, or may comprise Al (OH)3And a B-containing compound, or may comprise Al (OH)3And a Si-containing compound, or may comprise a B-containing compound and a Si-containing compound. That is, since the surface treatment layer includes a plurality of compounds, the lithium secondary battery has effects of improving high-temperature and room-temperature life characteristics, thermal stability, and expansion characteristics under high voltage conditions.
Specifically, in the present invention, as one of a plurality of compounds for surface-treating a lithium-containing compound, al (oh) may be contained3. The aluminum-containing compound is used for the structural stability of the positive electrode active material, and the aluminum-containing compound plays a role of reinforcing the bonding structure by reinforcing the bonding of the metal and oxygen. In particular, among the aluminum-containing compounds, Al (OH)3It is extremely preferable that the crystal structure be stabilized and the surface resistance of the positive electrode active material be reduced.
In the present invention, the B-containing compound may be included as one of a plurality of compounds for surface treatment of the lithium-containing compound. In this case, it is preferable that the B-containing compound is used to improve the thermal stability of the lithium secondary battery, and the B-containing compound is selected from B which exhibits heat absorption characteristics at a temperature of about 160 to 200 ℃2O3、HB(OH)2And H3BO3Most preferably, the B-containing compound is HB (OH)2But is not limited thereto. At this time, B may be2O3After dissolution in water or ethanol, heat treatment at about 100 ℃ to Obtain HB (OH)2，HB(OH)2Exhibiting the property of absorbing a large amount of heat at a temperature of about 200 c or so.
Fig. 1 is a graph showing thermal characteristics of a B-containing compound.
As shown in fig. 1, the DSC analysis results showed that the B-containing compound has a characteristic of absorbing heat at a temperature of about 160 to 200 ℃, and when the B-containing compound is included as one of a plurality of compounds for surface treatment of the lithium compound, the thermal stability of the lithium secondary battery can be greatly improved.
Further, in the present invention, as one of the compounds for surface treatment of the lithium-containing compound, a Si-containing compound may be contained. The important factor that rapidly degrades the life characteristics of lithium secondary batteries at high temperatures is that HF generated by the reaction between the electrolyte and the moisture in the electrolyte attacks the metal components (Ni, Co, Mn, etc.) of the positive electrode active material to elute metals. In this case, the Si-containing compound has excellent reactivity with HF, and thus the lithium-containing compound and HF cannot react. Specifically, the Si-containing compound may be Si or SiO2。
That is, the surface treatment layer contains Al (OH)3The B-containing compound and the Si-containing compound, the stability of the crystal structure, low surface resistance, thermal stability and excellent life characteristics at high temperatures can be ensured.
The surface treatment layer contains Al (OH)3In the case of the B-containing compound and the Si-containing compound, the amount of the compound is adjusted to 100 parts by weight of Al (OH)3It may contain 20 to 100 parts by weight of the B-containing compound and 30 to 100 parts by weight of the Si-containing compound.
The surface treatment layer contains Al (OH)3And a B compound, based on 100 parts by weight of Al (OH)3And may contain 20 parts by weight of the compound containing B in an amount of 100 parts by weight.
The surface treatment layer contains Al (OH)3And Si-containing compound, based on 100 parts by weight of Al (OH)3And may contain the Si-containing compound in an amount of 30 to 100 parts by weight.
When the surface treatment layer contains a B-containing compound and an Si-containing compound, the surface treatment layer contains 100 parts by weight of Al (OH)3And may contain the Si-containing compound in an amount of 50 to 200 parts by weight.
In the particle distribution of the positive electrode active material, when the 50% cumulative mass particle size distribution diameter is D50, the high-temperature life characteristics and high output characteristics of the small particles having a D50 of 5 to 7 μm are improved as compared with those of the large particles having a D50 of 11 to 13 μm, but the present invention is not limited thereto.
The present invention also provides a method for preparing a positive electrode active material for a lithium secondary battery, the method comprising: step a, preparing a lithium-containing compound; step b, preparing a composition comprising a metal selected from the group consisting of Al (OH)3A surface treatment solution of two or more solutions selected from the group consisting of a solution, a solution containing a compound B and a solution containing a compound Si; and a step c of adding the lithium-containing compound prepared in the step a to the surface treatment solution prepared in the step b, followed by mixing and drying.
First, in order to prepare a positive electrode active material for a lithium secondary battery, a lithium-containing compound is prepared (step a). The lithium-containing compound is described above.
Next, in order to prepare a positive electrode active material for a lithium secondary battery, a positive electrode active material containing a metal selected from the group consisting of Al (OH)3A solution for surface treatment, a solution containing a compound B and a solution containing a compound Si, and a solution containing at least two of the above-mentioned components (step B).
Al (OH) mentioned above3The solution, the solution containing the B compound, or the solution containing Si may use water or 95% or less ethanol as a solvent. When ethanol having a high purity of more than 95% is used as a solvent, there is a problem that improvement in the life and reliability characteristics of the lithium secondary battery cannot be achieved. In the present invention, B is2O3The aqueous solution is used as a solution containing a compound B2O3After being dissolved in water, heat-treated at a temperature of about 100 ℃ to Obtain HB (OH) as a B-containing compound2。
In the above-mentioned Al (OH)3The concentration of each solute in the solution, the B-containing compound solution, or the Si-containing compound solution may be 1ppm to 1000 ppm. In this case, in Al (OH)3The solution, the B compound-containing solution or the Si compound-containing solution has the advantages that the concentration of each solute is maintained between 1ppm and 1000ppm, thereby reducing the cost and maximizing the performance of the lithium secondary battery by using a small amount of surface treatment substanceAnd (4) point.
Next, to prepare a positive electrode active material for a lithium secondary battery, there is provided a method for preparing a positive electrode active material for a lithium secondary battery, the method comprising: and c, adding the lithium-containing compound prepared in the step a to the surface treatment solution prepared in the step b, and then mixing and drying the mixture.
Preferably, the weight ratio of the surface treatment solution to the lithium-containing compound is 0.5: 1 to 1: 3, but is not limited thereto. In this case, the weight ratio of the surface treatment solution to the lithium-containing compound is less than 0.5: 1, there is a problem that uniform surface treatment cannot be performed due to the shortage of the surface treatment solution, and the weight ratio of the surface treatment solution to the lithium-containing compound is more than 1: 3, since the surface treatment solution is too much, the drying process takes too much time, which causes an economical problem.
The mixing and drying may be performed simultaneously. As described above, in order to simultaneously perform mixing and drying, the apparatus shown in fig. 2 may be used. The above apparatus is characterized in that the surface treatment and the drying can be simultaneously performed.
Specifically, it is preferable that the above mixing and drying is performed at a temperature of 50 to 150 ℃ for 1 to 10 hours, but not limited thereto. At this time, the mixing and drying are performed at the temperature in the above range, thereby having advantages based on the minimization of equipment investment and the simplification of processes.
Alternatively, in order to prepare a positive electrode active material for a lithium secondary battery, the present invention may further include a step d of performing additional heat treatment at a higher temperature than the drying temperature in the above step c.
Specifically, the above additional heat treatment is preferably performed at a temperature of 100 to 700 ℃ for 1 to 10 hours, but is not limited thereto. In this case, the additional heat treatment is performed at a temperature within the above range for a time within the above range, so that the short-time heat treatment is performed at a relatively low temperature, thereby providing an economical advantage.
The present invention also provides a lithium secondary battery including the positive electrode active material.
Specifically, the positive electrode active material may provide a lithium secondary battery including: a positive electrode including a conductive material and a binder; a negative electrode including an active material; and an electrolyte. The lithium secondary battery includes a positive electrode, a negative electrode, and a separation film, and the separation film for insulating the motor between the positive electrode and the negative electrode is a polyolefin-based separation film, and a load separation film in which an organic-inorganic composite layer is formed on the polyolefin-based material may be used.
The present invention can provide a medium-or large-sized battery module or battery pack in which a plurality of lithium secondary batteries are electrically connected. The middle or large-sized battery module or the battery pack may be used for a Power source for middle or large-sized devices including one or more of a heavy machine Tool (Power Tool), an Electric Vehicle (EV), a Hybrid Electric Vehicle (HEV), and a Plug-in Hybrid Electric Vehicle (PHEV), an Electric truck, an Electric commercial Vehicle, or a system for storing Electric Power.
Hereinafter, preferred embodiments are proposed to aid understanding of the present invention. However, the following examples are only for easier understanding of the present invention, and the present invention is not limited to the following examples.
Examples
Example 1
Mixing Ni under the condition of L i/Me (Ni + Co + Mn) 1.03-1.050.5Co0.2Mn0.3(OH)2Precursors (manufacturer: Bangpu) and L i2CO3(manufacturer: Rockwood) thereafter, using an RHK continuous furnace having a length of 40m, heat-treated at a temperature of 910 ℃ to 930 ℃ for 10 hours in an air atmosphere to prepare L ixNi0.5Co0.2Mn0.3O2Pulverizing L i using a winnowing machinexNi0.5Co0.2Mn0.3O2Thereafter, the lithium-containing compound L-1 was prepared by filtration (sieve) through 400 mesh.
In the preparation of Al (OH)3Aqueous solution (manufacturer: Sinuo chemical, China) (Al (OH))3Concentration (w/w) 1000ppm,B2O3Aqueous solutions (manufacturer: pure chemical) (B)2O3Concentration (w/w) ═ 300ppm) and n-SiO2Aqueous solution (manufacturer: Aladdin) (n-SiO)2After the concentration (w/w) was set to 500ppm, the above components were mixed in the same weight ratio to prepare a surface treatment solution S-1.
Then, the lithium-containing compound L-1 was gradually added to the surface treatment solution S-1 by the apparatus shown in fig. 1 and stirred until the weight ratio of the surface treatment solution S-1 to the lithium-containing compound L-1 was 1: 2, and after the addition was completed, additional stirring was performed for about 1 hour, and then, mixing and drying were performed at a temperature of 100 ℃ for 3 to 5 hours, and then, additional heat treatment was performed at a temperature of 500 ℃ for 5 hours, and finally, classification was performed by 400mesh to prepare a positive electrode active material for a lithium secondary battery.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 2
In the preparation of Al (OH)3Aqueous solution (manufacturer: Sinuo chemical, China) (Al (OH))3Concentration (w/w) ═ 1000ppm), B2O3Aqueous solutions (manufacturer: pure chemical) (B)2O3Concentration (w/w) ═ 500ppm) and n-SiO2Aqueous solution (manufacturer: Aladdin) (n-SiO)2After the concentration (w/w) was set to 300ppm, the above components were mixed in the same weight ratio to prepare a surface treatment solution S-2.
Then, the lithium-containing compound L-1 was gradually added to the surface treatment solution S-2 by using the apparatus shown in fig. 1, and stirred until the weight ratio of the surface treatment solution S-2 to the lithium-containing compound L-1 became 1: 2, and after the addition was completed, additional stirring was performed for about 1 hour, and then, mixing and drying were performed at a temperature of 100 ℃ for 4 to 6 hours, and then, additional heat treatment was performed at a temperature of 300 ℃ for 5 hours, and finally, classification was performed by 400mesh to prepare a positive electrode active material for a lithium secondary battery.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 3
In the preparation of Al (OH)3Aqueous solution (manufacturer: Sinuo chemical, China) (Al (OH))3Concentration (w/w) ═ 500ppm), B2O3Aqueous solutions (manufacturer: pure chemical) (B)2O3Concentration (w/w) ═ 500ppm) and n-SiO2Aqueous solution (manufacturer: Aladdin) (n-SiO)2After the concentration (w/w) was set to 500ppm, the above components were mixed in the same weight ratio to prepare a surface treatment solution S-3.
Then, the lithium-containing compound L-1 was gradually added to the surface treatment solution S-3 by using the apparatus shown in fig. 1, and stirred until the weight ratio of the surface treatment solution S-3 to the lithium-containing compound L-1 was 1: 2, and after the addition was completed, additional stirring was performed for about 1 hour, and then, mixing and drying were performed at a temperature of 100 ℃ for 3 to 5 hours, and then, additional heat treatment was performed at a temperature of 700 ℃ for 5 hours, and finally, classification was performed by 400mesh to prepare a positive electrode active material for a lithium secondary battery.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 4
In the preparation of Al (OH)3Aqueous solution (manufacturer: Sinuo chemical, China) (Al (OH))3Concentration (w/w) ═ 500ppm), B2O3Aqueous solutions (manufacturer: pure chemical) (B)2O3Concentration (w/w) ═ 100ppm) and n-SiO2Aqueous solution (manufacturer: Aladdin) (n-SiO)2After the concentration (w/w) was set to 500ppm, the above components were mixed in the same weight ratio to prepare a surface treatment solution S-4.
Then, the lithium-containing compound L-1 was gradually added to the surface treatment solution S-4 by using the apparatus shown in fig. 2, and stirred until the weight ratio of the surface treatment solution S-4 to the lithium-containing compound L-1 became 1: 2, and after the addition was completed, additional stirring was performed for about 1 hour, and then, mixing and drying were performed at a temperature of 100 ℃ for 3 to 5 hours, and then, additional heat treatment was performed at a temperature of 500 ℃ for 5 hours, and finally, classification was performed by 400mesh to prepare a positive electrode active material for a lithium secondary battery, and a scanning electron microscope photograph showing observation of the positive electrode active material for a lithium secondary battery is shown in part (a) of fig. 3.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 5
Mixing Ni under the condition of L i/Me (Ni + Co + Mn) 1.03-1.050.6Co0.2Mn0.2(OH)2Precursors (manufacturer: Bangpu) and L i2CO3(manufacturer: Loxowood) was followed by heat treatment at 860 ℃ to 880 ℃ for 10 hours in an air atmosphere using an RHK continuous furnace having a length of 40m to prepare L ixNi0.6Co0.2Mn0.2O2Pulverizing L i using a winnowing machinexNi0.6Co0.2Mn0.2O2Thereafter, the lithium-containing compound L-2 was prepared by filtration (sieve) through 400 mesh.
Next, a positive electrode active material for a lithium secondary battery was prepared in the same manner as in example 1, except that a lithium-containing compound L-2 was used instead of the lithium-containing compound L-1, and a scanning electron micrograph for observing the above-described positive electrode active material for a lithium secondary battery is shown in fig. 3 (b).
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 6
A positive electrode active material for a lithium secondary battery was prepared in the same manner as in example 2, except that a lithium-containing compound L-2 was used instead of the lithium-containing compound L-1, and a scanning electron microscope photograph for observing the above-described positive electrode active material for a lithium secondary battery is shown in part (c) of fig. 3.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 7
A positive electrode active material for a lithium secondary battery was finally prepared by the same method as in example 3, except that the lithium-containing compound L-2 prepared in example 5 was used instead of the lithium-containing compound L-1.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 8
A positive electrode active material for a lithium secondary battery was finally prepared by the same method as example 4, except that the lithium-containing compound L-2 prepared in example 5 was used instead of the lithium-containing compound L-1.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 9
Mixing Ni under the condition of L i/Me (Ni + Co + Mn) 1.03-1.050.7Co0.15Mn0.15(OH)2Precursors (manufacturer: Bangpu) and L i2CO3(manufacturer: Rockwood) thereafter, heat-treated at 780 to 800 ℃ for 10 hours in an air atmosphere using an RHK continuous furnace having a length of 40m to prepare L ixNi0.7Co0.2Mn0.15O2Pulverizing L i using a winnowing machinexNi0.7Co0.15Mn0.15O2Thereafter, the lithium-containing compound L-3 was prepared by filtration (sieve) through 400 mesh.
Thereafter, a positive electrode active material for a lithium secondary battery was finally prepared by the same method as example 1, except that the lithium-containing compound L-3 was used instead of the lithium-containing compound L-1.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 10
A positive electrode active material for a lithium secondary battery was finally prepared by the same method as example 2, except that the lithium-containing compound L-3 prepared in example 9 was used instead of the lithium-containing compound L-1.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 11
A positive electrode active material for a lithium secondary battery was finally prepared by the same method as in example 3, except that the lithium-containing compound L-3 prepared in example 9 was used instead of the lithium-containing compound L-1.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 12
A positive electrode active material for a lithium secondary battery was finally prepared by the same method as in example 4, except that the lithium-containing compound L-3 prepared in example 9 was used instead of the lithium-containing compound L-1.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 13
In the preparation of Al (OH)3Aqueous solution (manufacturer: Sinuo chemical, China) (Al (OH))3Concentration (w/w) ═ 1000ppm), B2O3Aqueous solutions (manufacturer: pure chemical) (B)2O3After the concentration (w/w) was 3000ppm, the above components were mixed in the same weight ratio to prepare a surface treatment solution S-5.
Thereafter, a positive electrode active material for a lithium secondary battery was finally prepared by the same method as example 1, except that the surface treatment solution S-5 was used instead of the surface treatment solution S-1.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 14
In the preparation of Al (OH)3Aqueous solution (manufacturer: Sinuo chemical, China) (Al (OH))3Concentration (w/w) ═ 500ppm) and n-SiO2Aqueous solution (manufacturer: Aladdin) (n-SiO)2After the concentration (w/w) was set to 300ppm, the above components were mixed in the same weight ratio to prepare a surface treatment solution S-6.
Thereafter, a positive electrode active material for a lithium secondary battery was finally prepared by the same method as example 2, except that the surface treatment solution S-6 was used instead of the surface treatment solution S-2.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 15
In the separate preparation of B2O3Aqueous solutions (manufacturer: pure chemical) (B)2O3Concentration (w/w) ═ 500ppm) and n-SiO2Aqueous solution (manufacturer: Aladdin) (n-SiO)2After the concentration (w/w) was set to 500ppm, the above components were mixed in the same weight ratio to prepare a surface treatment solution S-7.
Thereafter, a positive electrode active material for a lithium secondary battery was finally prepared by the same method as in example 3, except that the surface treatment solution S-7 was used instead of the surface treatment solution S-2.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Example 16
Mixing Ni under the condition of L i/Me (Ni + Co + Mn) 1.030.8Co0.1Mn0.1(OH)2Precursors (manufacturer: Bangpu) and L i2CO3(manufacturer: Rockwood) thereafter, L i was prepared by heat-treating at 760 ℃ for 10 hours in an air atmosphere using an RHK continuous furnace having a length of 40mxNi0.8Co0.1Mn0.1O2Pulverizing L i using a winnowing machinexNi0.8Co0.1Mn0.1O2Thereafter, the lithium-containing compound L-4 was prepared by filtration (sieve) through 400 mesh.
Thereafter, a positive electrode active material for a lithium secondary battery was finally prepared by the same method as example 1, except that a lithium-containing compound L-4 was used in place of the lithium-containing compound L-1 and additional heat treatment was performed at a temperature of 400 ℃ for about 5 hours.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 5 to 7 μm.
Example 17
Except that 1000ppm of Al was used as the coating material2O3And 1000ppm of ZrO2Instead of L ixNi0.8Co0.1Mn0.1O2Powder preparation L ixNi0.8Co0.1Mn0.08Al0.01Zr0.01O2Except for this, a positive electrode active material for a lithium secondary battery was finally prepared by the same method as in example 16.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 5 to 7 μm.
Example 18
Except that 2000ppm of Al was used as the coating material2O3And 1000ppm of ZrO2Instead of L ixNi0.8Co0.1Mn0.1O2Powder preparation L ixNi0.8Co0.1Mn0.07Al0.02Zr0.01O2Except for this, a positive electrode active material for a lithium secondary battery was finally prepared by the same method as in example 16.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 5 to 7 μm.
Example 19
Except that 3000ppm of Al was used as the coating material2O3And 1000ppm of ZrO2Instead of L ixNi0.8Co0.1Mn0.1O2Powder preparation L ixNi0.8Co0.1Mn0.06Al0.03Zr0.01O2Except for this, a positive electrode active material for a lithium secondary battery was finally prepared by the same method as in example 16.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 5 to 7 μm.
Comparative example 1
The lithium-containing compound L-1 prepared in example 1 was used as a positive electrode active material for a lithium secondary battery.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Comparative example 2
The lithium-containing compound L-2 prepared in example 5 was used as a positive electrode active material for a lithium secondary battery, and a scanning electron micrograph for observing the positive electrode active material for a lithium secondary battery is shown in part (d) of fig. 3.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Comparative example 3
The lithium-containing compound L-3 prepared in example 9 was used as a positive electrode active material for a lithium secondary battery.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Comparative example 4
Preparation of commercial L iCoO by lithium-containing Compound L42B was prepared as a surface treatment solution S-72O3Aqueous solutions (manufacturer: pure chemical) (B)2O3The concentration (w/w) was 300 ppm.
Then, the lithium-containing compound L-4 was slowly added to the surface treatment solution S-7 by using the apparatus shown in fig. 1, and stirred until the weight ratio of the surface treatment solution S-7 to the lithium-containing compound L-4 reached 1: 2, and after the addition was completed, additional stirring was performed for 1 hour, and then, mixing and drying were performed at 100 ℃ for about 3 to 6 hours, and finally, classification was performed by 40mesh to prepare a positive electrode active material for a lithium secondary battery.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Comparative example 5
A positive electrode active material for a lithium secondary battery was finally prepared by the same method as comparative example 4, except that mixing and drying were performed at a temperature of 300 ℃.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Comparative example 6
A positive electrode active material for a lithium secondary battery was finally prepared by the same method as comparative example 4, except that mixing and drying were performed at a temperature of 500 ℃.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Comparative example 7
A positive electrode active material for a lithium secondary battery was finally prepared by the same method as comparative example 4, except that mixing and drying were performed at a temperature of 700 ℃.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Comparative example 8
A UM NCM111 product manufactured by U.S. corporation was prepared as a positive electrode active material for a lithium secondary battery.
As a result of analyzing the finally prepared positive electrode active material by a particle size analyzer, D50 was 11 to 13 μm.
Comparative example 9
A UM NCM523 product manufactured by U.S. corporation was prepared as a positive electrode active material for a lithium secondary battery.
As a result of analyzing the final other positive electrode active material by a particle size analyzer, D50 was 11 μm to 13 μm.
TABLE 1
Figure GDA0001836292300000181
Figure GDA0001836292300000191
Examples of the experiments
(1) X-ray diffraction crystal structure of positive electrode active material
The positive electrode active materials finally prepared in example 2 and comparative example 1 were subjected to X-ray diffraction crystal structure analysis, and the results are shown in fig. 4.
As shown in fig. 4, in the case of surface treatment by a plurality of compounds as in example 2, it was confirmed that small angle shift (low angle shift) occurred as compared with the case of not performing surface treatment as in comparative example 1. This phenomenon occurs because the lattice constant increases as a result of the surface treatment.
In particular, in the case of example 2, since surface coating (surface painting) was performed by adding heat treatment after the surface treatment, it was confirmed that small-angle shift occurred by increasing the lattice constant of the unit cell of the crystal structure.
(2) Evaluation of the Life characteristics of button cells
In the finally prepared positive active materials in examples and comparative examples, the weight ratio of the conductive material to the binder was 95: 2.5: 2.5, and after preparing positive active material slurry using NMP solution, a positive electrode plate was prepared under the condition of plate density of 3.3g/cc using L i metal negative electrode and EC/DMC/DEC [1/1/1 ]]+1MLiPF6Electrolyte is used for preparing the button cell in a drying chamber. Thereafter, initial charge-discharge was performed under 0.1C/0.1C charge-discharge conditions.
After the initial charge and discharge, the coin cell was evaluated for its normal temperature life characteristics by performing charge and discharge at a temperature of 25 ℃ under 4.5 to 3.0V1C/1C (or 0.5C/0.5C) charge and discharge conditions, and the results are shown in FIGS. 5a to 5 d.
After the initial charge and discharge, the coin cell was evaluated for its high-temperature life characteristics by performing charge and discharge under 4.5 to 3.0V1C/1C (or 0.5C/0.5C) charge and discharge conditions at a temperature of 45 ℃, and the results are shown in FIGS. 6a to 6 e.
As shown in fig. 5a to 5d and fig. 6a to 6e, in the case of performing the surface treatment by a plurality of compounds as in the example, the button cell was confirmed to have excellent life characteristics at normal temperature and high temperature as compared with the case of not performing the surface treatment as in the comparative example.
Specifically, in the cases of examples 1 to 3 and example 13, the improvement in the capacity retention rate of the coin cell by about 2% after 60 cycles was confirmed, as compared with comparative example 1, and the excellent room temperature life characteristics of the coin cell were confirmed (see fig. 5a and 5 b).
In addition, in the case of examples 1 to 3 and example 13, the improvement in the capacity retention rate of the coin cell was confirmed to be about 4% after 80 cycles compared to comparative example 1, and in the case of example 13, the improvement in the capacity retention rate of the coin cell was confirmed to be about 0.5% after 70 cycles compared to comparative example 1, and the coin cell was confirmed to have excellent high-temperature life characteristics (see fig. 6a and 6 b).
In example 18, the capacity retention rate of the button cell was improved by about 4% after 50 cycles, and the high-temperature life characteristics of the button cell were confirmed to be excellent, as compared to example 16 (fig. 10). This is because a specific element is applied to the lithium-containing compound, and preferably, a composite coating is performed. In examples 16 and 18, when the 50% cumulative mass particle size distribution diameter in the particle distribution of the positive electrode active material was D50, the button cell was confirmed to have excellent high-temperature life characteristics in the case of using the fine particles corresponding to the fine particles having a D50 of 5 μm to 7 μm.
(3) Evaluation of Life characteristic of Fuel cell
In the finally prepared positive electrode active materials of examples 2 and 13 and comparative example 1, the weight ratio of the conductive material to the binder was 92: 5: 3, and after preparing positive electrode active material slurry using NMP solution, positive electrode plates were prepared under the condition of plate density of 3.3 to 3.4g/cc using L i metal negative electrode and EC/DMC/DEC [1/1/1 ]]+1M LiPF6Electrolyte to make angular fuel cells. Thereafter, initial charge-discharge was performed under 0.1C/0.1C charge-discharge conditions.
After the initial charge and discharge was performed, the normal temperature life characteristics of the fuel cell were evaluated by performing charge and discharge under 4.2 to 3.0V1C/1C charge and discharge conditions at a temperature of 25 ℃, and the results are shown in FIG. 5 e.
After the initial charge and discharge was performed, the high-temperature life characteristics of the fuel cell were evaluated by performing charge and discharge under 4.2 to 3.0V1C/1C (or 0.5C/0.5C) charge and discharge conditions at a temperature of 45 ℃, and the results are shown in fig. 6 f.
As shown in fig. 5e and 6f, in the case of surface treatment by a plurality of compounds as in examples 2 and 13, the fuel cell was confirmed to have excellent life characteristics at normal temperature and high temperature as compared with the case of not surface-treated as in comparative example 1.
(4) Evaluation based on C-rate change of button cell
In (2), coin cells were prepared by the above-described method using the cathode active materials finally prepared in example 10 and comparative example 3. After that, under the 0.1C/0.1C charge-discharge condition, after the initial charge-discharge was performed, the capacity retention rate of the coin cell was evaluated by changing the C-rate in the order of 0.2C, 0.33C, 0.5C, 1.0C, 3.0C, and 5.0C, and the above results are shown in fig. 7.
As shown in fig. 7, in example 10, the coin cell was also confirmed to have a higher capacity retention rate under the conditions of 3.0C and 5.0C, as compared with comparative example 3.
(5) Evaluation of thermal stability of button cell (coin cell)
Coin cells were prepared by the method described in (2) using the cathode active materials finally prepared in examples 2, 13 to 15, and comparative example 1. Thereafter, the coin cell charged at 4.3V was released in the drying chamber to separate the plates. About 10mg of the positive active material coated on the aluminum foil was extracted from the separated electrode plate and subjected to DSC analysis by 910DSC (product of TA instruments). In the DSC analysis, scanning is performed at a temperature rise rate of 3 ℃/min in a temperature range of 25 to 300 ℃ in an air atmosphere. The DSC analysis results are shown in fig. 8.
As shown in fig. 8, in examples 2 and 13 to 15, the peak value of the heat flow rate based on the temperature was not high as compared with comparative example 1, and it was confirmed that the heat stability was excellent.
(6) Evaluation of expansion characteristics based on Fuel cell
A fuel cell was produced by the method described in (2) using the cathode active material finally produced in example 2 and comparative examples 1, 8, and 9. After that, after being left at a temperature of 60 ℃ for 7 days, the phenomenon of high temperature expansion (hot swelling) of the fuel cell was compared with each other, and the phenomenon of low temperature expansion (cold swelling) of the fuel cell was compared with each other by lowering the temperature to the normal temperature (25 ℃), and the above results are shown in fig. 9.
As shown in fig. 9, in example 2, improvement in expansion characteristics was observed as compared with comparative examples 1, 8, and 9. In particular, in the case of example 2, it was confirmed that the fuel cell had an excellent high-temperature swelling effect in a state where the fuel cell was left at 60 ℃.
(7) Evaluation based on C-rate variation of fuel cell
A fuel cell was produced by the method described in (2) using the cathode active materials finally produced in examples 18 and 19. After that, under the 0.1C/0.1C charge-discharge condition, after the initial charge-discharge was performed, the C-rate was changed in the order of 2C and 4C and the high output characteristics of the fuel cell were evaluated, and the above results are shown in fig. 11.
As shown in fig. 11, in example 19, it was confirmed that the discharge phenomenon was more likely to occur than in example 18, and the discharge amount was larger than in L ow C-rate, and therefore, in order to ensure High output characteristics, it was necessary to adjust the amount of the specific element to be applied to the lithium-containing compound.
In examples 18 and 19, it was confirmed that the high output characteristics of the fuel cell were excellent when the fine particles were used, in which the particle size distribution diameter of 50% cumulative mass was D50 in the particle distribution of the positive electrode active material, and the D50 was 5 μm to 7 μm.
The above description of the present invention is intended to be illustrative, and it will be readily apparent to those skilled in the art that the present invention may be modified into other specific forms without departing from the spirit or essential characteristics thereof. Therefore, the above-described embodiments are illustrative in all respects and are not intended to limit the present invention.

Claims (7)

1. A method for preparing a positive electrode active material for a lithium secondary battery,
the method comprises the following steps:
step a, preparing a lithium-containing compound;
step b, preparing a mixture containing Al (OH)3Solution B2O3Solution and n-SiO2A solution for surface treatment;
a step c of performing mixing and drying at a temperature of 50 to 100 ℃ for 1 to 10 hours after adding the lithium-containing compound prepared in the above step a to the surface treatment solution prepared in the above step b; and
step d of performing additional heat treatment at a temperature of 300 to 500 ℃ for 1 to 10 hours,
in the step b, the amount of Al (OH) is adjusted to 100 parts by weight3Containing 30 to 50 parts by weight of B2O3And 30 to 50 parts by weight of n-SiO2，
In the step c, the weight ratio of the surface treatment solution to the lithium-containing compound is 0.5: 1 to 1: 3.
2. the method of manufacturing a positive electrode active material for a lithium secondary battery according to claim 1, wherein, in the step a, the lithium-containing compound includes one or more compounds selected from the group consisting of a lithium-nickel-cobalt-manganese-based compound, a lithium-nickel-cobalt-aluminum-based compound, and a lithium-cobalt-based compound.
3. The method of manufacturing a positive electrode active material for a lithium secondary battery according to claim 1, wherein, in the step a, the lithium-containing compound is a lithium-nickel-cobalt-manganese-based compound represented by the following chemical formula 1:
chemical formula 1
LixNi1-y-z-aCoyMnzMaA2
In the formula, x is more than or equal to 0.95 and less than or equal to 1.1, y is more than or equal to 0.05 and less than or equal to 0.2, z is more than or equal to 0.05 and less than or equal to 0.3, and a is more than or equal to 0.04, wherein M is more than or equal to one selected from the group consisting of Mg, Ti, Al and Zr, and A is selected from the group consisting of O, F, S and P.
4. The method of producing a positive electrode active material for a lithium secondary battery according to claim 1, wherein in the step a, when the 50% cumulative mass particle size distribution diameter in the particle distribution of the positive electrode active material is D50, D50 is 5 μm to 7 μm.
5. The method for preparing a positive electrode active material for a lithium secondary battery according to claim 1, wherein in the step b, Al (OH)3Solution B2O3Solutions or n-SiO2The solution uses water or 95% or less ethanol as a solvent.
6. The method for preparing a positive electrode active material for a lithium secondary battery according to claim 1, wherein in the step b, Al (OH)3Solution B2O3Solutions or n-SiO2The concentration of each solute in the solution is 1ppm to 1000 ppm.
7. The method of manufacturing a positive electrode active material for a lithium secondary battery according to claim 1, wherein in the step c, the mixing and the drying are performed simultaneously.
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