CN111200120A - Ternary cathode material, preparation method thereof and lithium ion battery - Google Patents

Ternary cathode material, preparation method thereof and lithium ion battery Download PDF

Info

Publication number
CN111200120A
CN111200120A CN201811384733.4A CN201811384733A CN111200120A CN 111200120 A CN111200120 A CN 111200120A CN 201811384733 A CN201811384733 A CN 201811384733A CN 111200120 A CN111200120 A CN 111200120A
Authority
CN
China
Prior art keywords
cobalt
cobalt borate
ternary
cathode material
nickel ternary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811384733.4A
Other languages
Chinese (zh)
Other versions
CN111200120B (en
Inventor
严武渭
温伟城
杨顺毅
黄友元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen City Battery Nanometer Technology Co ltd
Original Assignee
Shenzhen City Battery Nanometer Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen City Battery Nanometer Technology Co ltd filed Critical Shenzhen City Battery Nanometer Technology Co ltd
Priority to CN201811384733.4A priority Critical patent/CN111200120B/en
Publication of CN111200120A publication Critical patent/CN111200120A/en
Application granted granted Critical
Publication of CN111200120B publication Critical patent/CN111200120B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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 invention provides a ternary cathode material, a preparation method thereof and a lithium ion battery. The ternary cathode material mainly comprises a high-nickel ternary material core and a cobalt borate coating layer. The preparation method comprises the following steps: 1) mixing a boron source and a cobalt source, and sintering in a protective atmosphere to obtain cobalt borate; 2) mixing the cobalt borate with the high-nickel ternary material, and heating in an oxidizing atmosphere to obtain the ternary cathode material. The ternary cathode material provided by the invention has the advantages that the high-nickel ternary material core, the cobalt borate coating layer and the lithium cobalt borate positioned between the high-nickel ternary material core and the cobalt borate coating layer are matched with each other, so that the ternary cathode material is low in residual alkali content and good in rate discharge capacity and cycle performance. The preparation method provided by the invention has the advantages of short flow, simple operation and easy industrialized mass production.

Description

Ternary cathode material, preparation method thereof and lithium ion battery
Technical Field
The invention belongs to the technical field of energy storage materials, relates to a ternary cathode material, and particularly relates to a ternary cathode material, a preparation method thereof and a lithium ion battery.
Background
The lithium ion battery is widely applied to consumer electronics, energy storage, electric vehicles and other fields, especially the demand for high energy density is continuously increased due to the increase of the endurance mileage of the electric vehicles at present, and compared with the high capacity (more than or equal to 350mAh/g) of a graphite cathode system, the capacity of an anode material restricts the energy density of the lithium ion battery, so that the anode material with higher energy density needs to be developed. High-nickel ternary cathode material LizNi1-x-yCoxMyO2(z is more than or equal to 0.95 and less than or equal to 1.10, x is more than or equal to 0 and less than or equal to 0.20, y is more than or equal to 0 and less than or equal to 0.20, and M is one or more of Mn, Al, Mg, Ti and Nb), has higher discharge capacity (more than or equal to 180mAh/g) and voltage platform (3.8V), and becomes one of the most competitive anode materials at present. However, the high nickel ternary positive electrode material suffers from a problem of difficult processing caused by a high residual alkali (lithium hydroxide, lithium carbonate, etc.), and a disadvantage of poor high temperature cycle.
However, high nickel ternary positive electrode materials face high residual alkali (lithium hydroxide, lithium carbonate, lithium bicarbonate, etc.) yielding Ni3+Reduction to Ni2+And the generated active oxygen free radicals react with moisture and carbon dioxide in air with high humidity to intensify the rise of residual alkali. The alkaline substance can cause the C-F bond on the PVDF to be separated from HF to generate gel, and the battery generates carbon dioxide and water under high voltage, so that the defects of reduced coulombic efficiency, battery expansion and poor high-temperature cycle are caused. Residual alkali is a poor conductor of electrons and ions, which reduces the capacity and coulombic efficiency of the battery. In addition, the high-nickel ternary cathode material reacts with an electrolyte during circulation or high-temperature storage, causing dissolution of transition metal atoms, structural transformation and particle breakage, resulting in deterioration of cycle performance and reduction of safety performance. Thus, high nickel ternary materials are realizedFor industrial application, it is necessary to reduce the surface residual alkali and improve the electrochemical performance and safety performance.
CN105789625A discloses LiCoBO3The preparation method is characterized in that lithium hydroxide, lithium carbonate, cobalt oxide or cobalt carbonate are dispersed in absolute ethyl alcohol, mixed and ball-milled, sintered in inert atmosphere after being dried, and cooled along with the furnace; then mixing with boric acid in absolute ethyl alcohol, ball milling, drying, and sintering in inert atmosphere to obtain LiCoBO3And (3) a positive electrode material. However, the rate capability and cycle performance of the cathode material obtained by the method are still to be improved.
CN107482204A discloses a metal solid solution modified high-nickel ternary cathode material and a preparation method thereof, wherein the material is of a core-shell structure and sequentially comprises a high-nickel ternary cathode material substrate, a transition layer and a coating layer from inside to outside, the coating layer comprises a metal lithium salt and one or more solid solution cathode active substances generated by the reaction of heterogeneous metal precursors and the high-nickel ternary cathode material precursors, and the transition layer is a heterogeneous metal element doped high-nickel ternary cathode material. Although the rate capability and the specific capacity are relatively good, the preparation method is extremely complicated, the product structure is complex, and the cost is high.
CN108063223A discloses a preparation method of a modified high-nickel ternary cathode material, which comprises the following steps: and mixing the washed high-nickel ternary cathode material with a metal salt solution for reaction, and drying and sintering the mixture in sequence to obtain the modified high-nickel ternary cathode material. Although the method can reduce free lithium and pH value on the surface of the high-nickel ternary material to a certain extent, the rate capability and cycle performance of the method are still to be improved.
Therefore, the development of a high-nickel ternary cathode material which is simple in preparation method, has better rate capability and cycle performance and can solve the problem of residual alkali is of great significance to the field.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a ternary cathode material, a method for preparing the same, and a lithium ion battery. The ternary cathode material provided by the invention has the advantages of high rate capacity, excellent cycle performance, low residual alkali and good industrial application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a ternary cathode material consisting essentially of a high nickel ternary material core and a cobalt borate coating.
The ternary cathode material provided by the invention improves the discharge capacity, rate capacity and cycle performance of the ternary cathode material through the interaction of the high-nickel ternary material core and the cobalt borate coating layer, and reduces the residual alkali amount on the surface of the high-nickel ternary material core.
In the invention, the cobalt borate coating layer is positioned at the outermost side of the ternary cathode material.
In the invention, the high-nickel ternary material is a ternary material with the Ni content of more than or equal to 60 percent in metal elements except Li.
Besides the high-nickel ternary material core and the cobalt borate coating layer, the ternary cathode material provided by the invention can also comprise other components or structures.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the cobalt borate coating layer is Co2B2O5And (4) coating.
Preferably, the thickness of the cobalt borate coating is 2 to 50nm, such as 2nm, 4nm, 8nm, 10nm, 14nm, 18nm or 20nm, but not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 5 to 20 nm.
Preferably, the mass ratio of the cobalt borate cladding layer to the high nickel ternary material core is (0.001-0.01):1, such as 0.001:1, 0.003:1, 0.005:1, 0.007:1, 0.009:1 or 0.01:1, but not limited to the recited values, and other values not recited in this numerical range are equally applicable, preferably (0.001-0.005): 1. In the invention, if the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is less than 0.001:1, the coating effect is ineffective, and if the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is more than 0.005:1, the coating layer is too thick and uneven, the lithium ion migration is blocked, and the multiplying power and the cycling behavior are reduced.
As a preferable technical solution of the present invention, the ternary cathode material further comprises lithium cobalt borate (LiCoBO) between the high nickel ternary material core and the cobalt borate coating layer3). In the invention, the existence of the lithium cobalt borate can reduce the residual lithium hydroxide and lithium carbonate, thereby reducing the residual alkali amount. In addition, the lithium cobalt borate has electrochemical activity, the theoretical specific capacity is 215mAh/g, the voltage platform is 4.09V, and the lithium cobalt borate is an ion and electron conductor, so that the discharge capacity, the rate capacity and the cycle performance of the high-nickel ternary cathode material can be improved. On the other hand, lithium cobalt borate belongs to a polyanion structure and has higher thermal stability and safety performance, so that the dissolution of transition metal atoms at high temperature can be inhibited, the expansion of the cathode material during high-temperature storage can be reduced, and the stability of an SEI film of the cathode material in high-temperature circulation can be improved.
Preferably, the particle size D50 of the high-nickel ternary material is 1-20 μm, such as 1 μm, 3 μm, 5 μm, 7 μm, 9 μm, 11 μm, 13 μm, 15 μm, 17 μm, 18 μm, or 20 μm, but is not limited to the recited values, and other values not recited within this range are equally applicable, preferably 3-15 μm. In the present invention, if the particle size D50 of the high nickel ternary material is less than 3 μm, the tap density decreases, and there is a possibility that the side reaction of the positive electrode material with the electrolyte solution progresses and the cycle and safety are deteriorated. If the particle size D50 of the high nickel ternary material is larger than 15 μm, the specific surface area of the positive electrode material decreases, the interface with the electrolyte decreases, and the positive electrode resistance increases and the capacity decreases.
Preferably, the chemical formula of the high-nickel ternary material core is LizNi1-x-yCoxMyO2Wherein 0.95. ltoreq. z.ltoreq.1.10, e.g.z is 0.95, 0.98, 1.00, 1.05 or 1.10 etc., 0. ltoreq. x.ltoreq.0.20, e.g.x is 0, 0.05, 0.10, 0.15 or 0.20 etc0. ltoreq. y.ltoreq.0.20, e.g. y is 0, 0.05, 0.10, 0.15 or 0.20 etc., M is any one or a combination of at least two of Mn, Al, Mg, Ti or Nb, typical but not limiting combinations are: combinations of Mn and Al, combinations of Al and Mg, combinations of Ti and Nb, and the like. In the invention, if z is less than or equal to 0.95, the lithium content of the anode material is insufficient, so that the cycle behavior is reduced, and if z is more than or equal to 1.10, redundant residual lithium and Ni are generated on the surface of the material3+Reduction to Ni2+An increase in the production of lithium nickel mixed rows, which ultimately leads to an increase in impedance leading to a decrease in capacity and cycle, is therefore preferably 0.95. ltoreq. z.ltoreq.1.10.
In a second aspect, the present invention provides a method for preparing the ternary cathode material according to the first aspect, the method comprising the steps of:
(1) mixing a boron source and a cobalt source, and sintering in a protective atmosphere to obtain cobalt borate;
(2) and (2) mixing the cobalt borate and the high-nickel ternary material in the step (1), and heating in an oxidizing atmosphere to obtain the ternary cathode material.
In the preparation method provided by the invention, firstly, a boron source and a cobalt source react to form cobalt borate, and then the cobalt borate reacts with lithium hydroxide and lithium carbonate on the surface of the high-nickel ternary cathode material at high temperature to form lithium cobalt borate (LiCoBO)3)。
As a preferred embodiment of the present invention, the boron source in step (1) includes any one or a combination of at least two of orthoboric acid, metaboric acid, tetraboric acid, boron oxide, or ammonium borate, and typical but non-limiting combinations are: combinations of orthoboric acid and metaboric acid, metaboric acid and tetraboric acid, boron oxide and ammonium borate, and the like.
Preferably, the cobalt source in step (1) comprises any one of cobalt nitrate, cobalt hydroxide, cobalt carbonate, cobalt acetate or cobalt oxalate, or a combination of at least two of the following, typically but not limited to: a combination of cobalt nitrate and cobalt hydroxide, a combination of cobalt hydroxide and cobalt carbonate, a combination of cobalt carbonate, cobalt acetate, and cobalt oxalate, and the like.
Preferably, the mixing device used in step (1) is a mixer, preferably a high-speed mixer.
Preferably, the volume of each batch of mixed material is 1/2-3/4, e.g., 1/2, 2/3, or 3/4, etc., of the volume of the mixer, but is not limited to the recited values, and other values not recited within this range of values are equally applicable. Here, if the mixed substance is filled too little, the productivity cannot be improved; if the mixture is too filled, there is a possibility that the mixing is insufficient.
Preferably, the mixer is operated at a speed of 50-100rpm, such as 50rpm, 60rpm, 70rpm, 80rpm, 90rpm, or 100rpm, but not limited to the recited values, and other values not recited within the range are equally applicable.
Preferably, the mixing time in step (1) is 0.5 to 2 hours, such as 0.5 hour, 1 hour, 1.5 hour, 2 hours, etc., but not limited to the recited values, and other values not recited in the range of values are also applicable. Here, if the mixing speed time is too short, mixing unevenness is caused; if the mixing time is too long, the productivity is reduced.
In a preferred embodiment of the present invention, the sintering in step (1) is solid-phase sintering.
Preferably, the sintering temperature for the sintering in step (1) is 400-.
Preferably, the sintering time in step (1) is 3-5h, such as 3h, 3.5h, 4h, 4.5h or 5h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature rise rate of the sintering in step (1) is 3-5 deg.C/min, such as 3 deg.C/min, 3.5 deg.C/min, 4 deg.C/min, 4.5 deg.C/min, or 5 deg.C/min, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the protective atmosphere in step (1) is any one of a nitrogen atmosphere, an argon atmosphere or a carbon dioxide atmosphere or a combination of at least two of the above.
Preferably, the flow rate of the protective atmosphere gas introduced per 10kg of the mixture during the sintering in step (1) is 1-10L/h, such as 1L/h, 2L/h, 3L/h, 4L/h, 5L/h, 6L/h, 7L/h, 8L/h, 9L/h or 10L/h, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the sintering of step (1) is carried out in a box furnace or kiln.
Preferably, the cobalt borate in step (1) is Co2B2O5。
In a preferred embodiment of the present invention, the particle size D50 of the high nickel ternary material is 1 to 20 μm, for example, 1 μm, 3 μm, 5 μm, 7 μm, 9 μm, 11 μm, 13 μm, 15 μm, 17 μm, 18 μm, or 20 μm, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, preferably 3 to 15 μm.
Preferably, the chemical formula of the high-nickel ternary material in the step (2) is LizNi1-x-yCoxMyO2Wherein 0.95. ltoreq. z.ltoreq.1.10, e.g. z is 0.95, 0.98, 1.00, 1.05 or 1.10 etc., 0. ltoreq. x.ltoreq.0.20, e.g. x is 0, 0.05, 0.10, 0.15 or 0.20 etc., 0. ltoreq. y.ltoreq.0.20, e.g. y is 0, 0.05, 0.10, 0.15 or 0.20 etc., M is any one or a combination of at least two of Mn, Al, Mg, Ti or Nb, typically but not limited to: combinations of Mn and Al, combinations of Al and Mg, combinations of Ti and Nb, and the like. In the invention, if z is less than or equal to 0.95, the lithium content of the anode material is insufficient, so that the cycle behavior is reduced, and if z is more than or equal to 1.10, redundant residual lithium and Ni are generated on the surface of the material3+Reduction to Ni2+An increase in the production of lithium nickel mixed rows, which ultimately leads to an increase in impedance leading to a decrease in capacity and cycle, is therefore preferably 0.95. ltoreq. z.ltoreq.1.10.
Preferably, the mixing device used in the step (2) is a mixer, preferably a high-speed mixer.
Preferably, the volume of each batch of mixed material is 1/2-3/4, e.g., 1/2, 2/3, or 3/4, etc., of the volume of the mixer, but is not limited to the recited values, and other values not recited within this range of values are equally applicable. Here, if the mixed substance is filled too little, the productivity cannot be improved; if the mixture is filled too much, the mixing may be insufficient, and the crystallinity of the positive electrode material may be affected.
Preferably, the mixer is operated at a speed of 50-100rpm, such as 50rpm, 60rpm, 70rpm, 80rpm, 90rpm, or 100rpm, but not limited to the recited values, and other values not recited within the range are equally applicable. In the present invention, if the mixing speed is too low, mixing unevenness is caused; if the speed is too high, secondary particles on the surface of the positive electrode material are abraded, and the transfer rate of lithium ions and the cycle performance of the battery are affected.
Preferably, the mixing time in step (2) is 0.5-2h, such as 0.5h, 1h, 1.5h or 2h, but not limited to the recited values, and other values not recited in the range of values are also applicable. Here, if the mixing speed time is too short, mixing unevenness is caused; if the mixing time is too long, the productivity is reduced.
Preferably, in step (2), the mass ratio of the cobalt borate to the high nickel ternary material is (0.001-0.01):1, for example, 0.001:1, 0.003:1, 0.005:1, 0.007:1, 0.009:1 or 0.01:1, but not limited to the recited values, and other values not recited in this numerical range are equally applicable, preferably (0.001-0.005): 1. In the invention, if the mass ratio of the cobalt borate package to the high-nickel ternary material is less than 0.001:1, the coating effect is ineffective, and if the mass ratio of the cobalt borate package to the high-nickel ternary material is more than 0.005:1, the coating layer is too thick and uneven, the lithium ion migration is blocked, and the multiplying power and the cycle behavior are reduced.
And (3) heating from room temperature in the process of coating the high-nickel ternary material composite material with the cobalt borate in the step (2).
In the preferred embodiment of the present invention, in the step (2), the heating temperature is 200-500 ℃, for example, 200 ℃, 300 ℃, 400 ℃ or 500 ℃, but the heating temperature is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, in step (2), the heating time is 5-10h, such as 5h, 6h, 7h, 8h, 9h or 10h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, in step (2), the heating rate is 3-5 deg.C/min, such as 3 deg.C/min, 3.5 deg.C/min, 4 deg.C/min, 4.5 deg.C/min, or 5 deg.C/min, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, in the step (2), the oxidizing atmosphere is an oxygen atmosphere and/or an air atmosphere.
Preferably, the flow rate of the oxidizing atmosphere gas introduced per 10kg of the mixture during the heating in step (2) is 1 to 10L/h, for example, 1L/h, 2L/h, 3L/h, 4L/h, 5L/h, 6L/h, 7L/h, 8L/h, 9L/h or 10L/h, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the heating of step (2) is performed in a box furnace or kiln.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1) mixing a boron source and a cobalt source in a mixer at a rotating speed of 50-100rpm for 0.5-2h, heating to 400-600 ℃ at a heating rate of 3-5 ℃/min in a protective atmosphere, and sintering for 3-5h to obtain cobalt borate;
the protective atmosphere comprises any one or the combination of at least two of nitrogen atmosphere, argon atmosphere and carbon dioxide atmosphere, and the gas flow of the protective atmosphere introduced into every 10kg of mixed materials in the sintering process is 1-10L/h;
(2) mixing the cobalt borate and the high-nickel ternary material in the step (1) in a mixer at a rotating speed of 50-100rpm for 0.5-2h, and heating to 200-500 ℃ at a heating rate of 3-5 ℃/min in an oxidizing atmosphere for 5-10h to obtain the ternary cathode material;
wherein the mass ratio of the cobalt borate to the high-nickel ternary material is (0.001-0.005) to 1; the particle size D50 of the high-nickel ternary material is 3-15 mu m, the oxidizing atmosphere is an oxygen atmosphere and/or an air atmosphere, and the flow rate of oxidizing atmosphere gas introduced into each 10kg of mixed material in the heating process is 1-10L/h.
In a third aspect, the present invention provides a lithium ion battery comprising the ternary cathode material according to the first aspect. The ternary cathode material provided by the invention is used on a lithium ion battery, obviously improves the rate discharge capacity and the cycle performance of the battery, and has good industrial application prospect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the ternary cathode material provided by the invention has the advantages that the high-nickel ternary material core, the cobalt borate coating layer and the lithium cobalt borate positioned between the high-nickel ternary material core and the cobalt borate coating layer are matched with each other, so that the ternary cathode material provided by the invention is low in residual alkali content and good in rate discharge capacity and cycle performance. The residual alkali content can be controlled below 3500ppm, the minimum content is 2537ppm, the 0.1C capacity can reach 215mAh/g, the 4C capacity can reach 190mAh/g, and the capacity retention rate after 100 charge-discharge cycles can reach more than 90%.
(2) The preparation method provided by the invention has the advantages of short flow, simple operation and easy industrialized mass production, and can ensure that the cobalt borate reacts with the lithium hydroxide and the lithium carbonate on the surface of the high-nickel ternary material at high temperature to form the lithium cobalt borate, further reduce the residual alkali content of the product and improve the electrochemical performance of the product.
Drawings
Fig. 1a is a Scanning Electron Microscope (SEM) picture of the cobalt borate coated ternary cathode material prepared in example 1 of the present invention;
FIG. 1b is a Scanning Electron Microscope (SEM) picture of the cobalt borate coated ternary cathode material prepared in example 7 of the present invention;
FIG. 1c is a Scanning Electron Microscope (SEM) picture of the cobalt borate coated ternary cathode material prepared in example 8 of the present invention;
fig. 2 is a first charge-discharge curve of the ternary cathode material coated with cobalt borate prepared in example 1 of the present invention and the ternary cathode material uncoated with cobalt borate prepared in comparative example 1;
fig. 3 is a graph showing cycle performance of the ternary cathode material coated with cobalt borate prepared in example 1 according to the present invention and the ternary cathode material uncoated with cobalt borate prepared in comparative example 1.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
This example prepares a ternary cathode material as follows:
(1) mixing orthoboric acid and cobalt nitrate according to a molar ratio of B to Co of 1:1, putting the mixture into a high-speed mixer (a high-speed mixer for short), wherein the volume of the high-speed mixer is 1/5 (namely the loading amount is 1/5) which occupies the volume of the high-speed mixer, mixing the mixture for 0.5 hour at the speed of 100rpm, then filling the mixture into a sagger, putting the sagger into a kiln, heating the sagger to 400 ℃ at the speed of 5 ℃/min, preserving the heat for 5 hours, and introducing 1L/h of nitrogen into the kiln. After sintering, crushing, sieving by a 325-mesh sieving machine to obtain Co2B2O5。
(2) Mixing Co2B2O5With a high nickel ternary material Li with an average particle size of 3 mu m1.01Ni0.8Co0.1Mn0.1O2Mixing the materials for 1h at a rotating speed of 50rpm on a high-speed mixer according to a mass ratio of 0.001:1 and a loading amount of 1/5, then filling the materials into a sagger, putting the sagger into a kiln, heating the sagger to 500 ℃ at a speed of 4 ℃/min, keeping the temperature for 5h, introducing oxygen into the kiln, and ensuring that the gas flow required by 10kg of mixed materials is 1L/h. After sintering, crushing, sieving by a 325-mesh sieving machine to obtain Co2B2O5Coated Li1.01Ni0.8Co0.1M0.1O2The composite ternary positive electrode material of (1).
Fig. 1a is a Scanning Electron Microscope (SEM) image of the ternary cathode material coated with cobalt borate prepared in this embodiment, and it can be seen from the image that the surface coating layer of the ternary cathode material coated with cobalt borate prepared in this embodiment is thin and uniform.
The test results of the ternary cathode material prepared in this example are shown in table 1.
The ternary cathode material prepared in this embodiment mainly comprises a high-nickel ternary material core and a cobalt borate coating layer, and the ternary cathode material further comprises lithium cobalt borate located between the high-nickel ternary material core and the cobalt borate coating layer. The particle size D50 of the high-nickel ternary material is 3 mu m, the thickness of the cobalt borate coating layer is 5nm, and the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is 0.001: 1.
Example 2
This example prepares a ternary cathode material as follows:
(1) mixing boron oxide and cobalt hydroxide in a molar ratio of B to Co of 1:1 and 3/4 in a high-speed mixer at a speed of 50rpm for 2h, then filling in a sagger, then placing in a kiln, heating to 600 ℃ at a speed of 5 ℃/min, keeping the temperature for 3h, and introducing 5L/h argon into the kiln. After sintering, crushing, sieving by a 325-mesh sieving machine to obtain Co2B2O5。
(2) Mixing Co2B2O5With a high nickel ternary material Li with an average particle size of 15 mu m0.95Ni0.6Co0.2Mn0.2O2Mixing the materials for 1h at a rotating speed of 100rpm on a high-speed mixer according to a mass ratio of 0.005:1 and a loading amount of 3/4, then filling the materials into a sagger, putting the sagger into a kiln, raising the temperature to 500 ℃ at a speed of 5 ℃/min, preserving the temperature for 10h, introducing air into the kiln, and ensuring that the gas flow required by 10kg of mixed materials is 10L/h. After sintering, crushing, sieving by a 325-mesh sieving machine to obtain Co2B2O5Coated Li0.95Ni0.6Co0.2M0.2O2The composite ternary positive electrode material of (1).
The test results of the ternary cathode material prepared in this example are shown in table 1.
The ternary cathode material prepared in this embodiment mainly comprises a high-nickel ternary material core and a cobalt borate coating layer, and the ternary cathode material further comprises lithium cobalt borate located between the high-nickel ternary material core and the cobalt borate coating layer. The particle size D50 of the high-nickel ternary material is 15 mu m, the thickness of the cobalt borate coating layer is 20nm, and the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is 0.005: 1.
Example 3
This example prepares a ternary cathode material as follows:
(1) mixing a mixture of tetraboric acid and cobalt carbonate in a molar ratio of B to Co of 1:1 and 3/5 in a high-speed mixer at a speed of 60rpm for 1h, filling in a sagger, putting in a kiln, heating to 500 ℃ at a speed of 3 ℃/min, keeping the temperature for 4h, and introducing 10L/h carbon dioxide into the kiln. After sintering, crushing, sieving by a 325-mesh sieving machine to obtain Co2B2O5。
(2) Mixing Co2B2O5With a high nickel ternary material Li with an average particle size of 10 mu m1.0Ni0.65Co0.15Mn0.20O2Mixing the materials for 1.5h at a rotating speed of 70rpm on a high-speed mixer according to a mass ratio of 0.003:1 and a loading amount of 3/4, then filling the materials into a sagger, putting the sagger into a kiln, heating the sagger to 300 ℃ at a speed of 3 ℃/min, preserving the heat for 8h, and introducing air into the kiln, wherein the gas flow required by 10kg of mixed materials is 8L/h. After sintering, crushing, sieving by a 325-mesh sieving machine to obtain Co2B2O5Coated Li0.95Ni0.6Co0.2Mn0.2O2The composite ternary positive electrode material of (1).
The test results of the ternary cathode material prepared in this example are shown in table 1.
The ternary cathode material prepared in this embodiment mainly comprises a high-nickel ternary material core and a cobalt borate coating layer, and the ternary cathode material further comprises lithium cobalt borate located between the high-nickel ternary material core and the cobalt borate coating layer. The particle size D50 of the high-nickel ternary material is 10 mu m, the thickness of the cobalt borate coating layer is 15nm, and the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is 0.003: 1.
Example 4
This example prepares a ternary cathode material as follows:
(1) will be provided withMixing tetraboric acid and cobalt acetate in a molar ratio of B to Co of 1:1 and 1/2 in a high-speed mixer at a speed of 100rpm for 0.5h, filling in a sagger, placing in a kiln, heating to 450 ℃ at a speed of 4 ℃/min, keeping the temperature for 3h, and introducing 4L/h nitrogen into the kiln. After sintering, crushing, sieving by a 325-mesh sieving machine to obtain Co2B2O5。
(2) Mixing Co2B2O5With a high nickel ternary material Li with an average particle size of 8 mu m1.05Ni0.86Co0.10Mn0.4O2Mixing the materials for 0.5h at a rotating speed of 100rpm on a high-speed mixer according to a mass ratio of 0.002:1 and a loading amount of 3/4, then filling the materials into a sagger, putting the sagger into a kiln, heating the sagger to 300 ℃ at a speed of 4 ℃/min, preserving the heat for 10h, and introducing air into the kiln, wherein the gas flow required by 10kg of mixed materials is 5L/h. After sintering, crushing, sieving by a 325-mesh sieving machine to obtain Co2B2O5Coated Li1.05Ni0.86Co0.10Mn0.4O2The composite ternary positive electrode material of (1).
The test results of the ternary cathode material prepared in this example are shown in table 1.
The ternary cathode material prepared in this embodiment mainly comprises a high-nickel ternary material core and a cobalt borate coating layer, and the ternary cathode material further comprises lithium cobalt borate located between the high-nickel ternary material core and the cobalt borate coating layer. The particle size D50 of the high-nickel ternary material is 8 mu m, the thickness of the cobalt borate coating layer is 10nm, and the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is 0.002: 1.
Example 5
This example prepares a ternary cathode material as follows:
(1) mixing a mixture of tetraboric acid and cobalt oxalate at a molar ratio of B to Co of 1:1 and 1/2 in a high-speed mixer at a speed of 100rpm for 0.5h, filling in a sagger, placing in a kiln, heating to 450 ℃ at a speed of 4 ℃/min, keeping the temperature for 3h, and introducing 1L/h nitrogen into the kiln. After sintering, crushing, sieving by a 325-mesh sieving machine to obtain Co2B2O5。
(2) Mixing Co2B2O5With a high nickel ternary material Li with an average particle size of 5 mu m1.02Ni0.80Co0.10Mn0.10O2Mixing the materials for 0.5h at a rotating speed of 100rpm on a high-speed mixer according to a mass ratio of 0.002:1 and a loading amount of 3/4, then filling the materials into a sagger, putting the sagger into a kiln, heating the sagger to 300 ℃ at a speed of 4 ℃/min, preserving the heat for 10h, and introducing air into the kiln, wherein the gas flow required by 10kg of mixed materials is 1L/h. After sintering, crushing, sieving by a 325-mesh sieving machine to obtain Co2B2O5Coated Li1.02Ni0.80Co10Mn10O2The composite ternary positive electrode material of (1).
The test results of the ternary cathode material prepared in this example are shown in table 1.
The ternary cathode material prepared in this embodiment mainly comprises a high-nickel ternary material core and a cobalt borate coating layer, and the ternary cathode material further comprises lithium cobalt borate located between the high-nickel ternary material core and the cobalt borate coating layer. The particle size D50 of the high-nickel ternary material is 5 mu m, the thickness of the cobalt borate coating layer is 10nm, and the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is 0.002: 1.
Example 6
This example prepares a ternary cathode material as follows:
(1) mixing tetraboric acid and boric acid with a mixture of cobalt acetate and cobalt nitrate in a molar ratio of B to Co of 1:1 and 1/2 in a high-speed mixer at a speed of 100rpm for 1h, filling in a sagger, placing in a kiln, heating to 440 ℃ at 4 ℃/min, keeping the temperature for 5h, and introducing 10L/h nitrogen into the kiln. After sintering, crushing, sieving by a 325-mesh sieving machine to obtain Co2B2O5。
(2) Mixing Co2B2O5With a high nickel ternary material Li with an average particle size of 12 mu m1.03Ni0.80Co0.12Mn0.8O2At a mass ratio of 0.005:1 and a loading of 3/5 on a high-speed mixer at 100rAnd pm, mixing at a rotating speed of 1 hour, filling the mixture into a sagger, putting the sagger into a kiln, heating to 500 ℃ at a speed of 4 ℃/min, keeping the temperature for 8 hours, introducing air into the kiln, and controlling the gas flow required by 10kg of mixed materials to be 3L/h. After sintering, crushing, sieving by a 325-mesh sieving machine to obtain Co2B2O5Coated Li1.03Ni0.80Co0.12Mn0.8O2The composite ternary positive electrode material of (1).
The test results of the ternary cathode material prepared in this example are shown in table 1.
The ternary cathode material prepared in this embodiment mainly comprises a high-nickel ternary material core and a cobalt borate coating layer, and the ternary cathode material further comprises lithium cobalt borate located between the high-nickel ternary material core and the cobalt borate coating layer. The particle size D50 of the high-nickel ternary material is 12 mu m, wherein the thickness of the cobalt borate coating layer is 20nm, and the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is 0.005: 1.
Example 7
The specific preparation method of this example was as in example 1 except that in step (2), Co2B2O5With high nickel ternary material Li1.01Ni0.8Co0.1M0.1O2Coating is carried out according to the mass ratio of 0.01: 1.
Fig. 1b is a Scanning Electron Microscope (SEM) image of the ternary cathode material coated with cobalt borate prepared in this example, and it can be seen from the image that the ternary cathode material prepared in this example has a coating substance on it obviously because the coating quality is too high.
The test results of the ternary cathode material prepared in this example are shown in table 1.
The ternary cathode material prepared in this embodiment mainly comprises a high-nickel ternary material core and a cobalt borate coating layer, and the ternary cathode material further comprises lithium cobalt borate located between the high-nickel ternary material core and the cobalt borate coating layer. The particle size D50 of the high-nickel ternary material is 3 mu m, wherein the thickness of the cobalt borate coating layer is 50nm, and the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is 0.01: 1.
Example 8
The specific preparation process of this example was as in example 1 except that in step (2), Co was added2B2O5With high nickel ternary material Li1.01Ni0.8Co0.1Mn0.1O2Mixing was carried out at 110rpm for 0.5 h.
Fig. 1c is a Scanning Electron Microscope (SEM) image of the ternary cathode material coated with cobalt borate prepared in this example, and it can be seen from the image that the particle surface of the ternary cathode material prepared in this example is damaged due to the high rotation speed of the high-speed mixer.
The test results of the ternary cathode material prepared in this example are shown in table 1.
The ternary cathode material prepared in this embodiment mainly comprises a high-nickel ternary material core and a cobalt borate coating layer, and the ternary cathode material further comprises lithium cobalt borate located between the high-nickel ternary material core and the cobalt borate coating layer. The particle size D50 of the high-nickel ternary material is 3 mu m, the thickness of the cobalt borate coating layer is 5nm, and the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is 0.001: 1.
Example 9
The specific preparation method of this example refers to example 1, except that in step (2), the mixing time on the high-speed mixer is 2h, and the temperature is raised to 200 ℃ in the kiln for heat preservation.
The test results of the ternary cathode material prepared in this example are shown in table 1.
The ternary cathode material prepared in this embodiment mainly comprises a high-nickel ternary material core and a cobalt borate coating layer, and the ternary cathode material further comprises lithium cobalt borate located between the high-nickel ternary material core and the cobalt borate coating layer. The particle size D50 of the high-nickel ternary material is 3 mu m, the thickness of the cobalt borate coating layer is 5nm, and the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is 0.001: 1.
Example 10
The specific production method of this example refers to example 1 except that in step (2), a high nickel ternary material Li having an average particle diameter of 1 μm is used1.01Ni0.8Co0.1Mn0.1O2。
The test results of the ternary cathode material prepared in this example are shown in table 1.
The ternary cathode material prepared in this embodiment mainly comprises a high-nickel ternary material core and a cobalt borate coating layer, and the ternary cathode material further comprises lithium cobalt borate located between the high-nickel ternary material core and the cobalt borate coating layer. The particle size D50 of the high-nickel ternary material is 1 mu m, the thickness of the cobalt borate coating layer is 5nm, and the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is 0.001: 1.
Example 11
The specific production method of this example refers to example 1 except that in step (2), a high nickel ternary material Li having an average particle diameter of 20 μm is used1.01Ni0.8Co0.1Mn0.1O2。
The test results of the ternary cathode material prepared in this example are shown in table 1.
The ternary cathode material prepared in this embodiment mainly comprises a high-nickel ternary material core and a cobalt borate coating layer, and the ternary cathode material further comprises lithium cobalt borate located between the high-nickel ternary material core and the cobalt borate coating layer. The particle size D50 of the high-nickel ternary material is 20 mu m, the thickness of the cobalt borate coating layer is 5nm, and the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is 0.001: 1.
Comparative example 1
This comparative example uses the same high nickel ternary material (Li) as in example 11.01Ni0.8Co0.1Mn0.1O2) It was not coated at all for comparison.
Fig. 2 is a first charge and discharge curve of the ternary cathode material coated with cobalt borate prepared in example 1 of the present invention and the ternary cathode material uncoated with cobalt borate prepared in comparative example 1, and it can be seen from the figure that the first discharge capacity of the ternary cathode material coated with cobalt borate prepared in example 1 is 204mAh/g, which is higher than the discharge capacity of the ternary cathode material uncoated with cobalt borate in comparative example 1 by 200mAh/g, indicating that the coated cobalt borate reacts with lithium hydroxide and lithium carbonate of the high nickel ternary material to form lithium cobalt borate having electrochemical capacity, thus resulting in an increase in charge and discharge capacity of the coated ternary cathode material.
Fig. 3 is a cycle performance curve of the ternary cathode material coated with cobalt borate prepared in example 1 of the present invention and the ternary cathode material not coated with cobalt borate prepared in comparative example 1, and it can be seen from the curves that the cycle retention rate of 100 cycles of the ternary cathode material coated with cobalt borate prepared in example 1 is 93.2%, which is higher than the cycle retention rate of 82.5% of the ternary cathode material not coated with cobalt borate in comparative example 1, which indicates that the coated cobalt borate improves the surface stability of the ternary cathode material on the one hand, and the lithium cobalt borate has electronic and ionic conductivities on the other hand, so that the cycle retention rate of the ternary material is improved.
The test results of the high nickel ternary positive electrode material in this comparative example are shown in table 1.
Test method
The ternary positive electrode material products obtained in the above examples and comparative examples were subjected to performance testing by the following method.
The particle size of the anode material is tested by adopting a Malvern laser particle size tester MS 2000.
The surface appearance, particle size and the like of the sample were observed by a scanning electron microscope of Hitachi S4800.
Electrochemical cycling performance was tested using the following method: mixing a high-nickel ternary composite material coated with cobalt borate as a positive electrode material, conductive carbon black and a binder PVDF (polyvinylidene fluoride) according to a mass ratio of 80:10:10, adding NMP (N-methyl pyrrolidone) to prepare uniform slurry, coating the uniform slurry on a copper foil, drying the uniform slurry in an oven, rolling the uniform slurry under a pressure of 10Mpa, and cutting the uniform slurry into a circular pole piece with the diameter of 14 mm. Assembling a lithium ion battery according to an industrial CR2025 type button battery, wherein a diaphragm is a Cellgard diaphragm, and an electrolyte is 1mol/L LiPF (lithium ion power) with a solvent of EC/PC/DEC6The solution, the counter electrode is a lithium sheet. The whole assembly process is assembled in a glove box filled with argon, and the oxygen content and the moisture content in the glove box are controlled to be below 0.5 ppm. The lithium ion battery test conditions are as follows: temperature of 25 + -1 deg.C, charge-discharge cycleThe voltage range of (1) is 3.0V-4.2V, the current is 0.1C (20mAh/g), and the cycle test is carried out for 100 weeks by charging 0.5C to 1C.
The sample was tested for the amount of residual base using an automatic potentiometric titrator (model: METTLER TOLEDO G20).
The test results of the above tests are shown in table 1.
TABLE 1
Figure BDA0001872698010000181
Figure BDA0001872698010000191
It can be seen from the above examples and comparative examples that the ternary positive electrode materials prepared in examples 1 to 6 and example 9 had a suitable thickness of the cobalt borate coating layer and a suitable D50 for the high nickel ternary material, and reacted to form lithium cobalt borate, so that the rate discharge capacity and cycle performance were both excellent and the residual alkali content was low. The cobalt borate coating layer of example 7 was too thick to cause a decrease in capacity and cycle, and the high-speed mixer rotation speed in example 8 caused a particle surface destruction of the ternary positive electrode material, resulting in a decrease in discharge capacity and cycle behavior. The D50 for the high nickel ternary materials of examples 10 and 11 is not in the most preferred range, resulting in a reduction in performance compared to example 1. Comparative example 1 the capacity and 100 cycle are significantly inferior to example 1 because of the absence of the cobalt borate coating, indicating that coating cobalt borate under the conditions of the present application can improve capacity and cycle performance compared to no coating.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The ternary cathode material is characterized by mainly comprising a high-nickel ternary material core and a cobalt borate coating layer.
2. The ternary positive electrode material according to claim 1, wherein the cobalt borate coating layer is Co2B2O5A coating layer;
preferably, the thickness of the cobalt borate coating layer is 2-50nm, preferably 5-20 nm;
preferably, the mass ratio of the cobalt borate coating layer to the high-nickel ternary material core is (0.001-0.01):1, preferably (0.001-0.005): 1.
3. The ternary cathode material according to claim 1 or 2, further comprising lithium cobalt borate between the high nickel ternary material core and the cobalt borate coating layer;
preferably, the particle size D50 of the high-nickel ternary material is 1-20 μm, preferably 3-15 μm;
preferably, the chemical formula of the high-nickel ternary material core is LizNi1-x-yCoxMyO2Wherein z is more than or equal to 0.95 and less than or equal to 1.10, x is more than or equal to 0 and less than or equal to 0.20, y is more than or equal to 0 and less than or equal to 0.20, and M is any one or the combination of at least two of Mn, Al, Mg, Ti or Nb.
4. A method for preparing a ternary positive electrode material according to any one of claims 1 to 3, characterized in that it comprises the following steps:
(1) mixing a boron source and a cobalt source, and sintering in a protective atmosphere to obtain cobalt borate;
(2) and (2) mixing the cobalt borate and the high-nickel ternary material in the step (1), and heating in an oxidizing atmosphere to obtain the ternary cathode material.
5. The method according to claim 4, wherein the boron source of step (1) comprises any one of orthoboric acid, metaboric acid, tetraboric acid, boron oxide or ammonium borate or a combination of at least two thereof;
preferably, the cobalt source in step (1) comprises any one of cobalt nitrate, cobalt hydroxide, cobalt carbonate, cobalt acetate or cobalt oxalate or a combination of at least two of the above;
preferably, the mixing device used in the step (1) is a mixer, preferably a high-speed mixer;
preferably, the volume of each batch of mixed material is 1/2-3/4 of the volume of the mixer;
preferably, the rotation speed of the mixer is 50-100 rpm;
preferably, the mixing time of step (1) is 0.5-2 h.
6. The production method according to claim 4 or 5, wherein the sintering of step (1) is solid-phase sintering;
preferably, the sintering temperature of the sintering in the step (1) is 400-600 ℃;
preferably, the sintering time of the step (1) is 3-5 h;
preferably, the temperature rise speed of the sintering in the step (1) is 3-5 ℃/min;
preferably, the protective atmosphere in step (1) is any one or a combination of at least two of a nitrogen atmosphere, an argon atmosphere or a carbon dioxide atmosphere;
preferably, the flow rate of protective atmosphere gas introduced into each 10kg of mixed material in the sintering process in the step (1) is 1-10L/h;
preferably, the sintering of step (1) is carried out in a box furnace or kiln;
preferably, the cobalt borate in step (1) is Co2B2O5。
7. The method according to any one of claims 4 to 6, wherein the particle size D50 of the high-nickel ternary material is 1 to 20 μm, preferably 3 to 15 μm;
preferably, the chemical formula of the high-nickel ternary material in the step (2) is LizNi1-x-yCoxMyO2Wherein z is more than or equal to 0.95 and less than or equal to 1.10, x is more than or equal to 0 and less than or equal to 0.20, y is more than or equal to 0 and less than or equal to 0.20, and M is any one or the combination of at least two of Mn, Al, Mg, Ti or Nb;
preferably, the mixing device used in the step (2) is a mixer, preferably a high-speed mixer;
preferably, the volume of each batch of mixed material is 1/2-3/4 of the volume of the mixer;
preferably, the rotation speed of the mixer is 50-100 rpm;
preferably, the mixing time of the step (2) is 0.5-2 h;
preferably, in the step (2), the mass ratio of the cobalt borate to the high-nickel ternary material is (0.001-0.01):1, and preferably (0.001-0.005): 1.
8. The method according to any one of claims 4 to 7, wherein in the step (2), the heating temperature is 200 ℃ to 500 ℃;
preferably, in the step (2), the heating time is 5-10 h;
preferably, in the step (2), the heating rate is 3-5 ℃/min;
preferably, in the step (2), the oxidizing atmosphere is an oxygen atmosphere and/or an air atmosphere;
preferably, the flow rate of the oxidizing atmosphere gas introduced into each 10kg of the mixed material in the heating process in the step (2) is 1-10L/h;
preferably, the heating of step (2) is performed in a box furnace or kiln.
9. The method for preparing according to any one of claims 4 to 8, characterized in that it comprises the steps of:
(1) mixing a boron source and a cobalt source in a mixer at a rotating speed of 50-100rpm for 0.5-2h, heating to 400-600 ℃ at a heating rate of 3-5 ℃/min in a protective atmosphere, and sintering for 3-5h to obtain cobalt borate;
the protective atmosphere comprises any one or the combination of at least two of nitrogen atmosphere, argon atmosphere and carbon dioxide atmosphere, and the gas flow of the protective atmosphere introduced into every 10kg of mixed materials in the sintering process is 1-10L/h;
(2) mixing the cobalt borate and the high-nickel ternary material in the step (1) in a mixer at a rotating speed of 50-100rpm for 0.5-2h, and heating to 200-500 ℃ at a heating rate of 3-5 ℃/min in an oxidizing atmosphere for 5-10h to obtain the ternary cathode material;
wherein the mass ratio of the cobalt borate to the high-nickel ternary material is (0.001-0.005) to 1; the particle size D50 of the high-nickel ternary material is 3-15 mu m, the oxidizing atmosphere is an oxygen atmosphere and/or an air atmosphere, and the flow rate of oxidizing atmosphere gas introduced into each 10kg of mixed material in the heating process is 1-10L/h.
10. A lithium ion battery comprising the ternary cathode material of any of claims 1-3.
CN201811384733.4A 2018-11-20 2018-11-20 Ternary cathode material, preparation method thereof and lithium ion battery Active CN111200120B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811384733.4A CN111200120B (en) 2018-11-20 2018-11-20 Ternary cathode material, preparation method thereof and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811384733.4A CN111200120B (en) 2018-11-20 2018-11-20 Ternary cathode material, preparation method thereof and lithium ion battery

Publications (2)

Publication Number Publication Date
CN111200120A true CN111200120A (en) 2020-05-26
CN111200120B CN111200120B (en) 2022-08-19

Family

ID=70746534

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811384733.4A Active CN111200120B (en) 2018-11-20 2018-11-20 Ternary cathode material, preparation method thereof and lithium ion battery

Country Status (1)

Country Link
CN (1) CN111200120B (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111793824A (en) * 2020-07-21 2020-10-20 苏州华赢新能源材料科技有限公司 Surface-modified high-nickel cathode material and preparation method and application thereof
CN113451560A (en) * 2021-07-01 2021-09-28 清华大学深圳国际研究生院 Positive electrode active material, preparation method thereof, positive electrode and ternary lithium ion battery
CN113540466A (en) * 2021-07-20 2021-10-22 浙江帕瓦新能源股份有限公司 Metal boride and borate composite coated modified nickel-cobalt-manganese ternary material precursor and preparation method thereof
CN113830846A (en) * 2021-11-24 2021-12-24 湖南长远锂科股份有限公司 Coating modified cathode material and preparation method thereof
CN113903918A (en) * 2021-09-27 2022-01-07 蜂巢能源科技(马鞍山)有限公司 Cathode material, preparation method thereof and lithium ion battery
CN113921792A (en) * 2021-10-09 2022-01-11 远景动力技术(江苏)有限公司 Lithium ion battery positive pole piece and preparation method and application thereof
CN114122379A (en) * 2021-11-09 2022-03-01 远景动力技术(江苏)有限公司 Positive electrode material and preparation method and application thereof
WO2022127324A1 (en) * 2020-12-15 2022-06-23 广东邦普循环科技有限公司 High-nickel ternary positive electrode material, preparation method therefor and use thereof
CN115084516A (en) * 2021-07-28 2022-09-20 天津润光恒科技开发有限公司 Preparation method of boron-based multi-element composite material
WO2022206910A1 (en) * 2021-03-31 2022-10-06 蜂巢能源科技股份有限公司 Cobalt-free high-nickel positive electrode material, preparation method therefor and use thereof
CN115403081A (en) * 2022-11-02 2022-11-29 宜宾锂宝新材料有限公司 High-nickel ternary positive electrode material, preparation method thereof and battery
CN115849467A (en) * 2023-02-28 2023-03-28 宜宾锂宝新材料有限公司 Method for removing residual alkali from high-nickel material, ternary material, and preparation method and application thereof
WO2023184996A1 (en) * 2022-03-28 2023-10-05 广东邦普循环科技有限公司 Modified high-nickel ternary positive electrode material and preparation method therefor

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102891307A (en) * 2012-09-21 2013-01-23 东莞新能源科技有限公司 Composite anode material of high-voltage lithium ion battery and lithium ion battery
CN103066285A (en) * 2013-01-21 2013-04-24 中南大学 Preparation method of negative pole material of lithium ion battery
CN103682304A (en) * 2012-09-17 2014-03-26 华为技术有限公司 Lithium-rich solid solution anode composite and preparation method thereof, lithium ion battery anode plate and lithium ion battery
CN103985857A (en) * 2014-05-19 2014-08-13 青岛乾运高科新材料股份有限公司 Mixed lithium battery positive material and preparation method thereof
CN107437619A (en) * 2017-07-18 2017-12-05 南京创源天地动力科技有限公司 A kind of anode for lithium battery material and preparation method thereof
CN107994212A (en) * 2017-10-27 2018-05-04 合肥国轩高科动力能源有限公司 A kind of layered cathode material of lithium ion battery and preparation method thereof
US20180175371A1 (en) * 2015-06-03 2018-06-21 University Of Limerick A Nanowire Heterostructure
CN108807926A (en) * 2018-06-22 2018-11-13 格林美（无锡）能源材料有限公司 A kind of Co/B coats nickel cobalt manganese lithium ion anode material and preparation method thereof altogether

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103682304A (en) * 2012-09-17 2014-03-26 华为技术有限公司 Lithium-rich solid solution anode composite and preparation method thereof, lithium ion battery anode plate and lithium ion battery
CN102891307A (en) * 2012-09-21 2013-01-23 东莞新能源科技有限公司 Composite anode material of high-voltage lithium ion battery and lithium ion battery
CN103066285A (en) * 2013-01-21 2013-04-24 中南大学 Preparation method of negative pole material of lithium ion battery
CN103985857A (en) * 2014-05-19 2014-08-13 青岛乾运高科新材料股份有限公司 Mixed lithium battery positive material and preparation method thereof
US20180175371A1 (en) * 2015-06-03 2018-06-21 University Of Limerick A Nanowire Heterostructure
CN107437619A (en) * 2017-07-18 2017-12-05 南京创源天地动力科技有限公司 A kind of anode for lithium battery material and preparation method thereof
CN107994212A (en) * 2017-10-27 2018-05-04 合肥国轩高科动力能源有限公司 A kind of layered cathode material of lithium ion battery and preparation method thereof
CN108807926A (en) * 2018-06-22 2018-11-13 格林美（无锡）能源材料有限公司 A kind of Co/B coats nickel cobalt manganese lithium ion anode material and preparation method thereof altogether

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111793824A (en) * 2020-07-21 2020-10-20 苏州华赢新能源材料科技有限公司 Surface-modified high-nickel cathode material and preparation method and application thereof
WO2022127324A1 (en) * 2020-12-15 2022-06-23 广东邦普循环科技有限公司 High-nickel ternary positive electrode material, preparation method therefor and use thereof
WO2022206910A1 (en) * 2021-03-31 2022-10-06 蜂巢能源科技股份有限公司 Cobalt-free high-nickel positive electrode material, preparation method therefor and use thereof
CN113451560A (en) * 2021-07-01 2021-09-28 清华大学深圳国际研究生院 Positive electrode active material, preparation method thereof, positive electrode and ternary lithium ion battery
CN113540466A (en) * 2021-07-20 2021-10-22 浙江帕瓦新能源股份有限公司 Metal boride and borate composite coated modified nickel-cobalt-manganese ternary material precursor and preparation method thereof
CN115084516A (en) * 2021-07-28 2022-09-20 天津润光恒科技开发有限公司 Preparation method of boron-based multi-element composite material
CN113903918B (en) * 2021-09-27 2022-05-03 蜂巢能源科技(马鞍山)有限公司 Cathode material, preparation method thereof and lithium ion battery
CN113903918A (en) * 2021-09-27 2022-01-07 蜂巢能源科技(马鞍山)有限公司 Cathode material, preparation method thereof and lithium ion battery
CN113921792A (en) * 2021-10-09 2022-01-11 远景动力技术(江苏)有限公司 Lithium ion battery positive pole piece and preparation method and application thereof
CN114122379A (en) * 2021-11-09 2022-03-01 远景动力技术(江苏)有限公司 Positive electrode material and preparation method and application thereof
CN114122379B (en) * 2021-11-09 2023-09-05 远景动力技术(江苏)有限公司 Positive electrode material, preparation method and application thereof
CN113830846B (en) * 2021-11-24 2022-03-04 湖南长远锂科股份有限公司 Coating modified cathode material and preparation method thereof
CN113830846A (en) * 2021-11-24 2021-12-24 湖南长远锂科股份有限公司 Coating modified cathode material and preparation method thereof
WO2023184996A1 (en) * 2022-03-28 2023-10-05 广东邦普循环科技有限公司 Modified high-nickel ternary positive electrode material and preparation method therefor
CN115403081A (en) * 2022-11-02 2022-11-29 宜宾锂宝新材料有限公司 High-nickel ternary positive electrode material, preparation method thereof and battery
CN115849467A (en) * 2023-02-28 2023-03-28 宜宾锂宝新材料有限公司 Method for removing residual alkali from high-nickel material, ternary material, and preparation method and application thereof
CN115849467B (en) * 2023-02-28 2023-06-02 宜宾锂宝新材料有限公司 Method for removing residual alkali from high-nickel material, ternary material, preparation method and application thereof

Also Published As

Publication number Publication date
CN111200120B (en) 2022-08-19

Similar Documents

Publication Publication Date Title
CN111200120B (en) Ternary cathode material, preparation method thereof and lithium ion battery
CN111564605B (en) Layered oxide positive electrode, preparation method and application thereof, and sodium ion battery containing layered oxide positive electrode
CN109659542B (en) High-voltage lithium cobalt oxide cathode material with core-shell structure and preparation method thereof
CN112864385A (en) Ternary cathode material, preparation method thereof and lithium ion battery
CN109065858B (en) Surface modified ternary positive electrode material, preparation method thereof and battery prepared from surface modified ternary positive electrode material
JP2023534756A (en) Lithium ion battery positive electrode lithium replenishment additive and its preparation method and lithium ion battery
CN102738458A (en) Surface modification method of lithium-rich cathode material
CN111952547A (en) Surface-coated modified lithium ion battery positive electrode material and preparation method thereof
CN114284499B (en) Spinel structure coated modified lithium cobaltate-based material, preparation method and lithium battery
CN110534717B (en) Positive electrode material and preparation method thereof
CN102569788B (en) Negative material of a kind of lithium ion battery and preparation method thereof and a kind of lithium ion battery
CN108807920B (en) LASO-coated octahedral-structure lithium nickel manganese oxide composite material and preparation method thereof
CN113651304A (en) Organic carbon-coated lithium iron phosphate cathode material and preparation method thereof
CN113353995A (en) Cathode material with low cobalt content and preparation method and application thereof
CN114388812B (en) Nickel-manganese spinel type positive electrode material and preparation method and application thereof
CN113023790B (en) Positive electrode material and preparation method and application thereof
CN116998031A (en) Positive electrode active material, method for preparing same, secondary battery, and electricity using device
CN113937267A (en) Cathode material, preparation method thereof, cathode comprising cathode material and lithium ion battery
CN116314704B (en) Coated modified sodium ion layered cathode material and preparation method thereof
CN113013389A (en) Ternary positive electrode material coated with manganese oxide compound and preparation method thereof
CN116022859A (en) Method for preparing positive electrode material and positive electrode material
CN114122380A (en) Preparation method of zirconium-doped cerium fluoride-coated nickel-cobalt-manganese ternary positive electrode material and prepared positive electrode material
CN107017391A (en) Core shell structure anode composite material and preparation method thereof, lithium ion battery
CN104900860A (en) Lithium-rich positive electrode material surface modification method, positive electrode containing surface-modified lithium-rich positive electrode material, and lithium ion battery
CN116314759B (en) High-nickel positive electrode material, preparation method thereof and lithium ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant