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CN107681123B - Positive electrode material and preparation method thereof, positive electrode piece and lithium ion battery - Google Patents

Positive electrode material and preparation method thereof, positive electrode piece and lithium ion battery Download PDF

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CN107681123B
CN107681123B CN201610620230.7A CN201610620230A CN107681123B CN 107681123 B CN107681123 B CN 107681123B CN 201610620230 A CN201610620230 A CN 201610620230A CN 107681123 B CN107681123 B CN 107681123B
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positive electrode
electrode material
cobalt oxide
lithium cobalt
modified lithium
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CN107681123A (en
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王梦
徐磊敏
梁成都
王亮
王巍
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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    • H—ELECTRICITY
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    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • C01G51/44—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2
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    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
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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
    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

本发明提供一种正极材料及其制备方法、正极极片及锂离子电池。所述正极材料包括改性的钴酸锂正极材料A’以及改性的钴酸锂正极材料B’，两者的质量比为d:1；前者的D50为10μm～25μm、D99为30μm～60μm，形貌为单颗粒的类球形或片状；后者的D50为1μm～10μm、D99为8μm～30μm，形貌为单颗粒的类球形或二次颗粒的类球形；其中，两者的化学通式相同且均为Li1+ aCo1‑bMbO2+cXm，M选自Al、Mg、Y、Ni、Mn、La中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10，M位于钴酸锂的体相掺杂位置，X包覆于钴酸锂的表面。本发明的正极材料能提高压实后的正极极片的压实密度，进而显著提高锂离子电池高温高电压下的能量密度、安全性能、存储性能以及循环稳定性。The invention provides a positive electrode material and a preparation method thereof, a positive electrode pole piece and a lithium ion battery. The positive electrode material includes a modified lithium cobalt oxide positive electrode material A' and a modified lithium cobalt oxide positive electrode material B', and the mass ratio of the two is d:1; D50 of the former is 10 μm to 25 μm, and D99 is 30 μm to 60 μm. , the morphology is a single-particle quasi-spherical or flake-like; the D50 of the latter is 1 μm to 10 μm, and the D99 is 8 μm to 30 μm, and the morphology is a single-particle quasi-spherical or a secondary particle quasi-spherical; among them, the chemical The general formula is the same and both are Li 1+ a Co 1-b M b O 2+c X m , M is selected from one or more of Al, Mg, Y, Ni, Mn, La, X is selected from Mg, One or more of Al, Zr, Ti, Ni, Mn, Y, Nb, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m≤0.1, 0<d≤10 , M is located in the bulk doping position of lithium cobalt oxide, and X is coated on the surface of lithium cobalt oxide. The positive electrode material of the invention can improve the compaction density of the compacted positive electrode sheet, thereby significantly improving the energy density, safety performance, storage performance and cycle stability of the lithium ion battery under high temperature and high voltage.

Description

Positive electrode material and preparation method thereof, positive electrode piece and lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a positive electrode material and a preparation method thereof, a positive electrode plate and a lithium ion battery.
Background
With the increasing miniaturization and lightening of mobile devices such as mobile phones, digital cameras, notebook computers, portable DVDs and the like, the market demand for energy density, safety performance and cycle life of lithium ion batteries is also increasing.
Lithium ion batteries generally include: the battery comprises a positive pole piece, a negative pole piece, a separation film and electrolyte, wherein the separation film is arranged between the positive pole piece and the negative pole piece. The positive pole piece comprises a positive current collector and a positive material distributed on the positive current collector, and the negative pole piece comprises a negative current collector and a negative material distributed on the negative current collector. Lithium ion batteries currently used in consumer electronicsThe positive electrode material is mainly lithium cobaltate (LiCoO)2)。
At present, consumer electronic products, particularly mobile phones, have higher and higher requirements on the cruising ability of lithium ion batteries, and it is urgent to improve the energy density of the lithium ion batteries in order to meet market demands. Increasing the charge cut-off voltage is currently the most effective way to increase the energy density of lithium ion batteries. However, LiCoO2The structure is unstable under high voltage, irreversible phase transition occurs, the structure is easy to collapse during the circulation process, and the structure is suitable for LiCoO2Surface coating can only stabilize the surface structure against LiCoO2And reacts with the electrolyte, and the collapse of the bulk structure cannot be suppressed.
Various methods for modifying the positive electrode material have been disclosed in the prior art, for example, chinese patent CN101734728A published on 16.02/2010 discloses a method of liquid phase modification of Co3O4Coating Al on the surface, and lithiating the dried precursor to form LiCoO2So as to carry out bulk phase doping treatment on the anode material. However, when the bulk-doped cathode material is prepared according to the above method, the doping element Al is distributed only in Co3O4The doping element Al can not be ensured to be uniformly distributed on the LiCoO after lithiation2May lead to LiCoO during high voltage cycling2The local structure collapses, affecting the energy density, safety performance and charge-discharge cycle stability of the lithium ion battery.
Disclosure of Invention
In view of the problems in the background art, the present invention aims to provide a positive electrode material, a preparation method thereof, a positive electrode plate and a lithium ion battery, wherein the positive electrode material can significantly improve the energy density, the safety performance, the storage performance and the cycle stability of the lithium ion battery at high temperature and high voltage.
In order to achieve the above object, in a first aspect of the present invention, there is provided a positive electrode material comprising a modified lithium cobaltate positive electrode material a ' and a modified lithium cobaltate positive electrode material B ', the mass ratio of the modified lithium cobaltate positive electrode material a ' and the modified lithium cobaltate positive electrode material BIs d: 1; d50 of particles of the modified lithium cobaltate positive electrode material A 'is 10-25 mu m, D99 is 30-60 mu m, and the shape of the modified lithium cobaltate positive electrode material A' is in a single-particle spherical-like shape or a single-particle sheet shape; the D50 of the particles of the modified lithium cobaltate positive electrode material B 'is 1-10 mu m, the D99 is 8-30 mu m, and the morphology of the modified lithium cobaltate positive electrode material B' is a single-particle spherical-like shape or a secondary-particle spherical-like shape; the D50 of the particles of the modified lithium cobaltate positive electrode material a 'is greater than the D50 of the particles of the modified lithium cobaltate positive electrode material B'; the D99 of the particles of the modified lithium cobaltate positive electrode material a 'is greater than the D99 of the particles of the modified lithium cobaltate positive electrode material B'; wherein the chemical formulas of the modified lithium cobaltate positive electrode material A 'and the modified lithium cobaltate positive electrode material B' are the same and both are Li1+aCo1-bMbO2+cXmM is selected from one or more of Al, Mg, Y, Ni, Mn and La, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y and Nb, a is more than or equal to 0 and less than or equal to 0.1, b is more than 0 and less than or equal to 0.1, c is more than or equal to 0 and less than or equal to 1, M is more than 0 and less than or equal to 0.1, d is more than 0 and less than or equal to 10, M is positioned at the phase doping position of lithium cobaltate, and X is coated on the surface of the lithium cobaltate.
In a second aspect of the present invention, the present invention provides a method for preparing a cathode material, for preparing the cathode material according to the first aspect of the present invention, comprising the steps of: (1) adding a precipitant solution, a Co salt solution and a metal M salt solution into a reaction kettle, mixing, carrying out coprecipitation reaction, drying to obtain precipitates A and B with different particle sizes, wherein D50 of primary particles of the precipitates A is 1-5 mu M, D50 of secondary particles is 5-20 mu M, D50 of the primary particles of the precipitates B is 0.05-1 mu M, and D50 of the secondary particles is 1-10 mu M; (2) mixing the precipitate A and a lithium salt, performing primary sintering, and then mixing the precipitate A and a compound of a metal X, and performing secondary sintering to obtain a modified lithium cobaltate positive electrode material A ', wherein D50 of particles of the modified lithium cobaltate positive electrode material A ' is 10-25 μm, D99 is 30-60 μm, and the shape of the modified lithium cobaltate positive electrode material A ' is a single-particle sphere-like shape or a single-particle sheet shape; (3) mixing the precipitate B with lithium salt, sintering for the first time, mixing with compound of metal X, and performing secondary sinteringSintering to obtain a modified lithium cobaltate positive electrode material B ', wherein D50 of particles of the modified lithium cobaltate positive electrode material B ' is 1-10 mu m, D99 is 8-30 mu m, and the morphology of the modified lithium cobaltate positive electrode material B ' is spherical-like of single particles or spherical-like of secondary particles; (4) mixing the modified lithium cobaltate positive electrode material A 'and the modified lithium cobaltate positive electrode material B' according to a mass ratio D:1 to finish the preparation of the positive electrode material, wherein D50 of particles of the modified lithium cobaltate positive electrode material A 'is larger than D50 of particles of the modified lithium cobaltate positive electrode material B', D99 of particles of the modified lithium cobaltate positive electrode material A 'is larger than D99 of particles of the modified lithium cobaltate positive electrode material B', and the chemical formulas of the modified lithium cobaltate positive electrode material A 'and the modified lithium cobaltate positive electrode material B' are the same and are both Li1+aCo1-bMbO2+cXmM is selected from one or more of Al, Mg, Y, Ni, Mn and La, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y and Nb, a is more than or equal to 0 and less than or equal to 0.1, b is more than 0 and less than or equal to 0.1, c is more than or equal to 0 and less than or equal to 1, M is more than 0 and less than or equal to 0.1, and d is more than 0 and less than or equal to 10.
In a third aspect of the invention, the invention provides another positive electrode material, which comprises a modified lithium cobaltate positive electrode material a 'and a modified lithium cobaltate positive electrode material B', wherein the mass ratio of the modified lithium cobaltate positive electrode material a 'to the modified lithium cobaltate positive electrode material B' is d: 1; d50 of particles of the modified lithium cobaltate positive electrode material A 'is 10-25 mu m, D99 is 30-60 mu m, and the shape of the modified lithium cobaltate positive electrode material A' is in a single-particle spherical-like shape or a single-particle sheet shape; the D50 of the particles of the modified lithium cobaltate positive electrode material B 'is 1-10 mu m, the D99 is 8-30 mu m, and the morphology of the modified lithium cobaltate positive electrode material B' is a single-particle spherical-like shape or a secondary-particle spherical-like shape; the D50 of the particles of the modified lithium cobaltate positive electrode material a 'is greater than the D50 of the particles of the modified lithium cobaltate positive electrode material B'; the D99 of the particles of the modified lithium cobaltate positive electrode material a 'is greater than the D99 of the particles of the modified lithium cobaltate positive electrode material B'; wherein, the modified lithium cobaltate positive electrode material A 'and the modified lithium cobaltate positive electrode material B' are providedAre the same in chemical formula and are all Li1+aCo1-bMbO2+ cXmM is selected from one or more of Al, Mg, Y, Ni, Mn and La, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y and Nb, a is more than or equal to 0 and less than or equal to 0.1, b is more than 0 and less than or equal to 0.1, c is more than or equal to 0 and less than or equal to 1, M is more than 0 and less than or equal to 0.1, d is more than 0 and less than or equal to 10, M is positioned at the phase doping position of lithium cobaltate and the doping position of a solid solution transition layer, and X is coated on the surface of the lithium cobalt.
In a fourth aspect of the present invention, the present invention provides another method for preparing a positive electrode material, for preparing the positive electrode material according to the third aspect of the present invention, comprising the steps of: (1) adding a precipitant solution, a Co salt solution and a metal M salt solution into a reaction kettle, mixing, carrying out coprecipitation reaction, drying to obtain precipitates A and B with different particle sizes, wherein D50 of primary particles of the precipitates A is 1-5 mu M, D50 of secondary particles is 5-20 mu M, D50 of the primary particles of the precipitates B is 0.05-1 mu M, and D50 of the secondary particles is 1-10 mu M; (2) mixing the precipitate A, lithium salt and metal M salt, performing primary sintering, and then mixing with a compound of metal X, performing secondary sintering to obtain a modified lithium cobaltate positive electrode material A ', wherein D50 of particles of the modified lithium cobaltate positive electrode material A ' is 10-25 μ M, D99 is 30-60 μ M, and the shape of the modified lithium cobaltate positive electrode material A ' is spherical or flaky like of a single particle; (3) mixing the precipitate B, lithium salt and metal M salt, performing primary sintering, and then mixing with a compound of metal X, performing secondary sintering to obtain a modified lithium cobaltate positive electrode material B ', wherein D50 of particles of the modified lithium cobaltate positive electrode material B ' is 1-10 mu M, D99 is 8-30 mu M, and the shape of the modified lithium cobaltate positive electrode material B ' is spherical-like of single particles or spherical-like of secondary particles; (4) mixing the modified lithium cobaltate positive electrode material A ' and the modified lithium cobaltate positive electrode material B ' according to the mass ratio D:1 to finish the preparation of the positive electrode material, wherein the D50 of the particles of the modified lithium cobaltate positive electrode material A ' is larger than the D50 of the particles of the modified lithium cobaltate positive electrode material B ', and the D99 of the particles of the modified lithium cobaltate positive electrode material A ' is larger than the D99 of the particles of the modified lithium cobaltate positive electrode material BThe chemical formulas of the modified lithium cobaltate positive electrode material A 'and the modified lithium cobaltate positive electrode material B' are the same and are both Li1+aCo1-bMbO2+cXmM is selected from one or more of Al, Mg, Y, Ni, Mn and La, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y and Nb, a is more than or equal to 0 and less than or equal to 0.1, b is more than 0 and less than or equal to 0.1, c is more than or equal to 0 and less than or equal to 1, M is more than 0 and less than or equal to 0.1, and d is more than 0 and less than or equal to 10.
In a fifth aspect of the present invention, the present invention provides a positive electrode sheet comprising a positive electrode current collector and a positive electrode membrane. The positive diaphragm is arranged on the positive current collector and comprises a positive material, a conductive agent and a binder. Wherein the positive electrode material is the positive electrode material according to the first aspect of the invention or the positive electrode material is the positive electrode material according to the third aspect of the invention.
In a sixth aspect of the invention, the invention provides a lithium ion battery, which comprises the positive pole piece according to the fifth aspect of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the anode material provided by the invention can obviously improve the energy density, the safety performance, the storage performance and the cycling stability of the lithium ion battery under high temperature and high voltage.
Drawings
FIG. 1 shows precipitate B (Co) of step (2) of example 40.97Al0.03)(OH)0.03CO3SEM image of (d).
FIG. 2 shows precipitate A (Co) of step (1) of example 40.97Al0.03)(OH)0.03CO3SEM image of (d).
FIG. 3 shows a single-particle spheroidal morphology cathode material Li of step (1) of example 41.02Co0.97Al0.0 3O2.08Zr0.02Al0.03SEM image of (d).
FIG. 4 shows a positive electrode material Li of a spheroidal morphology of the secondary particles of step (2) of example 41.02Co0.97Al0.0 3O2.08Zr0.02Al0.03SEM image of (d).
Fig. 5 shows an SEM image of the cold pressed positive electrode sheet of example 4.
Detailed Description
The following describes the positive electrode material, the preparation method thereof, the positive electrode plate and the lithium ion battery in detail.
The positive electrode material according to the first aspect of the invention is first explained.
The positive electrode material according to the first aspect of the invention includes a modified lithium cobaltate positive electrode material a 'and a modified lithium cobaltate positive electrode material B', and the mass ratio of the modified lithium cobaltate positive electrode material a 'to the modified lithium cobaltate positive electrode material B' is d: 1. The particle D50 of the modified lithium cobaltate positive electrode material A 'is 10-25 mu m, the particle D99 is 30-60 mu m, and the morphology of the modified lithium cobaltate positive electrode material A' is single-particle sphere-like or sheet-like. The particle D50 of the modified lithium cobaltate positive electrode material B 'is 1-10 mu m, the particle D99 is 8-30 mu m, and the morphology of the modified lithium cobaltate positive electrode material B' is spherical-like of single particles or spherical-like of secondary particles. The D50 of the particles of the modified lithium cobaltate positive electrode material a 'is greater than the D50 of the particles of the modified lithium cobaltate positive electrode material B'; the D99 of the particles of the modified lithium cobaltate positive electrode material a 'is greater than the D99 of the particles of the modified lithium cobaltate positive electrode material B'. Wherein the chemical formulas of the modified lithium cobaltate positive electrode material A 'and the modified lithium cobaltate positive electrode material B' are the same and both are Li1+aCo1-bMbO2+cXmM is selected from one or more of Al, Mg, Y, Ni, Mn and La, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y and Nb, a is more than or equal to 0 and less than or equal to 0.1, b is more than 0 and less than or equal to 0.1, c is more than or equal to 0 and less than or equal to 1, M is more than 0 and less than or equal to 0.1, d is more than 0 and less than or equal to 10, M is positioned at the phase doping position of lithium cobaltate, and X is coated on the surface of the lithium cobaltate.
In the positive electrode material according to the first aspect of the invention, the modified lithium cobaltate positive electrode material a 'and the modified lithium cobaltate positive electrode material B' are modifications of conventional lithium cobaltate materials (particularly, layered lithium cobaltate), wherein the modifications of the conventional lithium cobaltate materials include element doping modification and element surface coating modification. In the positive electrode material according to the first aspect of the present invention, the element M is located at a bulk phase doping position of the lithium cobaltate, so as to perform doping modification on the lithium cobaltate. The coating of X on the surface of lithium cobaltate means that X is formed on the surface of lithium cobaltate as a coating layer, and serves the purpose of performing surface coating modification on lithium cobaltate.
In the positive electrode material according to the first aspect of the present invention, the positive electrode material includes both the modified lithium cobaltate positive electrode material a 'having a larger particle size and the modified lithium cobaltate positive electrode material B' having a smaller particle size, which is beneficial to increase the compacted density of the compacted positive electrode sheet, thereby increasing the volumetric energy density of the positive electrode material, and significantly increasing the energy density, the safety performance, the storage performance, and the cycle stability of the lithium ion battery at high temperature and high voltage.
In the positive electrode material according to the first aspect of the present invention, X is coated on the surface of lithium cobaltate in the form of an oxide.
Next, a method for producing a positive electrode material according to the second aspect of the present invention, which is used for producing the positive electrode material according to the first aspect of the present invention, will be described.
The method for producing a positive electrode material according to the second aspect of the invention comprises the steps of: (1) adding a precipitant solution, a Co salt solution and a metal M salt solution into a reaction kettle, mixing, carrying out coprecipitation reaction, drying to obtain precipitates A and B with different particle sizes, wherein D50 of primary particles of the precipitates A is 1-5 mu M, D50 of secondary particles is 5-20 mu M, D50 of the primary particles of the precipitates B is 0.05-1 mu M, and D50 of the secondary particles is 1-10 mu M; (2) mixing the precipitate A and a lithium salt, performing primary sintering (corresponding to the process of forming lithium cobaltate, the same below), and then mixing the precipitate A and a compound of metal X, performing secondary sintering to obtain a modified lithium cobaltate positive electrode material A ', wherein D50 of particles of the modified lithium cobaltate positive electrode material A ' is 10-25 μm, D99 is 30-60 μm, and the morphology of the modified lithium cobaltate positive electrode material A ' is in a single-particle spherical-like shape or a single-particle sheet shape; (3) mixing the precipitate B and lithium salt, sintering for the first time, mixing with compound of metal X, and sintering for the second time to obtainThe modified lithium cobaltate cathode material B 'is characterized in that D50 of particles of the modified lithium cobaltate cathode material B' is 1-10 mu m, D99 of the particles of the modified lithium cobaltate cathode material B 'is 8-30 mu m, and the morphology of the modified lithium cobaltate cathode material B' is spherical-like of single particles or spherical-like of secondary particles; (4) mixing the modified lithium cobaltate positive electrode material A 'and the modified lithium cobaltate positive electrode material B' according to a mass ratio D:1 to finish the preparation of the positive electrode material, wherein D50 of particles of the modified lithium cobaltate positive electrode material A 'is larger than D50 of particles of the modified lithium cobaltate positive electrode material B', D99 of particles of the modified lithium cobaltate positive electrode material A 'is larger than D99 of particles of the modified lithium cobaltate positive electrode material B', and the chemical formulas of the modified lithium cobaltate positive electrode material A 'and the modified lithium cobaltate positive electrode material B' are the same and are both Li1+aCo1-bMbO2+cXmM is selected from one or more of Al, Mg, Y, Ni, Mn, La and Ti, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y and Nb, a is more than or equal to 0 and less than or equal to 0.1, b is more than 0 and less than or equal to 0.1, c is more than 0 and less than or equal to 1, M is more than 0 and less than or equal to 0.1, and d is more than 0 and less than or equal to 10.
In the method for producing a positive electrode material according to the second aspect of the present invention, first, LiCoO is subjected to2Doping modification is performed to improve its structural stability at high voltage, followed by LiCoO2And the surface is coated and modified, so that the structural stability of the composite material under high voltage is further improved. In the first sintering process of the step (2) and the step (3), the element M enters the phase doping position of the lithium cobaltate to achieve the purpose of doping modification of the lithium cobaltate. In the secondary sintering process in the step (2) and the step (3), the element X (which can be in the form of an oxide) is coated on the surface of the lithium cobaltate, so that the purpose of coating and modifying the surface of the lithium cobaltate is achieved.
It is added here that the execution of step (2) and step (3) may be performed simultaneously, or step (2) is performed first and step (3) is performed later, or step (3) is performed first and step (2) is performed later, and the writing order is not limited.
In the method for producing a positive electrode material according to the second aspect of the invention, in step (1), precipitation is performedThe agent is selected from NH4HCO3、(NH4)2CO3、Na2CO3、NaHCO3One or more of LiOH and NaOH. The concentration of the precipitant solution is 40 g/L-250 g/L. The feed rate of the precipitant solution was 0.01m3/h～3m3/h。
In the method for preparing the cathode material according to the second aspect of the present invention, in the step (1), the Co salt is selected from one or more of cobalt nitrate, cobalt chloride, cobalt acetate, and cobalt sulfate. The concentration of the Co salt solution is 50 g/L-300 g/L. The Co salt solution feed rate was 0.1m3/h～1m3/h。
In the method for preparing a positive electrode material according to the second aspect of the present invention, in the step (1), the metal M salt is selected from one or more of nitrate, hydrochloride, acetate, and sulfate of the metal M. The concentration of the solution of the metal M salt is 1g/L to 100 g/L. The feed rate of the solution of the metal M salt was 0.1M3/h～0.8m3/h。
In the method for producing a positive electrode material according to the second aspect of the invention, in step (1), the mixing is performed by a co-current feeding method.
In the preparation method of the cathode material according to the second aspect of the present invention, in the step (1), the pH of the reaction system is controlled to 6 to 9.
In the method for preparing a positive electrode material according to the second aspect of the present invention, in the step (1), the reaction temperature is 30 to 60 ℃ and the reaction time is 4 to 200 hours.
In the method for preparing a positive electrode material according to the second aspect of the present invention, in the step (2), the lithium salt is selected from one or more of lithium carbonate and lithium hydroxide.
In the method for preparing a positive electrode material according to the second aspect of the present invention, in step (3), the lithium salt is selected from one or more of lithium carbonate and lithium hydroxide.
In the method for producing a positive electrode material according to the second aspect of the present invention, in the step (2), the compound of the metal X is one or more selected from the group consisting of a carbonate of the metal X, a nitrate of the metal X, a hydroxide of the metal X, an oxide of the metal X, and a basic carbonate of the metal X.
In the method for producing a positive electrode material according to the second aspect of the present invention, in the step (3), the compound of the metal X is one or more selected from the group consisting of a carbonate of the metal X, a nitrate of the metal X, a hydroxide of the metal X, an oxide of the metal X, and a basic carbonate of the metal X.
In the method for producing a positive electrode material according to the second aspect of the present invention, in the step (2), the temperature of the primary sintering is 600 to 1300 ℃, and the temperature of the secondary sintering is 600 to 1100 ℃. Preferably, the temperature of the secondary sintering is not greater than the temperature of the primary sintering.
In the method for producing a positive electrode material according to the second aspect of the present invention, in step (3), the temperature for the first sintering is 500 to 1200 ℃, and the temperature for the second sintering is 600 to 1100 ℃. Preferably, the temperature of the secondary sintering is not greater than the temperature of the primary sintering.
The positive electrode material according to the third aspect of the invention is explained again.
The positive electrode material according to the third aspect of the invention includes a modified lithium cobaltate positive electrode material a 'and a modified lithium cobaltate positive electrode material B', and the mass ratio of the modified lithium cobaltate positive electrode material a 'to the modified lithium cobaltate positive electrode material B' is d: 1. The particle D50 of the modified lithium cobaltate positive electrode material A 'is 10-25 mu m, the particle D99 is 30-60 mu m, and the morphology of the modified lithium cobaltate positive electrode material A' is single-particle sphere-like or sheet-like. The particle D50 of the modified lithium cobaltate positive electrode material B 'is 1-10 mu m, the particle D99 is 8-30 mu m, and the morphology of the modified lithium cobaltate positive electrode material B' is spherical-like of single particles or spherical-like of secondary particles. The D50 of the particles of the modified lithium cobaltate positive electrode material a 'is greater than the D50 of the particles of the modified lithium cobaltate positive electrode material B'; the D99 of the particles of the modified lithium cobaltate positive electrode material a 'is greater than the D99 of the particles of the modified lithium cobaltate positive electrode material B'. Wherein the chemical formulas of the modified lithium cobaltate positive electrode material A 'and the modified lithium cobaltate positive electrode material B' are the same and both are Li1+aCo1-bMbO2+cXmM is selected from one or more of Al, Mg, Y, Ni, Mn and La, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y and Nb, a is more than or equal to 0 and less than or equal to 0.1, b is more than 0 and less than or equal to 0.1, c is more than or equal to 0 and less than or equal to 1, M is more than 0 and less than or equal to 0.1, d is more than 0 and less than or equal to 10, M is positioned at the phase doping position of lithium cobaltate and the doping position of a solid solution transition layer, and X is coated on the surface of the lithium cobalt.
In the positive electrode material according to the third aspect of the invention, the modified lithium cobaltate positive electrode material a 'and the modified lithium cobaltate positive electrode material B' are modifications of conventional lithium cobaltate materials (particularly, layered lithium cobaltate), wherein the modifications of the conventional lithium cobaltate materials include element doping modification and element surface coating modification. In the positive electrode material according to the third aspect of the present invention, the element M is located at a bulk doping position of the lithium cobaltate and a solid solution transition layer doping position (between the bulk doping position and the surface coating position), and serves to modify the doping of the lithium cobaltate. The coating of X on the surface of lithium cobaltate means that X is formed on the surface of lithium cobaltate as a coating layer, and serves the purpose of performing surface coating modification on lithium cobaltate.
In the positive electrode material according to the third aspect of the present invention, the positive electrode material includes both the modified lithium cobaltate positive electrode material a 'having a larger particle size and the modified lithium cobaltate positive electrode material B' having a smaller particle size, which is beneficial to increase the compacted density of the compacted positive electrode sheet, thereby increasing the volumetric energy density of the positive electrode material, and significantly increasing the energy density, the safety performance, the storage performance, and the cycle stability of the lithium ion battery at high temperature and high voltage.
In the positive electrode material according to the third aspect of the present invention, X is coated on the surface of lithium cobaltate in the form of an oxide.
Next, a method for producing a positive electrode material according to the fourth aspect of the invention, which is used for producing the positive electrode material according to the third aspect of the invention, is explained.
The method for preparing the cathode material according to the fourth aspect of the invention includes the steps of: (1) adding a precipitant solution, a Co salt solution and a metal M salt solution into a reaction kettle for mixing and carrying out coprecipitation reactionDrying to obtain precipitate A and precipitate B with different particle sizes, wherein D50 of primary particles of the precipitate A is 1-5 μm, D50 of secondary particles is 5-20 μm, D50 of primary particles of the precipitate B is 0.05-1 μm, and D50 of secondary particles is 1-10 μm; (2) mixing the precipitate A, lithium salt and metal M salt, performing primary sintering, and then mixing with a compound of metal X, performing secondary sintering to obtain a modified lithium cobaltate positive electrode material A ', wherein D50 of particles of the modified lithium cobaltate positive electrode material A ' is 10-25 μ M, D99 is 30-60 μ M, and the shape of the modified lithium cobaltate positive electrode material A ' is spherical or flaky like of a single particle; (3) mixing the precipitate B, lithium salt and metal M salt, performing primary sintering, and then mixing with a compound of metal X, performing secondary sintering to obtain a modified lithium cobaltate positive electrode material B ', wherein D50 of particles of the modified lithium cobaltate positive electrode material B ' is 1-10 mu M, D99 is 8-30 mu M, and the shape of the modified lithium cobaltate positive electrode material B ' is spherical-like of single particles or spherical-like of secondary particles; (4) mixing the modified lithium cobaltate positive electrode material A 'and the modified lithium cobaltate positive electrode material B' according to a mass ratio D:1 to finish the preparation of the positive electrode material, wherein D50 of particles of the modified lithium cobaltate positive electrode material A 'is larger than D50 of particles of the modified lithium cobaltate positive electrode material B', D99 of particles of the modified lithium cobaltate positive electrode material A 'is larger than D99 of particles of the modified lithium cobaltate positive electrode material B', and the chemical formulas of the modified lithium cobaltate positive electrode material A 'and the modified lithium cobaltate positive electrode material B' are the same and are both Li1+aCo1-bMbO2+cXmM is selected from one or more of Al, Mg, Y, Ni, Mn and La, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y and Nb, a is more than or equal to 0 and less than or equal to 0.1, b is more than 0 and less than or equal to 0.1, c is more than or equal to 0 and less than or equal to 1, M is more than 0 and less than or equal to 0.1, and d is more than 0 and less than or equal to 10.
In the method for producing a positive electrode material according to the fourth aspect of the present invention, first, LiCoO is subjected2Doping modification is performed to improve its structural stability at high voltage, followed by LiCoO2And the surface is coated and modified, so that the structural stability of the composite material under high voltage is further improved. Wherein in the step ofIn the first sintering process of the step (2) and the step (3), the element M of the metal M salt added in the step (1) enters a phase doping position of the lithium cobaltate, and in the first sintering process of the step (2) and the step (3), the element M of the metal M salt added in the step (2) and the step (3) enters a solid solution transition layer doping position of the lithium cobaltate, so that the purpose of doping and modifying the lithium cobaltate is achieved. In the secondary sintering process in the step (2) and the step (3), the element X (which can be in the form of an oxide) is coated on the surface of the lithium cobaltate, so that the purpose of coating and modifying the surface of the lithium cobaltate is achieved.
It is added here that the execution of step (2) and step (3) may be performed simultaneously, or step (2) is performed first and step (3) is performed later, or step (3) is performed first and step (2) is performed later, and the writing order is not limited.
In the method for producing a positive electrode material according to the fourth aspect of the invention, in the step (1), the precipitant is selected from NH4HCO3、(NH4)2CO3、Na2CO3、NaHCO3One or more of LiOH and NaOH. The concentration of the precipitant solution is 40 g/L-250 g/L. The feed rate of the precipitant solution was 0.01m3/h～3m3/h。
In the method for preparing a positive electrode material according to the fourth aspect of the present invention, in the step (1), the Co salt is one or more selected from cobalt nitrate, cobalt chloride, cobalt acetate, and cobalt sulfate. The concentration of the Co salt solution is 50 g/L-300 g/L. The Co salt solution feed rate was 0.1m3/h～1m3/h。
In the method for producing a positive electrode material according to the fourth aspect of the invention, in the step (1), the metal M salt is one or more selected from a nitrate, a hydrochloride, an acetate, and a sulfate of the metal M. The concentration of the solution of the metal M salt is 1g/L to 100 g/L. The feed rate of the solution of the metal M salt was 0.1M3/h～0.8m3/h。
In the method for producing a positive electrode material according to the fourth aspect of the invention, in step (1), the mixing is performed by a co-current feeding method.
In the method for preparing the cathode material according to the fourth aspect of the present invention, in the step (1), the pH of the reaction system is controlled to 6 to 9.
In the method for preparing a positive electrode material according to the fourth aspect of the present invention, in the step (1), the reaction temperature is 30 to 60 ℃ and the reaction time is 4 to 200 hours.
In the method for producing a positive electrode material according to the fourth aspect of the invention, in the step (2), the temperature of the primary sintering is 600 to 1300 ℃, and the temperature of the secondary sintering is 600 to 1100 ℃. Preferably, the temperature of the secondary sintering is not greater than the temperature of the primary sintering.
In the method for producing a positive electrode material according to the fourth aspect of the invention, in the step (3), the temperature for the first sintering is 500 to 1200 ℃, and the temperature for the second sintering is 600 to 1100 ℃. Preferably, the temperature of the secondary sintering is not greater than the temperature of the primary sintering. In the method for producing a positive electrode material according to the fourth aspect of the invention, in the step (2), the lithium salt is selected from one or more of lithium carbonate and lithium hydroxide.
In the method for producing a positive electrode material according to the fourth aspect of the present invention, in step (3), the lithium salt is selected from one or more of lithium carbonate and lithium hydroxide.
In the method for producing a positive electrode material according to the fourth aspect of the present invention, in the step (2), the compound of the metal X is one or more selected from the group consisting of a carbonate of the metal X, a nitrate of the metal X, a hydroxide of the metal X, an oxide of the metal X, and a basic carbonate of the metal X.
In the method for producing a positive electrode material according to the fourth aspect of the present invention, in step (3), the compound of the metal X is one or more selected from the group consisting of a carbonate of the metal X, a nitrate of the metal X, a hydroxide of the metal X, an oxide of the metal X, and a basic carbonate of the metal X.
In the method for producing a positive electrode material according to the fourth aspect of the invention, in the step (2), the metal M salt is one or more selected from a nitrate, a hydrochloride, an acetate, and a sulfate of the metal M.
In the method for producing a positive electrode material according to the fourth aspect of the invention, in the step (3), the metal M salt is one or more selected from a nitrate, a hydrochloride, an acetate, and a sulfate of the metal M.
In the method for producing a positive electrode material according to the fourth aspect of the present invention, the metal M salt added in step (1) may be the same as or different from the metal M salt added in step (2) and step (3).
The positive electrode sheet according to the fifth aspect of the invention is explained next.
The positive electrode sheet according to the fifth aspect of the present invention includes a positive electrode current collector and a positive electrode membrane. The positive diaphragm is arranged on the positive current collector and comprises a positive material, a conductive agent and a binder. Wherein the positive electrode material is the positive electrode material according to the first aspect of the invention or the positive electrode material is the positive electrode material according to the third aspect of the invention.
In the positive electrode plate according to the fifth aspect of the present invention, the positive electrode plate has a compacted density of not less than 4.0g/cm after being compacted3。
Next, a lithium ion battery according to a sixth aspect of the present invention is described, which includes a positive electrode plate, a negative electrode plate, a separator interposed between the positive electrode plate and the negative electrode plate, and an electrolyte, wherein the positive electrode plate is the positive electrode plate according to the fifth aspect of the present invention.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
Example 1
(1) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 286.7g/L cobalt nitrate solution, 4.05g/L magnesium acetate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, the feed rate of the lithium hydroxide solution was 0.1m3H, magnesium acetateThe feed rate of the solution was 0.12m3H, 60h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate A) having a primary particle D50 of 2 μm and a secondary particle D50 of 13 μm.
Uniformly mixing 119g of precursor precipitate and 100g of lithium carbonate by ball milling, sintering at 1000 ℃ for 10h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling and uniformly mixing the mixture, and sintering the mixture at 980 ℃ for 10 hours to obtain a single-particle spherical anode material Li with D50 of 17 mu m and D99 of 40 mu m1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
(2) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 286.7g/L cobalt nitrate solution, 4.05g/L magnesium acetate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH value to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.15m3/h、NH4HCO3The feed rate of the solution was 0.28m3H, the feed rate of the lithium hydroxide solution was 0.05m3The feed rate of the magnesium acetate solution is 0.12m3H, 24h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water to a filtrate pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate B) having a primary particle D50 of 0.1 μm and a secondary particle D50 of 5 μm.
Uniformly mixing 119g of precursor precipitate and 100g of lithium carbonate by ball milling, sintering at 950 ℃ for 10h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 900 ℃ for 10h to obtain the anode material Li with the sphere-like morphology of secondary particles with the D50 of 6.3 mu m and the D99 of 25 mu m1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(correspondingly modifiedLithium cobaltate positive electrode material B').
(3) And (3) mechanically mixing the cathode material obtained in the step (1) with the cathode material obtained in the step (2) according to the mass ratio of 7:3 to obtain the final cathode material.
Example 2
(1) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 286.7g/L cobalt nitrate solution, 4.05g/L magnesium acetate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, the feed rate of the lithium hydroxide solution was 0.05m3The feed rate of the magnesium acetate solution is 0.12m3H, 50h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate A) having a primary particle D50 of 1 μm and a secondary particle D50 of 8 μm.
Uniformly mixing 119g of precursor precipitate and 100g of lithium carbonate by ball milling, sintering at 850 ℃ for 12h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 850 ℃ for 11h to obtain the single-particle sheet-shaped positive electrode material Li with the D50 of 17 mu m and the D99 of 40 mu m1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
(2) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 286.7g/L cobalt nitrate solution, 4.05g/L magnesium acetate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH value to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.15m3/h、NH4HCO3The feed rate of the solution was 0.28m3H, introduction of lithium hydroxide solutionThe material velocity is 0.1m3The feed rate of the magnesium acetate solution is 0.12m3H, 24h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water to a filtrate pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate B) having a primary particle D50 of 0.1 μm and a secondary particle D50 of 5 μm.
Uniformly mixing 119g of precursor precipitate and 100g of lithium carbonate by ball milling, sintering at 950 ℃ for 10h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 900 ℃ for 10h to obtain the spherical-like positive electrode material Li of secondary particles with the D50 of 6.3 mu m and the D99 of 25 mu m1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
(3) And (3) mechanically mixing the cathode material obtained in the step (1) with the cathode material obtained in the step (2) according to the mass ratio of 7:3 to obtain the final cathode material.
Example 3
(1) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 286.7g/L cobalt nitrate solution, 4.05g/L magnesium acetate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, the feed rate of the lithium hydroxide solution was 0.1m3The feed rate of the magnesium acetate solution is 0.12m3H, 50h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate A) having a primary particle D50 of 1 μm and a secondary particle D50 of 8 μm.
Uniformly mixing 119g of precursor precipitate and 100g of lithium carbonate by ball milling, sintering at 850 ℃ for 12h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 930 ℃ for 11h to obtain the single-particle sheet-shaped positive electrode material Li with the D50 of 17 mu m and the D99 of 40 mu m1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
(2) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 286.7g/L cobalt nitrate solution, 4.05g/L magnesium acetate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH value to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.15m3/h、NH4HCO3The feed rate of the solution was 0.28m3H, the feed rate of the lithium hydroxide solution was 0.05m3The feed rate of the magnesium acetate solution is 0.12m3H, 24h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water to a filtrate pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate B) having a primary particle D50 of 0.1 μm and a secondary particle D50 of 5 μm.
Uniformly mixing 119g of precursor precipitate and 100g of lithium carbonate by ball milling, sintering at 950 ℃ for 10h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 900 ℃ for 10h to obtain the spherical-like positive electrode material Li of secondary particles with the D50 of 6.3 mu m and the D99 of 25 mu m1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
(3) And (3) mechanically mixing the cathode material obtained in the step (1) and the cathode material obtained in the step (2) according to the mass ratio of 8:2 to obtain the final cathode material.
Example 4
(1) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 282.3g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution were added by a peristaltic pump to the solutionPutting the mixture into a reaction kettle containing 5L of deionized water for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, the feed rate of the lithium hydroxide solution was 0.1m3The feed rate of the aluminum nitrate solution was 0.12m3H, 60h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate A) having a primary particle D50 of 2 μm and a secondary particle D50 of 13 μm.
Uniformly mixing 119g of precursor precipitate and 100g of lithium carbonate by ball milling, sintering at 1000 ℃ for 10h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling and uniformly mixing the mixture, and sintering the mixture at 980 ℃ for 10 hours to obtain a single-particle spherical anode material Li with D50 of 17 mu m and D99 of 40 mu m1.02Co0.97Al0.03O2.08Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
(2) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 282.3g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH value to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.15m3/h、NH4HCO3The feed rate of the solution was 0.28m3H, the feed rate of the lithium hydroxide solution was 0.05m3The feed rate of the aluminum nitrate solution was 0.12m3H, 24h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water to a filtrate pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate B) having a primary particle D50 of 0.1 μm and a secondary particle D50 of 5 μm.
Uniformly mixing 119g of precursor precipitate and 100g of lithium carbonate by ball milling, sintering at 950 ℃ for 10h to form lithium cobaltate, and obtaining the cobalt acidLithium with 1.48g Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 900 ℃ for 10h to obtain the spherical-like positive electrode material Li of secondary particles with the D50 of 6.3 mu m and the D99 of 25 mu m1.02Co0.97Al0.03O2.08Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
(3) And (3) mechanically mixing the cathode material obtained in the step (1) with the cathode material obtained in the step (2) according to the mass ratio of 7:3 to obtain the final cathode material.
Example 5
(1) Feeding NH with a concentration of 80g/L in a cocurrent manner4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, the feed rate of the lithium hydroxide solution was 0.1m3The feed rate of the aluminum nitrate solution was 0.12m3H, 60h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate A) having a primary particle D50 of 2 μm and a secondary particle D50 of 13 μm.
119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate are uniformly ball-milled and sintered at 1000 ℃ for 10 hours to form lithium cobaltate, and then the obtained lithium cobaltate is mixed with 1.48g of Al2O3And 2.46g ZrO2Ball-milling and uniformly mixing the mixture, and sintering the mixture at 980 ℃ for 10 hours to obtain a single-particle spherical anode material Li with D50 of 17 mu m and D99 of 40 mu m1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
(2) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3Solution, 280g/L cobalt nitrate solution and 11.25g/L aluminum nitrateThe solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH value to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.15m3/h、NH4HCO3The feed rate of the solution was 0.28m3H, the feed rate of the lithium hydroxide solution was 0.05m3The feed rate of the aluminum nitrate solution was 0.12m3H, 24h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water to a filtrate pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate B) having a primary particle D50 of 0.1 μm and a secondary particle D50 of 5 μm.
Uniformly mixing 119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate by ball milling, sintering at 950 ℃ for 10h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 900 ℃ for 10h to obtain the spherical-like positive electrode material Li of secondary particles with the D50 of 6.3 mu m and the D99 of 25 mu m1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
(3) And (3) mechanically mixing the positive electrode material obtained in the step (1) with the positive electrode material obtained in the step (2) according to the mass ratio of 7:3 to obtain the final modified lithium cobaltate positive electrode material.
Example 6
(1) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, the feed rate of the lithium hydroxide solution was 0.1m3The feed rate of the aluminum nitrate solution was 0.12m3H, 60h of continuous feed. Then stopping stirring and filteringThe precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate A) having a primary particle D50 of 1 μm and a secondary particle D50 of 8 μm.
119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate are uniformly ball-milled and sintered at 850 ℃ for 12h to form lithium cobaltate, and then the obtained lithium cobaltate is mixed with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 850 ℃ for 11h to obtain the single-particle sheet-shaped positive electrode material Li with the D50 of 17 mu m and the D99 of 40 mu m1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
(2) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH value to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.15m3/h、NH4HCO3The feed rate of the solution was 0.28m3H, the feed rate of the lithium hydroxide solution was 0.05m3The feed rate of the aluminum nitrate solution was 0.12m3H, 24h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water to a filtrate pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate B) having a primary particle D50 of 0.1 μm and a secondary particle D50 of 5 μm.
Uniformly mixing 119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate by ball milling, sintering at 950 ℃ for 10h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling and uniformly mixing, and sintering at 930 ℃ for 10h to obtain the spherical-like positive electrode material Li of secondary particles with the D50 of 6.3 mu m and the D99 of 25 mu m1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
(3) And (3) mechanically mixing the cathode material obtained in the step (1) with the cathode material obtained in the step (2) according to the mass ratio of 7:3 to obtain the final cathode material.
Example 7
(1) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, the feed rate of the lithium hydroxide solution was 0.1m3The feed rate of the aluminum nitrate solution was 0.12m3H, 60h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate A) having a primary particle D50 of 1 μm and a secondary particle D50 of 8 μm.
119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate are uniformly ball-milled and sintered at 850 ℃ for 12h to form lithium cobaltate, and then the obtained lithium cobaltate is mixed with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 850 ℃ for 11h to obtain the single-particle sheet-shaped positive electrode material Li with the D50 of 17 mu m and the D99 of 40 mu m1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
(2) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH value to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.15m3/h、NH4HCO3The feed rate of the solution was 0.28m3H, of lithium hydroxide solutionThe feed rate was 0.05m3The feed rate of the aluminum nitrate solution was 0.12m3H, 24h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate B) having a primary particle D50 of 0.1 μm and a secondary particle D50 of 2 μm.
Uniformly mixing 119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate by ball milling, sintering at 950 ℃ for 10h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling and uniformly mixing the mixture, and sintering the mixture for 8 hours at 880 ℃ to obtain the anode material Li with the sphere-like morphology of secondary particles with the D50 being 3.2 mu m and the D99 being 25 mu m1.02Co0.96Al0.0 3Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
(3) And (3) mechanically mixing the cathode material obtained in the step (1) and the cathode material obtained in the step (2) according to the mass ratio of 8:2 to obtain the final cathode material.
Example 8
(1) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, the feed rate of the lithium hydroxide solution was 0.1m3The feed rate of the aluminum nitrate solution was 0.12m3H, 60h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate A) having a primary particle D50 of 1 μm and a secondary particle D50 of 8 μm.
119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate are ball-milled, mixed evenly and sintered at 850 ℃ for 12h to form lithium cobaltateThen the obtained lithium cobaltate was mixed with 1.48g Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 980 ℃ for 10h to obtain the single-particle sheet-shaped positive electrode material Li with the D50 of 17 mu m and the D99 of 40 mu m1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
(2) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH value to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.10m3/h、NH4HCO3The feed rate of the solution was 0.20m3H, the feed rate of the lithium hydroxide solution was 0.5m3The feed rate of the aluminum nitrate solution was 0.12m3H, 20h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water to a filtrate pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate B) having a primary particle D50 of 0.05 μm and a secondary particle D50 of 1 μm.
119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate are uniformly ball-milled and sintered at 850 ℃ for 10h to form lithium cobaltate, and then the obtained lithium cobaltate is mixed with 1.48g of Al2O3And 2.46g ZrO2Ball-milling and uniformly mixing the mixture, and sintering the mixture at 800 ℃ for 10 hours to obtain a single-particle anode material Li with 2 mu m D50 and 15 mu m D99 and similar-spherical morphology1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
(3) And (3) mechanically mixing the cathode material obtained in the step (1) and the cathode material obtained in the step (2) according to the mass ratio of 8:2 to obtain the final cathode material.
Example 9
(1) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3Solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, the feed rate of the lithium hydroxide solution was 0.1m3The feed rate of the aluminum nitrate solution was 0.12m3H, continuous feeding for 55 h. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water to a filtrate pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate a) having a primary particle D50 of 1.5 μm and a secondary particle D50 of 10 μm.
119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate are uniformly ball-milled and sintered at 980 ℃ for 10 hours to form lithium cobaltate, and then the obtained lithium cobaltate is mixed with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 950 ℃ for 10h to obtain a single-particle spherical anode material Li with D50 of 14.1 mu m and D99 of 35 mu m1.02Co0.96Al0.0 3Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
(2) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH value to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.15m3/h、NH4HCO3The feed rate of the solution was 0.28m3H, the feed rate of the lithium hydroxide solution was 0.05m3The feed rate of the aluminum nitrate solution was 0.12m3H, 24h of continuous feed. Stirring was then stopped and suction filtration was carried out, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate B) having primary particles D50 of 0.1 μm and secondary particles D50 of 5 μm.
Uniformly mixing 119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate by ball milling, sintering at 950 ℃ for 10h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 900 ℃ for 10h to obtain the spherical-like positive electrode material Li of secondary particles with the D50 of 6.3 mu m and the D99 of 25 mu m1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
(3) And (3) mechanically mixing the cathode material obtained in the step (1) with the cathode material obtained in the step (2) according to the mass ratio of 5:5 to obtain the final cathode material.
Example 10
(1) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, the feed rate of the lithium hydroxide solution was 0.1m3The feed rate of the aluminum nitrate solution was 0.12m3H, 50h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate A) having a primary particle D50 of 1.2 μm and a secondary particle D50 of 9.5. mu.m.
119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate are uniformly ball-milled and sintered at 1000 ℃ for 10 hours to form lithium cobaltate, and then the obtained lithium cobaltate is mixed with 1.48g of Al2O3And 2.46g ZrO2Ball-milling and uniformly mixing the mixture, and sintering the mixture at 950 ℃ for 12 hours to obtain a single-particle spherical anode material Li with D50 of 12.3 mu m and D99 of 55 mu m1.02Co0.96Al0.0 3Mg0.01O2.07Zr0.02Al0.03(correspond toModified lithium cobaltate cathode material a').
(2) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH value to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.15m3/h、NH4HCO3The feed rate of the solution was 0.28m3H, the feed rate of the lithium hydroxide solution was 0.05m3The feed rate of the aluminum nitrate solution was 0.12m3H, continuous feeding for 35 h. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate B) having primary particles D50 of 0.8 μm and secondary particles D50 of 6 μm.
Uniformly mixing 119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate by ball milling, sintering at 950 ℃ for 10h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling and uniformly mixing, and sintering at 900 ℃ for 11h to obtain the spherical-like positive electrode material Li of secondary particles with the D50 of 8 mu m and the D99 of 32 mu m1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
(3) And (3) mechanically mixing the cathode material obtained in the step (1) with the cathode material obtained in the step (2) according to the mass ratio of 9:1 to obtain the final cathode material.
Example 11
(1) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution is0.7m3H, the feed rate of the lithium hydroxide solution was 0.1m3The feed rate of the aluminum nitrate solution was 0.12m3H, continuous feeding for 80 h. Stirring was then stopped and suction filtration was carried out, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate A) having primary particles D50 of 2 μm and secondary particles D50 of 20 μm.
119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate are uniformly ball-milled and sintered at 1000 ℃ for 10 hours to form lithium cobaltate, and then the obtained lithium cobaltate is mixed with 1.48g of Al2O3And 2.46g ZrO2Ball-milling and uniformly mixing the mixture, and sintering the mixture at 980 ℃ for 12 hours to obtain a single-particle spherical anode material Li with the D50 of 23.5 mu m and the D99 of 55 mu m1.02Co0.96Al0.0 3Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
(2) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH value to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.15m3/h、NH4HCO3The feed rate of the solution was 0.28m3H, the feed rate of the lithium hydroxide solution was 0.05m3The feed rate of the aluminum nitrate solution was 0.12m3H, continuous feeding for 35 h. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate B) having primary particles D50 of 0.8 μm and secondary particles D50 of 6 μm.
Uniformly mixing 119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate by ball milling, sintering at 950 ℃ for 10h to form lithium cobaltate, and mixing the obtained lithium cobaltate with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, mixing, and sintering at 950 deg.C for 9h to obtain spherical-like shape of secondary particles with D50 of 8 μm and D99 of 32 μmPositive electrode material Li1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
(3) And (3) mechanically mixing the cathode material obtained in the step (1) with the cathode material obtained in the step (2) according to the mass ratio of 3:7 to obtain the final cathode material.
Comparative example 1
(1) NH with the concentration of 200g/L is added in a cocurrent feeding mode4HCO3The solution and 286.7g/L cobalt nitrate solution were added by a peristaltic pump to a reaction kettle to which 5L deionized water had been previously added to conduct coprecipitation reaction. Controlling the temperature of the reaction kettle at 40 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, 60h of continuous feed. Stirring was then stopped and suction filtered, the precipitate was washed with deionized water to a filtrate pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate with a primary particle D50 of 1.1 μm and a secondary particle D50 of 14 μm.
119g of the precursor precipitate and 100g of lithium carbonate were ball-milled, mixed uniformly and sintered at 1000 ℃ for 10 hours to form lithium cobaltate (unmodified lithium cobaltate), and then the obtained lithium cobaltate was mixed with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 980 ℃ for 12h to obtain a single-particle anode material LiCoO with a quasi-spherical morphology, wherein D50 is 17.5 mu m, and D99 is 45 mu m2.08Zr0.02Al0.03。
(2) NH with the concentration of 200g/L is added in a cocurrent feeding mode4HCO3The solution and 286.7g/L cobalt nitrate solution were added by a peristaltic pump to a reaction kettle to which 5L deionized water had been previously added to conduct coprecipitation reaction. Controlling the temperature of the reaction kettle to be 35 ℃, adjusting the pH to be 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.15m3/h、NH4HCO3The feed rate of the solution was 0.28m3H, 24h of continuous feed. Then stopping stirring and filtering, washing the precipitate with deionized water until the pH of the filtrate is less than 7, drying at 90 deg.C to obtain spherical precursor precipitate, and collecting the precipitate onceThe D50 of the particles was 0.5 μm and the D50 of the secondary particles was 5 μm.
119g of the precursor precipitate and 100g of lithium carbonate were ball-milled, mixed uniformly and sintered at 900 ℃ for 10 hours to form lithium cobaltate (unmodified lithium cobaltate), and then the obtained lithium cobaltate was mixed with 1.48g of Al2O3And 2.46g ZrO2Ball-milling, uniformly mixing and sintering at 900 ℃ for 10 hours to obtain the LiCoO serving as the cathode material with the sphere-like morphology of secondary particles with the D50 of 6.5 mu m and the D99 of 28 mu m2.08Zr0.02Al0.03。
(3) And (3) mechanically mixing the cathode material obtained in the step (1) with the cathode material obtained in the step (2) according to the mass ratio of 7:3 to obtain the final cathode material.
Comparative example 2
Only the positive electrode material Li having a spheroidal morphology of secondary particles with D50 of 6.3 μm and D99 of 25 μm in step (2) in example 6 was used1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
Comparative example 3
Only a single-particle positive electrode material Li having a spheroidal morphology with D50 of 23.5 μm and D99 of 55 μm in step (1) in example 11 was used1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
Comparative example 4
(1) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, the feed rate of the lithium hydroxide solution was 0.05m3The feed rate of the aluminum nitrate solution was 0.12m3H, continuous feeding for 90 h. Then stopping stirring and filtering, and using deionized waterThe precipitate was washed with water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate A) having a primary particle D50 of 3 μm and a secondary particle D50 of 25 μm.
119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate are uniformly ball-milled and sintered at 1000 ℃ for 10 hours to form lithium cobaltate, and then the obtained lithium cobaltate is mixed with 1.48g of Al2O3And 2.46g ZrO2Ball-milling and uniformly mixing the mixture, and sintering the mixture at 980 ℃ for 12 hours to obtain a single-particle anode material Li with a quasi-spherical morphology, wherein D50 is 28 microns and D99 is 62 microns1.02Co0.96Al0.03Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
(2) NH with the concentration of 80g/L is added in a cocurrent feeding mode4HCO3The solution, 280g/L cobalt nitrate solution, 11.25g/L aluminum nitrate solution and 40g/L lithium hydroxide solution are added into a reaction kettle which is added with 5L deionized water in advance through a peristaltic pump for coprecipitation reaction. Controlling the temperature of the reaction kettle at 50 ℃, adjusting the pH to 8, and adjusting the feeding speed of the cobalt nitrate solution to be 0.3m3/h、NH4HCO3The feed rate of the solution was 0.7m3H, the feed rate of the lithium hydroxide solution was 0.1m3The feed rate of the aluminum nitrate solution was 0.12m3H, 50h of continuous feed. Stirring was then stopped and suction filtration was carried out, and the precipitate was washed with deionized water until the filtrate had a pH of less than 7 and dried at 90 ℃ to give a spherical precursor precipitate (corresponding to precipitate B) having a primary particle D50 of 1.1 μm and a secondary particle D50 of 10.5. mu.m.
119g of precursor precipitate, 100g of lithium carbonate and 0.84g of magnesium carbonate are uniformly ball-milled and sintered at 1000 ℃ for 10 hours to form lithium cobaltate, and then the obtained lithium cobaltate is mixed with 1.48g of Al2O3And 2.46g ZrO2Ball-milling and uniformly mixing, and sintering at 950 ℃ for 10h to obtain the spherical-like positive electrode material Li of secondary particles with the D50 of 12 mu m and the D99 of 40 mu m1.02Co0.96Al0.0 3Mg0.01O2.07Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
(3) And (3) mechanically mixing the positive electrode material obtained in the step (1) with the positive electrode material obtained in the step (2) according to the mass ratio of 7:3 to obtain the final modified lithium cobaltate positive electrode material.
Comparative example 5
Only a single-particle positive electrode material Li having a spheroidal morphology and a D50 of 17 μm and a D99 of 40 μm in step (1) in example 1 was used1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material a').
Comparative example 6
Only the positive electrode material Li having a spheroidal morphology of secondary particles with D50 of 6.3 μm and D99 of 25 μm in step (2) in example 1 was used1.02Co0.97Mg0.03O2.08Zr0.02Al0.03(corresponding to modified lithium cobaltate positive electrode material B').
Comparative example 7
The positive electrode material was prepared in the same manner as in example 2 except that the mass ratio of the positive electrode material of step (1) to the positive electrode material of step (2) was 11: 1.
The preparation of the lithium ion battery is explained below.
Preparing a positive pole piece: the positive electrode materials prepared in examples 1 to 11 and comparative examples 1 to 7 were used as positive electrode materials of lithium ion batteries, Super-P was used as a conductive agent, and PVDF was used as a binder, the positive electrode materials, the conductive agent, and the binder were added to NMP at a mass ratio of 97:1:2, stirred uniformly, coated on both sides of a positive current collector aluminum foil (thickness of 12 μm), and dried, cold-pressed, and cut to obtain a positive electrode sheet.
Preparing a negative pole piece: mixing the artificial graphite serving as the negative electrode material, the thickening agent CMC and the binder SBR according to the weight ratio of 98:1:1, adding deionized water, uniformly stirring, coating the mixture on two surfaces of a copper foil (the thickness is 8 mu m) of a negative electrode current collector, and drying, cold pressing and slitting to obtain a negative electrode pole piece.
Preparing an electrolyte: the electrolyte comprises organic solvent and lithium salt, wherein the organic solvent is mixture of diethyl carbonate (DEC), dimethyl carbonate (DMC) and Ethylene Carbonate (EC)The volume ratio of the three organic solvents is 1:1:1, and the lithium salt is LiPF6The concentration is 1 mol/L.
Preparing a lithium ion battery: winding the positive pole piece, the negative pole piece and the isolating film (PE film) by a conventional process, and then carrying out terminal welding, packaging aluminum foil packaging, liquid injection, packaging formation and air exhaust molding to obtain the flexible package lithium ion battery.
Next, performance tests of the lithium ion battery are explained.
1. Compaction density testing of positive pole pieces
Taking the cold-pressed positive pole piece, and cutting to obtain the positive pole piece with the area of 1540.25mm2The small round piece is h in thickness measured after cold pressing1(mm), the thickness of the aluminum foil of the positive current collector is h2(mm), the weight of the small round piece is m (g), and the compacted density PD of the positive pole piece is 1000m/1540.25 (h)1-h2) (unit: g/cm3)。
2. Cycle performance testing of lithium ion batteries
The lithium ion battery was charged at 25 ℃ at a constant current of 0.5C (1225mA) to 4.45V, at a constant voltage of 4.45V to 0.05C (123mA), and then discharged at 0.5C (1225mA) to 3.0V, and the above charge and discharge cycles were repeated to record the number of cycles until the capacity retention rate of the lithium ion battery had decayed to 80%.
3. High temperature storage performance testing of lithium ion batteries
Charging to 4.45V at a constant current of 0.5C (1225mA), constant voltage of 4.45V to 0.05C (123mA), and then discharging to 3.0V at 0.5C (1225mA) at 25 deg.C, and recording the first discharge capacity; subsequently, the lithium ion battery was charged at 25 ℃ at a constant current of 0.5C (1225mA) to 4.45V and at a constant voltage of 4.45V to 0.05C (123mA), and the thickness of the lithium ion battery before storage was measured. And then, storing the fully charged lithium ion battery in an oven at 85 ℃ for 6 hours, and testing the thickness of the stored lithium ion battery while the lithium ion battery is hot. The thickness expansion rate after storage of the lithium ion battery is (thickness of the lithium ion battery after storage-thickness of the lithium ion battery before storage)/(thickness of the lithium ion battery before storage) × 100%.
4. Safety performance test of lithium ion battery
Charging to 4.50V at a constant current of 0.5C (1225mA) and keeping the voltage of 4.50V to 0.05C (123mA) at 25 ℃, disassembling the lithium ion battery in an argon-protected glove box, taking out a positive pole piece, cleaning in a DMC solution, scraping the positive pole material from the surface of the positive pole piece after DMC is completely volatilized, weighing 10mg of the positive pole material, putting the positive pole material into a special aluminum crucible, adding 0.1 mu L of electrolyte (the same as the preparation process of the lithium ion battery), and sealing for DSC test. The scanning temperature range of DSC test is 50-500 ℃, the heating rate is 10 ℃/min, and the temperature corresponding to the test main peak is the oxygen release temperature.
TABLE 1 results of Performance test of examples 1 to 11 and comparative examples 1 to 7
Figure BDA0001066370930000221
Figure BDA0001066370930000231
As can be seen from table 1, the positive electrode sheet prepared from the positive electrode material of the present invention has a higher compacted density, the number of cycles of the lithium ion battery is increased, the thickness expansion rate after high temperature storage is reduced, and the oxygen release temperature of the positive electrode material is increased, so that the lithium ion battery having better cycle performance, storage performance and safety performance can be obtained.
Referring to fig. 1 and 2, SEM of precipitate B and precipitate a in example 4, respectively. Referring to fig. 3 and 4, SEM images of the large-particle-diameter modified lithium cobaltate positive electrode material a 'and the small-particle-diameter modified lithium cobaltate positive electrode material B' of example 4 are shown, respectively. Fig. 5 is an SEM image of the cold-pressed positive electrode sheet of example 4. As can be seen from fig. 5, the particles of the positive electrode material are in a close-packed state, and therefore the compaction density of the positive electrode sheet is high.
In comparative example 1, no bulk phase doping was performed on lithium cobaltate, resulting in poor cycle performance, storage performance, and safety performance of the lithium ion battery. In comparative examples 2 and 6, only a single small-particle-size modified lithium cobaltate positive electrode material B 'is used, so that the compaction density of a positive electrode piece is low, the cycle performance of the lithium ion battery is deteriorated, the oxygen release temperature of the positive electrode material is reduced, and the safety performance of the lithium ion battery is deteriorated, and the thickness expansion rate of the lithium ion battery after high-temperature storage is obviously increased and the storage performance is seriously deteriorated due to the larger specific surface area of the small-particle-size modified lithium cobaltate positive electrode material B' in contact with the electrolyte. In comparative examples 3 and 5, only a single large-particle-size modified lithium cobaltate positive electrode material a 'is used, so that the compaction density of the positive electrode piece is low, the polarization of the large-particle-size modified lithium cobaltate positive electrode material a' is large, and the positive electrode material particles in the cold-pressed positive electrode piece are easy to break, so that the positive electrode material at the broken part reacts with the electrolyte, and the cycle performance of the lithium ion battery is poor. In comparative example 4, the particle sizes of the modified lithium cobaltate positive electrode material a 'and the modified lithium cobaltate positive electrode material B' were both too high, which in turn resulted in a decrease in the compacted density of the positive electrode sheet and a deterioration in the performance of the lithium ion battery. In comparative example 7, the mass ratio of the modified lithium cobaltate positive electrode material a ' to the modified lithium cobaltate positive electrode material B ' was too large, and the ratio of the modified lithium cobaltate positive electrode material a ' having a large particle size in the obtained positive electrode material was too large, which easily caused the positive electrode material particles in the cold-pressed positive electrode sheet to be crushed, so that the positive electrode material at the crushed position reacted with the electrolyte, and rather caused the performance of the lithium ion battery to be deteriorated.

Claims (13)

1.一种正极材料，其特征在于，所述正极材料包括改性的钴酸锂正极材料A’以及改性的钴酸锂正极材料B’，所述改性的钴酸锂正极材料A’以及所述改性的钴酸锂正极材料B’的质量比为d:1；1. a positive electrode material, it is characterized in that, described positive electrode material comprises modified lithium cobalt oxide positive electrode material A' and modified lithium cobalt oxide positive electrode material B', described modified lithium cobalt oxide positive electrode material A' And the mass ratio of the modified lithium cobalt oxide cathode material B' is d:1; 所述改性的钴酸锂正极材料A’的颗粒的D50为10μm～25μm、D99为30μm～60μm，所述改性的钴酸锂正极材料A’的形貌为单颗粒的类球形或片状；The particles of the modified lithium cobalt oxide positive electrode material A' have a D50 of 10 μm to 25 μm and a D99 of 30 μm to 60 μm, and the morphology of the modified lithium cobalt oxide positive electrode material A' is a single particle of spherical shape or sheet shape; 所述改性的钴酸锂正极材料B’的颗粒的D50为1μm～10μm、D99为8μm～30μm，所述改性的钴酸锂正极材料B’的形貌为单颗粒的类球形或二次颗粒的类球形；The particles of the modified lithium cobalt oxide positive electrode material B' have a D50 of 1 μm to 10 μm and a D99 of 8 μm to 30 μm, and the morphology of the modified lithium cobalt oxide positive electrode material B′ is a single particle, spherical or two The sub-particles are spherical; 所述改性的钴酸锂正极材料A’的颗粒的D50大于所述改性的钴酸锂正极材料B’的颗粒的D50；The D50 of the particles of the modified lithium cobalt oxide positive electrode material A' is greater than the D50 of the particles of the modified lithium cobalt oxide positive electrode material B'; 所述改性的钴酸锂正极材料A’的颗粒的D99大于所述改性的钴酸锂正极材料B’的颗粒的D99；The D99 of the particles of the modified lithium cobalt oxide positive electrode material A' is greater than the D99 of the particles of the modified lithium cobalt oxide positive electrode material B'; 其中，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’的化学通式相同且均为Li1+aCo1-bMbO2+cXm，M选自Al、Mg、Y、Ni、Mn、La中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10，M位于钴酸锂的体相掺杂位置，X包覆于钴酸锂的表面。Wherein, the modified lithium cobalt oxide positive electrode material A' and the modified lithium cobalt oxide positive electrode material B' have the same general chemical formula and are both Li 1+a Co 1-b M b O 2+c X m , M is selected from one or more of Al, Mg, Y, Ni, Mn, La, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y, Nb, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m≤0.1, 0<d≤10, M is located at the bulk doping position of lithium cobaltate, and X is coated on the lithium cobalt oxide. surface. 2.根据权利要求1所述的正极材料，其特征在于，X以氧化物的形态包覆于钴酸锂的表面。2 . The positive electrode material according to claim 1 , wherein X is coated on the surface of the lithium cobalt oxide in the form of an oxide. 3 . 3.一种正极材料的制备方法，用于制备权利要求1-2中任一项所述的正极材料，包括步骤：3. a preparation method of a positive electrode material, for preparing the positive electrode material according to any one of claims 1-2, comprising the steps: (1)将沉淀剂溶液、Co盐溶液、金属M盐的溶液加入反应釜中混合进行共沉淀反应，干燥后分别得到不同粒径的沉淀物A和沉淀物B，沉淀物A的一次颗粒的D50为1μm～5μm、二次颗粒的D50为5μm～20μm，沉淀物B的一次颗粒的D50为0.05μm～1μm、二次颗粒的D50为1μm～10μm；(1) the solution of precipitant solution, Co salt solution, metal M salt is added in the reactor and mixed to carry out co-precipitation reaction, after drying, the precipitate A and the precipitate B of different particle sizes are obtained respectively, and the primary particle of the precipitate A is D50 is 1μm～5μm, D50 of secondary particles is 5μm～20μm, D50 of primary particles of precipitate B is 0.05μm～1μm, D50 of secondary particles is 1μm～10μm; (2)将沉淀物A、锂盐混合并进行首次烧结后，再与金属X的化合物混合进行二次烧结，得到改性的钴酸锂正极材料A’，所述改性的钴酸锂正极材料A’的颗粒的D50为10μm～25μm、D99为30μm～60μm，所述改性的钴酸锂正极材料A’的形貌为单颗粒的类球形或片状；(2) After the precipitation A and the lithium salt are mixed and sintered for the first time, they are mixed with the compound of metal X for secondary sintering to obtain a modified lithium cobalt oxide positive electrode material A', the modified lithium cobalt oxide positive electrode The D50 of the particles of the material A' is 10 μm-25 μm, and the D99 is 30 μm-60 μm, and the morphology of the modified lithium cobalt oxide positive electrode material A' is a single particle of spherical or flake shape; (3)将沉淀物B、锂盐混合并进行首次烧结后，再与金属X的化合物混合进行二次烧结，得到改性的钴酸锂正极材料B’，所述改性的钴酸锂正极材料B’的颗粒的D50为1μm～10μm、D99为8μm～30μm，所述改性的钴酸锂正极材料B’的形貌为单颗粒的类球形或二次颗粒的类球形；(3) After the precipitate B and the lithium salt are mixed and sintered for the first time, they are mixed with the compound of metal X for secondary sintering to obtain a modified lithium cobalt oxide positive electrode material B'. The modified lithium cobalt oxide positive electrode The D50 of the particles of the material B' is 1 μm-10 μm, and the D99 is 8 μm-30 μm, and the morphology of the modified lithium cobalt oxide positive electrode material B' is a single particle quasi-spherical or a secondary particle quasi-spherical; (4)将所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’按质量比d:1混合，即完成正极材料的制备，其中，所述改性的钴酸锂正极材料A’的颗粒的D50大于所述改性的钴酸锂正极材料B’的颗粒的D50，所述改性的钴酸锂正极材料A’的颗粒的D99大于所述改性的钴酸锂正极材料B’的颗粒的D99，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’的化学通式相同且均为Li1+aCo1-bMbO2+cXm，M选自Al、Mg、Y、Ni、Mn、La中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10。(4) Mixing the modified lithium cobalt oxide positive electrode material A' and the modified lithium cobalt oxide positive electrode material B' in a mass ratio of d:1, that is, to complete the preparation of the positive electrode material, wherein the modified lithium cobalt oxide positive electrode material is prepared. The D50 of the particles of the modified lithium cobalt oxide cathode material A' is greater than the D50 of the particles of the modified lithium cobalt oxide cathode material B', and the D99 of the particles of the modified lithium cobalt oxide cathode material A' is greater than that of the modified lithium cobalt oxide cathode material A'. D99 of the particles of the modified lithium cobalt oxide cathode material B', the chemical formula of the modified lithium cobalt oxide cathode material A' and the modified lithium cobalt oxide cathode material B' are the same and both are Li 1+ a Co 1-b M b O 2+c X m , M is selected from one or more of Al, Mg, Y, Ni, Mn, La, X is selected from Mg, Al, Zr, Ti, Ni, Mn One or more of , Y and Nb, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m≤0.1, 0<d≤10. 4.根据权利要求3所述的正极材料的制备方法，其特征在于，在步骤(1)中，4. the preparation method of positive electrode material according to claim 3, is characterized in that, in step (1), 沉淀剂选自NH4HCO3、(NH4)2CO3、Na2CO3、NaHCO3、LiOH、NaOH中的一种或几种；The precipitant is selected from one or more of NH 4 HCO 3 , (NH 4 ) 2 CO 3 , Na 2 CO 3 , NaHCO 3 , LiOH, and NaOH; Co盐选自硝酸钴、氯化钴、醋酸钴、硫酸钴中的一种或几种；Co salt is selected from one or more of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate; 金属M盐选自金属M的硝酸盐、盐酸盐、醋酸盐、硫酸盐中的一种或几种。The metal M salt is selected from one or more of metal M nitrate, hydrochloride, acetate and sulfate. 5.根据权利要求3所述的正极材料的制备方法，其特征在于，在步骤(2)和步骤(3)中，5. the preparation method of positive electrode material according to claim 3 is characterized in that, in step (2) and step (3), 锂盐选自碳酸锂、氢氧化锂中的一种或几种；The lithium salt is selected from one or more of lithium carbonate and lithium hydroxide; 金属X的化合物选自金属X的碳酸盐、金属X的硝酸盐、金属X的氢氧化物、金属X的氧化物、金属X的碱式碳酸盐中的一种或几种。The compound of metal X is selected from one or more of metal X carbonate, metal X nitrate, metal X hydroxide, metal X oxide, and metal X hydroxycarbonate. 6.一种正极材料，其特征在于，所述正极材料包括改性的钴酸锂正极材料A’以及改性的钴酸锂正极材料B’，所述改性的钴酸锂正极材料A’以及所述改性的钴酸锂正极材料B’的质量比为d:1；6. A positive electrode material, characterized in that the positive electrode material comprises a modified lithium cobalt oxide positive electrode material A' and a modified lithium cobalt oxide positive electrode material B', and the modified lithium cobalt oxide positive electrode material A' And the mass ratio of the modified lithium cobalt oxide cathode material B' is d:1; 所述改性的钴酸锂正极材料A’的颗粒的D50为10μm～25μm、D99为30μm～60μm，所述改性的钴酸锂正极材料A’的形貌为单颗粒的类球形或片状；The particles of the modified lithium cobalt oxide positive electrode material A' have a D50 of 10 μm to 25 μm and a D99 of 30 μm to 60 μm, and the morphology of the modified lithium cobalt oxide positive electrode material A' is a single particle of spherical shape or sheet shape; 所述改性的钴酸锂正极材料B’的颗粒的D50为1μm～10μm、D99为8μm～30μm，所述改性的钴酸锂正极材料B’的形貌为单颗粒的类球形或二次颗粒的类球形；The particles of the modified lithium cobalt oxide positive electrode material B' have a D50 of 1 μm to 10 μm and a D99 of 8 μm to 30 μm, and the morphology of the modified lithium cobalt oxide positive electrode material B′ is a single particle, spherical or two The sub-particles are spherical; 所述改性的钴酸锂正极材料A’的颗粒的D50大于所述改性的钴酸锂正极材料B’的颗粒的D50；The D50 of the particles of the modified lithium cobalt oxide positive electrode material A' is greater than the D50 of the particles of the modified lithium cobalt oxide positive electrode material B'; 所述改性的钴酸锂正极材料A’的颗粒的D99大于所述改性的钴酸锂正极材料B’的颗粒的D99；The D99 of the particles of the modified lithium cobalt oxide positive electrode material A' is greater than the D99 of the particles of the modified lithium cobalt oxide positive electrode material B'; 其中，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’的化学通式相同且均为Li1+aCo1-bMbO2+cXm，M选自Al、Mg、Y、Ni、Mn、La中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10，M位于钴酸锂的体相掺杂位置和固溶体过渡层掺杂位置，X包覆于钴酸锂的表面。Wherein, the modified lithium cobalt oxide positive electrode material A' and the modified lithium cobalt oxide positive electrode material B' have the same general chemical formula and are both Li 1+a Co 1-b M b O 2+c X m , M is selected from one or more of Al, Mg, Y, Ni, Mn, La, X is selected from one or more of Mg, Al, Zr, Ti, Ni, Mn, Y, Nb, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m≤0.1, 0<d≤10, M is located at the bulk doping position of lithium cobalt oxide and the doping position of the solid solution transition layer, X Coated on the surface of lithium cobalt oxide. 7.根据权利要求6所述的正极材料，其特征在于，X以氧化物的形态包覆于钴酸锂的表面。7 . The positive electrode material according to claim 6 , wherein X is coated on the surface of the lithium cobalt oxide in the form of an oxide. 8 . 8.一种正极材料的制备方法，用于制备权利要求6-7中任一项所述的正极材料，包括步骤：8. A preparation method of a positive electrode material, for preparing the positive electrode material according to any one of claims 6-7, comprising the steps: (1)将沉淀剂溶液、Co盐溶液、金属M盐的溶液加入反应釜中混合进行共沉淀反应，干燥后分别得到不同粒径的沉淀物A和沉淀物B，沉淀物A的一次颗粒的D50为1μm～5μm、二次颗粒的D50为5μm～20μm，沉淀物B的一次颗粒的D50为0.05μm～1μm、二次颗粒的D50为1μm～10μm；(1) the solution of precipitant solution, Co salt solution, metal M salt is added in the reactor and mixed to carry out co-precipitation reaction, after drying, the precipitate A and the precipitate B of different particle sizes are obtained respectively, and the primary particle of the precipitate A is D50 is 1μm～5μm, D50 of secondary particles is 5μm～20μm, D50 of primary particles of precipitate B is 0.05μm～1μm, D50 of secondary particles is 1μm～10μm; (2)将沉淀物A、锂盐以及金属M盐混合并进行首次烧结后，再与金属X的化合物混合进行二次烧结，得到改性的钴酸锂正极材料A’，所述改性的钴酸锂正极材料A’的颗粒的D50为10μm～25μm、D99为30μm～60μm，所述改性的钴酸锂正极材料A’的形貌为单颗粒的类球形或片状；(2) after mixing the precipitate A, lithium salt and metal M salt and performing primary sintering, and then mixing with the compound of metal X for secondary sintering to obtain a modified lithium cobalt oxide positive electrode material A', the modified The particles of the lithium cobalt oxide positive electrode material A' have a D50 of 10 μm to 25 μm and a D99 of 30 μm to 60 μm, and the morphology of the modified lithium cobalt oxide positive electrode material A' is a single particle of spherical or flake shape; (3)将沉淀物B、锂盐以及金属M盐混合并进行首次烧结后，再与金属X的化合物混合进行二次烧结，得到改性的钴酸锂正极材料B’，所述改性的钴酸锂正极材料B’的颗粒的D50为1μm～10μm、D99为8μm～30μm，所述改性的钴酸锂正极材料B’的形貌为单颗粒的类球形或二次颗粒的类球形；(3) after mixing the precipitate B, lithium salt and metal M salt and performing primary sintering, and then mixing with the compound of metal X for secondary sintering to obtain a modified lithium cobalt oxide positive electrode material B', the modified The D50 of the particles of the lithium cobalt oxide positive electrode material B' is 1 μm to 10 μm, and the D99 is 8 μm to 30 μm, and the morphology of the modified lithium cobalt oxide positive electrode material B' is a single particle or a secondary particle. ; (4)将所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’按质量比d:1混合，即完成正极材料的制备，其中，所述改性的钴酸锂正极材料A’的颗粒的D50大于所述改性的钴酸锂正极材料B’的颗粒的D50，所述改性的钴酸锂正极材料A’的颗粒的D99大于所述改性的钴酸锂正极材料B’的颗粒的D99，所述改性的钴酸锂正极材料A’和所述改性的钴酸锂正极材料B’的化学通式相同且均为Li1+aCo1-bMbO2+cXm，M选自Al、Mg、Y、Ni、Mn、La中的一种或几种，X选自Mg、Al、Zr、Ti、Ni、Mn、Y、Nb中的一种或几种，0≤a≤0.1，0＜b≤0.1，0≤c≤1，0＜m≤0.1，0＜d≤10。(4) Mixing the modified lithium cobalt oxide positive electrode material A' and the modified lithium cobalt oxide positive electrode material B' in a mass ratio of d:1, that is, to complete the preparation of the positive electrode material, wherein the modified lithium cobalt oxide positive electrode material is prepared. The D50 of the particles of the modified lithium cobalt oxide cathode material A' is greater than the D50 of the particles of the modified lithium cobalt oxide cathode material B', and the D99 of the particles of the modified lithium cobalt oxide cathode material A' is greater than that of the modified lithium cobalt oxide cathode material A'. D99 of the particles of the modified lithium cobalt oxide cathode material B', the chemical formula of the modified lithium cobalt oxide cathode material A' and the modified lithium cobalt oxide cathode material B' are the same and both are Li 1+ a Co 1-b M b O 2+c X m , M is selected from one or more of Al, Mg, Y, Ni, Mn, La, X is selected from Mg, Al, Zr, Ti, Ni, Mn One or more of , Y and Nb, 0≤a≤0.1, 0<b≤0.1, 0≤c≤1, 0<m≤0.1, 0<d≤10. 9.根据权利要求8所述的正极材料的制备方法，其特征在于，在步骤(1)中，9. The preparation method of positive electrode material according to claim 8, characterized in that, in step (1), 沉淀剂选自NH4HCO3、(NH4)2CO3、Na2CO3、NaHCO3、LiOH、NaOH中的一种或几种；The precipitant is selected from one or more of NH 4 HCO 3 , (NH 4 ) 2 CO 3 , Na 2 CO 3 , NaHCO 3 , LiOH, and NaOH; Co盐选自硝酸钴、氯化钴、醋酸钴、硫酸钴中的一种或几种；Co salt is selected from one or more of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate; 金属M盐选自金属M的硝酸盐、盐酸盐、醋酸盐、硫酸盐中的一种或几种。The metal M salt is selected from one or more of metal M nitrate, hydrochloride, acetate and sulfate. 10.根据权利要求8所述的正极材料的制备方法，其特征在于，在步骤(2)和步骤(3)中，10. The preparation method of positive electrode material according to claim 8, wherein in step (2) and step (3), 金属M盐选自金属M的硝酸盐、盐酸盐、醋酸盐、硫酸盐中的一种或几种；The metal M salt is selected from one or more of the nitrate, hydrochloride, acetate and sulfate of metal M; 锂盐选自碳酸锂、氢氧化锂中的一种或几种；The lithium salt is selected from one or more of lithium carbonate and lithium hydroxide; 金属X的化合物选自金属X的碳酸盐、金属X的硝酸盐、金属X的氢氧化物、金属X的氧化物、金属X的碱式碳酸盐中的一种或几种。The compound of metal X is selected from one or more of metal X carbonate, metal X nitrate, metal X hydroxide, metal X oxide, and metal X hydroxycarbonate. 11.一种正极极片，包括：11. A positive pole piece, comprising: 正极集流体；以及a positive current collector; and 正极膜片，设置于正极集流体上且包括正极材料、导电剂以及粘结剂；a positive electrode membrane, which is arranged on the positive electrode current collector and includes a positive electrode material, a conductive agent and a binder; 其特征在于，It is characterized in that, 所述正极材料为根据权利要求1-2、6-7中任一项所述的正极材料。The positive electrode material is the positive electrode material according to any one of claims 1-2 and 6-7. 12.根据权利要求11所述的正极极片，其特征在于，所述正极极片在压实后达到的压实密度≥4.0g/cm3。12 . The positive pole piece according to claim 11 , wherein the compacted density of the positive pole piece after compaction is greater than or equal to 4.0 g/cm 3 . 13 . 13.一种锂离子电池，其特征在于，包括根据权利要求11或12所述的正极极片。13. A lithium ion battery, characterized in that it comprises the positive electrode plate according to claim 11 or 12.
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