CN111370653A - Positive electrode material precursor, preparation method thereof, positive electrode material and battery - Google Patents

Positive electrode material precursor, preparation method thereof, positive electrode material and battery Download PDF

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CN111370653A
CN111370653A CN201811588428.7A CN201811588428A CN111370653A CN 111370653 A CN111370653 A CN 111370653A CN 201811588428 A CN201811588428 A CN 201811588428A CN 111370653 A CN111370653 A CN 111370653A
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coating layer
positive electrode
clad layer
primary particles
electrode material
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曹文玉
徐茶清
肖怀曙
苟中平
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Shenzhen BYD Auto R&D Co Ltd
Shenzhen BYD Lithium Battery Co Ltd
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Shenzhen BYD Auto R&D Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a positive electrode material precursor, a preparation method thereof, a positive electrode material and a battery. The anode material precursor comprises a core and a coating layer for coating the core, wherein the number n of the coating layer is more than or equal to 3, the coating layer comprises a 1 st coating layer and a 2 nd coating layer … …, the number n of the coating layer is more than or equal to 1+ m of the coating layer, m is a positive integer, n is less than or equal to 1+ m, and the particle size of primary particles in the coating layer with the odd number in any two adjacent layers is more than or equal to that of primary particles in the coating layer with the even number; the 1 st coating layer is in contact with the core, and the particle size of primary particles in the core is smaller than that of the 1 st coating layer; the metal hydroxide is NixCoyMn1-x-y (OH)2, wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.2.

Description

Positive electrode material precursor, preparation method thereof, positive electrode material and battery
Technical Field
The invention relates to a positive electrode material precursor, a preparation method thereof, a positive electrode material and a battery containing the positive electrode material.
Background
At present, the shape of the ternary material precursor is mostly secondary spherical particles consisting of primary particles without coating layers, and the particle size of the secondary particles is 10-11 microns (used for conventional ternary materials) or 3-5 microns (used for single crystal ternary materials). From the internal structure of the precursor: the precursor for the conventional ternary material is usually produced by adopting a continuous method, and the process has the advantages of high productivity, but wide diameter distribution of the secondary spherical particles; the precursor for the single crystal ternary material is usually produced by an intermittent method, the secondary spheres prepared by the process have narrow particle size distribution, better consistency and lower productivity, and the obtained ternary material precursor has a structure that the surface of a core is coated with a coating layer which is of a single-layer structure. The ternary material obtained by sintering the two ternary material precursors is easy to crack in the using process, and the cyclicity, the rate capability and the safety performance of the battery are influenced.
Disclosure of Invention
The invention aims to at least solve at least one technical problem in the prior art, and therefore provides a multilayer positive electrode material precursor, a preparation method thereof and a prepared positive electrode material thereof.
In order to achieve the aim, the invention provides a positive electrode material precursor, which comprises a core and a coating layer for coating the core, wherein the number n of the coating layer is more than or equal to 3; the coating layers comprise a 1 st coating layer and a 2 nd coating layer … …, wherein m is a positive integer, 1+ m is less than or equal to n, and the particle size of primary particles in the coating layer with the odd number in any two adjacent layers is more than or equal to that of primary particles in the coating layer with the even number; the 1 st coating layer is in contact with the core, and the primary particles in the core have a small particle sizeThe particle size of the primary particles in the 1 st coating layer; the core and the coating layer contain metal hydroxide, and the metal hydroxide is NixCoyMn1-x-y(OH)2Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.2.
The application provides an anode material precursor is multilayer structure, the particle diameter variation of primary particle in arbitrary adjacent two-layer, preferred adoption contains the less primary particle layer of particle diameter and contains the great primary particle layer of particle diameter, layer upon layer the cladding forms the high anode material precursor of compactness in turn, and simultaneously, in the transition region of contact between adjacent two-layer, the granule quantity of the less primary particle of particle diameter is more, arrange, the great primary particle nonconformity of growth direction and particle diameter, it is comparatively mixed and disorderly, be favorable to the stress release of follow-up sintering process. Meanwhile, compared with primary particles with larger particle sizes, the primary particles with smaller particle sizes are larger in number, more in holes and larger in porosity of a coating layer where the primary particles with smaller particle sizes are located, the prepared anode material is good in consistency and less in cracking, and the cyclicity and the stability of the battery are further improved.
The second aspect of the present invention provides a method for preparing a precursor of a positive electrode material, the method comprising:
1) mixing nickel salt, cobalt salt and manganese salt according to the molar ratio of x to y to 1-x-y to obtain mixed salt solution with the total concentration of 1-3 mol/L; preparing ammonia water solution with the concentration of 4-13 mol/L; preparing a sodium hydroxide solution with the concentration of 2-8 mol/L;
2) adding water into a reaction container as reaction base liquid, dropwise adding the ammonia water solution and the sodium hydroxide solution in the step 1) into the water at a constant temperature of 45-60 ℃, and stirring to obtain the reaction base liquid with the pH of 12-13 and the ammonia concentration of 0.3-0.8 mol/L;
3) continuously adding the mixed salt solution, the ammonia water solution and the sodium hydroxide solution in the step 1) into a reaction container, and stirring; in the first reaction stage, the ammonia concentration is adjusted to be 0.3-0.8mol/L, the pH is adjusted to be 12-13, the temperature is 45-60 ℃, and the reaction time is 1-15 hours; in the second reaction stage, the ammonia concentration is adjusted to be 0.3-0.8mol/L, the pH is adjusted to be 11-12, the temperature is 45-60 ℃, and the reaction time is 1-30 hours; repeating the first reaction stage and the second reaction stage; in this order, the reaction times in each of the first reaction stages are the same or different; the reaction time in each second reaction stage is the same or different;
5) aging, separating and washing the reactant to obtain the metal hydroxide NixCoyMn1-x-y (OH)2, wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.2.
The invention provides a positive electrode material, and the positive electrode material is prepared from the positive electrode precursor. The particle size distribution interval of the precursor of the positive electrode material is narrow, the particle size distribution interval of the positive electrode material obtained after sintering is also narrow, and the consistency of the positive electrode material is good. By regulating the number of layers of the precursor of the positive electrode material and the particle size of the primary particles in different layers, compared with the precursor of the positive electrode material with a multilayer structure prepared in the prior art (figure 5), the precursor of the positive electrode material prepared by the method has smaller difference of the particle size of the primary particles in different layers, and the consistency of the positive electrode material obtained after sintering is better.
In a fourth aspect, the present invention provides a battery comprising a positive electrode, a negative electrode, and an electrolytic solution or a solid electrolyte, wherein the positive electrode contains the positive electrode material. The lithium ion battery containing the anode material has good charge-discharge rate performance and safety performance, and the preparation method has simple procedures.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
Fig. 1 is an SEM image of a positive electrode material precursor in one embodiment of the present invention, at an enlarged scale of × 20000.
Fig. 2 is an SEM image of a cross-section of a precursor of a positive electrode material at an enlarged scale of × 20000 according to an embodiment of the present invention.
Fig. 3 is an SEM image of a cross-section of a precursor of a positive electrode material, on an enlarged scale × 7000, in accordance with an embodiment of the present invention.
Fig. 4 is an SEM image of a cross section of the precursor of the positive electrode material in comparative example 1, at an enlarged scale of × 10000.
Fig. 5 is an SEM image of a cross-section of the precursor of the positive electrode material in comparative example 2, enlarged at × 30000.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The existing commercial ternary material of the secondary sphere or the single crystal ternary material is easy to crack in the charging and discharging process of the battery, and the cyclicity, the rate capability and the safety performance of the battery are influenced. The reason for this analysis may be: the ternary material precursor in the ternary material of the secondary sphere is not coated, as shown in fig. 4, the arrangement direction of primary particles is disordered, and the consistency of the particle size of the prepared secondary sphere is poor, so that the electrical property of the ternary material is influenced. The structure of the ternary material precursor in the single crystal ternary material is a core and a coating layer coated on the core, the coating layer is a single layer as shown in fig. 5, the size difference of primary particles in the core and the coating layer is large, the primary particles in the coating layer are large in particle size, the number of the primary particles with large particle size in the ternary material precursor is large, the coating layer is thick, the consistency of the prepared anode material is poor, and therefore the electrical property of the anode material is influenced.
In order to solve the technical problems, the invention provides a positive electrode material precursor, which comprises a core and a coating layer for coating the core, wherein the number n of the coating layer is more than or equal to 3; the coating layers comprise a 1 st coating layer and a 2 nd coating layer … …, wherein m is a positive integer, 1+ m is less than or equal to n, and the particle size of primary particles in the coating layer with the odd number in any two adjacent layers is more than or equal to that of primary particles in the coating layer with the even number; the 1 st coating layer is in contact with the core, and the particle size of primary particles in the core is smaller than that of the 1 st coating layer; the core and the cladding contain metal hydroxide, and the metal hydroxide is NixCoyMn1-x-y (OH)2, wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.2.
The application provides an anode material precursor is multilayer structure, the particle diameter variation of the primary particle in arbitrary adjacent two-layer, the preferred layer that adopts the less primary particle of particle diameter and the layer that contains the great primary particle of particle diameter, layer upon layer alternate cladding forms the high anode material precursor of compactness, and simultaneously, in the transition region of contact between adjacent two-layer, the granule quantity of the less primary particle of particle diameter is more, arrange, the growth direction is inconsistent with the great primary particle of particle diameter, it is comparatively mixed and disorderly, be favorable to the stress release of follow-up sintering process. Meanwhile, compared with primary particles with larger particle sizes, the primary particles with smaller particle sizes are larger in number, more in holes and larger in porosity of a coating layer where the primary particles with smaller particle sizes are located, the prepared anode material is good in consistency and less in cracking, and the cyclicity and the stability of the battery are further improved.
Preferably, the number of the coating layers n may be any one of 3, 4, 5, 6, 7, 8, 9 and 10, the coating layers include a 1 st coating layer, a 2 nd coating layer and a 3 rd coating layer, the 1 st coating layer, the 2 nd coating layer and the 3 rd coating layer sequentially coat the core, and the 1 st coating layer is in contact with the core; the particle size of the primary particles in the core is 0.05-0.2 micrometer, the particle size of the primary particles in the 1 st coating layer is 0.4-1.5 micrometer, the particle size of the primary particles in the 2 nd coating layer is 0.05-0.2 micrometer, and the particle size of the primary particles in the 3 rd coating layer is 0.2-1.1 micrometer.
In the above-described cathode material precursor, the particle diameter of the primary particle in the core is smaller than the particle diameter of the primary particle in the 1 st coating layer, the particle diameter of the primary particle in the 1 st coating layer is larger than the particle diameter of the primary particle in the 2 nd coating layer, and the particle diameter of the primary particle in the 2 nd coating layer is smaller than the particle diameter of the primary particle in the 3 rd coating layer; compared with the prior art (fig. 4 and 5), the number of layers of the precursor of the positive electrode material, the particle size of the primary particles in two adjacent layers and the particle size difference of the primary particles in different layers are regulated and controlled to be smaller; meanwhile, in a transition region where two adjacent layers are in contact, primary particles with smaller particle sizes are more in number, and the arrangement and growth directions of the primary particles are inconsistent with those of the primary particles with larger particle sizes, so that the primary particles are more disordered, and stress release in the subsequent sintering process is facilitated; and compared with primary particles with larger particle sizes, the primary particles with smaller particle sizes are larger in number, more in holes and larger in porosity of the coating layer where the primary particles with smaller particle sizes are located, so that the prepared anode material is good in consistency and less in cracking, and the cyclicity and stability of the battery are further improved.
Preferably, the coating layer comprises a 1 st coating layer, a 2 nd coating layer, a 3 rd coating layer, a 4 th coating layer and a 5 th coating layer, the 1 st coating layer, the 2 nd coating layer, the 3 rd coating layer, the 4 th coating layer and the 5 th coating layer sequentially coat the core, and the 1 st coating layer is in contact with the core; the particle size of the primary particles in the core is 0.05-0.2 micrometer, the particle size of the primary particles in the 1 st coating layer is 0.6-1.5 micrometer, the particle size of the primary particles in the 2 nd coating layer is 0.05-0.2 micrometer, the particle size of the primary particles in the 3 rd coating layer is 0.3-1 micrometer, the particle size of the primary particles in the 4 th coating layer is 0.05-0.2 micrometer, and the particle size of the primary particles in the 5 th coating layer is 0.4-2 micrometer.
In the above-described cathode material precursor, the particle diameter of the primary particle in the core is smaller than the particle diameter of the primary particle in the 1 st coating layer, the particle diameter of the primary particle in the 1 st coating layer is larger than the particle diameter of the primary particle in the 2 nd coating layer, the particle diameter of the primary particle in the 2 nd coating layer is smaller than the particle diameter of the primary particle in the 3 rd coating layer, the particle diameter of the primary particle in the 3 rd coating layer is larger than the particle diameter of the primary particle in the 4 th coating layer, and the particle diameter of the primary particle in the 4 th coating layer is smaller than the particle diameter of the primary particle in the 5 th coating layer; compared with the prior art (fig. 4 and 5), the number of layers of the precursor of the positive electrode material, the particle size of the primary particles in two adjacent layers and the particle size difference of the primary particles in different layers are regulated and controlled to be smaller; meanwhile, in a transition region where two adjacent layers are in contact, primary particles with smaller particle sizes are more in number, and the arrangement and growth directions of the primary particles are inconsistent with those of the primary particles with larger particle sizes, so that the primary particles are more disordered, and stress release in the subsequent sintering process is facilitated; and compared with primary particles with larger particle sizes, the primary particles with smaller particle sizes are larger in number, more in holes and larger in porosity of the coating layer where the primary particles with smaller particle sizes are located, so that the prepared anode material is good in consistency and less in cracking, and the cyclicity and stability of the battery are further improved. Preferably, the number of layers of the precursor of the cathode material can be randomly regulated, and the metal hydroxide in each layer structure is uniformly distributed.
Preferably, the average particle diameter of the positive electrode material precursor is 3 to 18 μm, and may be one of 3, 3.5, 4, 4.6, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.6, 10, 10.6, 11, 11.3, 11.8, 12, 12.6, 12.8, and 13. Under the condition that the average particle size of the precursor of the positive electrode material is constant, the more the number of layers is, the thinner each layer is, the smaller the particle size of the primary particles in each layer is, the smaller the particle size difference of the primary particles between layers is, the smaller the particle size difference of the prepared positive electrode material is, and the better the consistency of the positive electrode material is.
Preferably, when the number n of the coating layers is 3, the diameter of the core is 0.5 to 2 micrometers, the thickness of the 1 st coating layer is 0.4 to 1.5 micrometers, the thickness of the 2 nd coating layer is 0.2 to 1.1 micrometers, and the thickness of the 3 rd coating layer is 0.2 to 1.1 micrometers.
Preferably, when the number n of the coating layers is 5, the diameter of the core is 0.5 to 2 micrometers, the thickness of the 1 st coating layer is 0.6 to 1.5 micrometers, the thickness of the 2 nd coating layer is 0.2 to 0.5 micrometers, the thickness of the 3 rd coating layer is 0.3 to 1 micrometer, the thickness of the 4 th coating layer is 0.3 to 0.7 micrometer, and the thickness of the 5 th coating layer is 0.3 to 1.1 micrometer.
The second aspect of the present invention provides a method for preparing a precursor of a positive electrode material, the method comprising:
1) mixing nickel salt, cobalt salt and manganese salt according to the molar ratio of x to y to 1-x-y to obtain mixed salt solution with the total concentration of 1-3 mol/L; preparing ammonia water solution with the concentration of 4-13 mol/L; preparing a sodium hydroxide solution with the concentration of 2-8 mol/L;
2) adding water into a reaction container as reaction base liquid, dropwise adding the ammonia water solution and the sodium hydroxide solution in the step 1) into the water at a constant temperature of 45-60 ℃, and stirring to obtain the reaction base liquid with the pH of 12-13 and the ammonia concentration of 0.3-0.8 mol/L;
3) continuously adding the mixed salt solution, the ammonia water solution and the sodium hydroxide solution in the step 1) into a reaction container, and stirring; in the first reaction stage, the ammonia concentration is adjusted to be 0.3-0.8mol/L, the pH is adjusted to be 12-13, the temperature is 45-60 ℃, and the reaction time is 1-15 hours; in the second reaction stage, the ammonia concentration is adjusted to be 0.3-0.8mol/L, the pH is adjusted to be 11-12, the temperature is 45-60 ℃, and the reaction time is 1-30 hours; repeating the first reaction stage and the second reaction stage; in this order, the reaction times in each of the first reaction stages are the same or different; the reaction time in each second reaction stage is the same or different;
5) aging, separating and washing the reactant to obtain the metal hydroxide NixCoyMn1-x-y(OH)2Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.2.
Preferably, the molar ratio of the nickel salt, the cobalt salt and the manganese salt in the mixed salt solution is one of 8:1:1, 6:2:2, 5:2:3, 2:1:1 and 1:1: 1.
Preferably, the reaction vessel is a reaction kettle. The stirring function is provided, the complete reaction is facilitated, and the components of the prepared precursor of the anode material are more uniform.
Preferably, the nickel salt is selected from one or more of nickel sulfate, nickel chloride and nickel nitrate; the cobalt salt is selected from one or more of cobalt sulfate, cobalt chloride and cobalt nitrate; the manganese salt is selected from one or more of manganese sulfate, manganese chloride and manganese nitrate.
The invention provides a positive electrode material, and the positive electrode material is prepared from the positive electrode precursor. By regulating and controlling the number of layers of the precursor of the anode material and the particle size of the primary particles in different layers, the difference of the particle size of the primary particles in different layers is small, the obtained precursor of the anode material is good in consistency, and the further prepared anode material is good in consistency.
The preparation method for preparing the cathode material by using the cathode material precursor is a common process in the field, and is not described herein again.
In a fourth aspect, the present invention provides a battery comprising a positive electrode, a negative electrode, and an electrolytic solution or a solid electrolyte, wherein the positive electrode contains the positive electrode material. The consistency of the anode material is good, the lithium ion battery containing the anode material has good charge-discharge rate performance and safety performance, and the preparation method has simple procedures.
The battery system applied to the anode material can be a liquid lithium ion battery, an all-solid-state lithium ion battery, a polymer lithium ion battery, or a pre-solid-state or quasi-solid-state lithium ion battery.
The anode, the cathode, the electrolyte and the solid electrolyte are common existing materials in the field, can be directly purchased or prepared by self, and the preparation method is the existing preparation process in the field.
The preparation process of the battery is a common preparation process in the field and is not described in detail herein.
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Preparation of positive electrode material precursor
1) Mixing nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of 8:1:1 to obtain a mixed salt solution with the total concentration of 2 mol/L; preparing a sodium hydroxide solution with the concentration of 5 mol/L; preparing an ammonia water solution with the concentration of 5 mol/L;
2) adding 5L of water into a reaction kettle to serve as reaction base liquid, heating in a water bath to control the constant temperature of the base liquid to be 55 ℃, dropwise adding the sodium hydroxide solution and the ammonia water solution prepared in the step 1) into the aqueous solution, and stirring to obtain the reaction base liquid with the pH value of 12.3 and the ammonia concentration of 0.5 mol/L;
3) continuously adding the mixed salt solution, the ammonia water solution and the sodium hydroxide solution in the step 1) into a reaction kettle with a stirrer, and adjusting the ammonia concentration to be 0.5mol/L, the pH value to be 12.3, the temperature to be 55 ℃ and the reaction time to be 2 hours in a first reaction stage (inner core); adjusting the flow rates of the ammonia water solution and the sodium hydroxide solution, and entering a second reaction stage (a coating layer 1), wherein the ammonia concentration is 0.5mol/L, the pH value is 11.2, the temperature is 55 ℃, and the reaction time is 18 hours; repeating the first reaction stage (coating layer 2), and adjusting the reaction time from 2 hours to 3 hours; repeating the two stages (the 3 rd coating layer), and adjusting the reaction time from 18 hours to 6 hours;
4) aging for 2 hours, separating and washing the reactant to obtain the metal hydroxide Ni0.8Co0.1Mn0.1(OH)2The shape of the obtained precursor of the cathode material is shown in fig. 1, the number of the coating layers is 3, and the particle sizes of primary particles in different layers are different.
Preparation of positive electrode material and battery
And uniformly mixing the precursor of the positive electrode material and a lithium source according to the molar ratio of 1:1.1, then roasting in a muffle furnace for multiple stages, and raising the roasting temperature to 850 ℃ at the heating rate of 3 ℃/min. The roasting time is 16H, and the nickel cobalt lithium manganate positive electrode material is obtained by cooling, crushing and sieving after multi-stage roasting.
Example 2
Preparation of positive electrode material precursor
1) Mixing nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of 5:2:3 to obtain a mixed salt solution with the total concentration of 2 mol/L; preparing a sodium hydroxide solution with the concentration of 5 mol/L; preparing an ammonia water solution with the concentration of 5 mol/L;
2) adding 5L of water into a reaction kettle to serve as reaction base liquid, heating in a water bath to control the constant temperature of the base liquid to be 55 ℃, dropwise adding the sodium hydroxide solution and the ammonia water solution prepared in the step 1) into the aqueous solution, and stirring to obtain the reaction base liquid with the pH value of 12.9 and the ammonia concentration of 0.3 mol/L;
3) continuously adding the mixed salt solution, the ammonia water solution and the sodium hydroxide solution in the step 1) into a reaction kettle with a stirrer, and in the first reaction stage, adjusting the ammonia concentration to be 0.3mol/L, the pH value to be 12.9, the temperature to be 55 ℃ and the reaction time to be 4 hours; adjusting the flow rates of the ammonia water solution and the sodium hydroxide solution, and entering a second reaction stage, wherein the ammonia concentration is 0.3mol/L, the pH value is 11.5, the temperature is 55 ℃, and the reaction time is 16 hours; repeating the first reaction stage, wherein the reaction time is adjusted from 4 hours to 14 hours; repeating the second reaction stage, wherein the reaction time is adjusted from 16 hours to 10 hours
4) Aging for 2 hours, separating and washing the reactant to obtain the metal hydroxide Ni0.5Co0.2Mn0.3(OH)2The cross section of the obtained positive electrode material precursor is shown in fig. 2, the number of coating layers is 3, and the primary particles in different layers have different particle sizes.
Preparation of cathode material
And uniformly mixing the precursor of the positive electrode material and a lithium source according to the molar ratio of 1:1.1, then roasting in a muffle furnace for multiple stages, and raising the roasting temperature to 920 ℃ at the temperature rise speed of 2 ℃/min. The roasting time is 16H, and the nickel cobalt lithium manganate positive electrode material is obtained by cooling, crushing and sieving after multi-stage roasting.
Example 3
Preparation of positive electrode material precursor
1) Mixing nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of 5:2:3 to obtain a mixed salt solution with the total concentration of 3 mol/L; preparing a sodium hydroxide solution with the concentration of 8 mol/L; preparing an ammonia water solution with the concentration of 8 mol/L;
2) adding 5L of water into a reaction kettle to serve as reaction base liquid, heating in a water bath to control the constant temperature of the base liquid to be 60 ℃, dropwise adding the sodium hydroxide solution and the ammonia water solution prepared in the step 1) into the aqueous solution, and stirring to obtain the reaction base liquid with the pH value of 13 and the ammonia concentration of 0.75 mol/L;
3) continuously adding the mixed salt solution, the ammonia water solution and the sodium hydroxide solution in the step 1) into a reaction kettle with a stirrer, and in the first reaction stage, adjusting the ammonia concentration to be 0.75mol/L, the pH value to be 13, the temperature to be 60 ℃ and the reaction time to be 5 hours; adjusting the flow rates of the ammonia water solution and the sodium hydroxide solution, and entering a second reaction stage, wherein the ammonia concentration is 0.75mol/L, the pH value is 11.7, the temperature is 60 ℃, and the reaction time is 20 hours; a third reaction stage: repeating the first reaction stage, wherein the reaction time is adjusted from 5 hours to 6 hours; a fourth reaction stage: repeating the second reaction stage, wherein the reaction time is adjusted from 20 hours to 26 hours;
4) aging for 2 hours, separating and washing the reactant to obtain the metal hydroxide Ni0.5Co0.2Mn0.3(OH)2。
Preparation of cathode material
And uniformly mixing the precursor of the positive electrode material and a lithium source according to the molar ratio of 1:1.1, then roasting in a muffle furnace for multiple stages, and raising the roasting temperature to 920 ℃ at the temperature rise speed of 2 ℃/min. The roasting time is 16H, and the nickel cobalt lithium manganate positive electrode material is obtained by cooling, crushing and sieving after multi-stage roasting.
Example 4
Preparation of positive electrode material precursor
1) Mixing nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of 6:2:2 to obtain a mixed salt solution with the total concentration of 2 mol/L; preparing a sodium hydroxide solution with the concentration of 5 mol/L; preparing an ammonia water solution with the concentration of 5 mol/L;
2) adding 5L of water into a reaction kettle to serve as reaction base liquid, heating in a water bath to control the constant temperature of the base liquid to be 55 ℃, dropwise adding the sodium hydroxide solution and the ammonia water solution prepared in the step 1) into the aqueous solution, and stirring to obtain the reaction base liquid with the pH value of 12.6 and the ammonia concentration of 0.6 mol/L;
3) continuously adding the mixed salt solution, the ammonia water solution and the sodium hydroxide solution in the step 1) into a reaction kettle with a stirrer, and in the first reaction stage, adjusting the ammonia concentration to be 0.6mol/L, the pH value to be 12.6, the temperature to be 55 ℃ and the reaction time to be 5 hours; adjusting the flow rates of the ammonia water solution and the sodium hydroxide solution, and entering a second reaction stage, wherein the ammonia concentration is 0.6mol/L, the pH value is 11.7, the temperature is 55 ℃, and the reaction time is 20 hours; repeating the first reaction stage and the second reaction stage, and prolonging the reaction time in the second reaction stage to 26 hours; repeating the first reaction stage and the second reaction stage again, wherein the reaction time in the first reaction stage is prolonged to 15 hours, and the reaction time in the second reaction stage is prolonged to 30 hours;
4) aging for 2 hours, separating and washing the reactant to obtain the metal hydroxide Ni0.6Co0.2Mn0.2(OH)2The cross-sectional view of the obtained positive electrode material precursor is shown in fig. 3, the number of coating layers is 5, and the primary particles in different layers have different particle sizes.
Preparation of cathode material
And uniformly mixing the precursor of the positive electrode material and a lithium source according to the molar ratio of 1:1.1, then roasting in a muffle furnace for multiple stages, and raising the roasting temperature to 920 ℃ at the temperature rise speed of 2 ℃/min. The roasting time is 16H, and the nickel cobalt lithium manganate positive electrode material is obtained by cooling, crushing and sieving after multi-stage roasting.
Example 5
Preparation of positive electrode material precursor
1) Mixing nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of 6:2:2 to obtain a mixed salt solution with the total concentration of 2 mol/L; preparing a sodium hydroxide solution with the concentration of 5 mol/L; preparing an ammonia water solution with the concentration of 5 mol/L;
2) adding 5L of water into a reaction kettle to serve as reaction base liquid, heating in a water bath to control the constant temperature of the base liquid to be 55 ℃, dropwise adding the sodium hydroxide solution and the ammonia water solution prepared in the step 1) into the aqueous solution, and stirring to obtain the reaction base liquid with the pH value of 12.8 and the ammonia concentration of 0.4 mol/L;
3) continuously adding the mixed salt solution, the ammonia water solution and the sodium hydroxide solution in the step 1) into a reaction kettle with a stirrer, and in the first reaction stage, adjusting the ammonia concentration to be 0.4mol/L, the pH value to be 12.8, the temperature to be 55 ℃ and the reaction time to be 5 hours; adjusting the flow rates of the ammonia water solution and the sodium hydroxide solution, and entering a second reaction stage, wherein the ammonia concentration is 0.4mol/L, the pH value is 11.4, the temperature is 55 ℃, and the reaction time is 16 hours; repeating the first reaction stage and the second reaction stage, and prolonging the reaction time in the second reaction stage to 22 hours; repeating the first reaction stage and the second reaction stage again, wherein the reaction time in the first reaction stage is prolonged to 10 hours, and the reaction time in the second reaction stage is prolonged to 36 hours;
4) aging for 2 hours, separating and washing the reactant to obtain the metal hydroxide Ni0.6Co0.2Mn0.2(OH)2。
Preparation of cathode material
And uniformly mixing the precursor of the positive electrode material and a lithium source according to the molar ratio of 1:1.1, then roasting in a muffle furnace for multiple stages, and raising the roasting temperature to 920 ℃ at the temperature rise speed of 2 ℃/min. The roasting time is 16H, and the nickel cobalt lithium manganate positive electrode material is obtained by cooling, crushing and sieving after multi-stage roasting.
Example 6
Preparation of positive electrode material precursor
1) Mixing nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of 5:2:3 to obtain a mixed salt solution with the total concentration of 1 mol/L; preparing a sodium hydroxide solution with the concentration of 2 mol/L; preparing an ammonia water solution with the concentration of 4 mol/L;
2) adding 10L of water into a reaction kettle to serve as reaction base liquid, heating in a water bath to control the constant temperature of the base liquid to be 60 ℃, dropwise adding the sodium hydroxide solution and the ammonia water solution prepared in the step 1) into the aqueous solution, and stirring to obtain the reaction base liquid with the pH value of 12.2 and the ammonia concentration of 0.3 mol/L;
3) continuously adding the mixed salt solution, the ammonia water solution and the sodium hydroxide solution in the step 1) into a reaction kettle with a stirrer, and in the first reaction stage, adjusting the ammonia concentration to be 0.3mol/L, the pH value to be 12.2, the temperature to be 60 ℃ and the reaction time to be 5 hours; adjusting the flow rates of the ammonia water solution and the sodium hydroxide solution, and entering a second reaction stage, wherein the ammonia concentration is 0.3mol/L, the pH value is 11.3, the temperature is 60 ℃, and the reaction time is 15 hours; repeating the first reaction stage and the second reaction stage, and prolonging the reaction time in the second reaction stage to 20 hours; repeating the first reaction stage and the second reaction stage again, wherein the reaction time in the first reaction stage is prolonged to 12 hours, and the reaction time in the second reaction stage is prolonged to 24 hours;
4) aging for 2 hours, separating and washing the reactant to obtain the metal hydroxide Ni0.5Co0.2Mn0.3(OH)2。
Preparation of cathode material
And uniformly mixing the precursor of the positive electrode material and a lithium source according to the molar ratio of 1:1.1, then roasting in a muffle furnace for multiple stages, and raising the roasting temperature to 920 ℃ at the temperature rise speed of 2 ℃/min. The roasting time is 16H, and the nickel cobalt lithium manganate positive electrode material is obtained by cooling, crushing and sieving after multi-stage roasting.
Comparative example 1
Preparation of positive electrode material precursor
1) Mixing nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of 8:1:1 to obtain a mixed salt solution with the total concentration of 2 mol/L; preparing a sodium hydroxide solution with the concentration of 5 mol/L; preparing an ammonia water solution with the concentration of 5 mol/L;
2) adding 5L of water into a reaction kettle to serve as reaction base liquid, heating in a water bath to control the constant temperature of the base liquid to be 55 ℃, dropwise adding the sodium hydroxide solution and the ammonia water solution prepared in the step 1) into the aqueous solution, and stirring to obtain the reaction base liquid with the pH value of 12.0 and the ammonia concentration of 0.5 mol/L;
3) continuously adding the mixed salt solution, the ammonia water solution and the sodium hydroxide solution in the step 1) into a reaction kettle with a stirrer, and in the first reaction stage, adjusting the ammonia concentration to be 0.5mol/L, the pH value to be 12, the temperature to be 55 ℃ and the reaction time to be 30 hours;
4) aging for 2 hours, separating and washing the reactant to obtain the metal hydroxide Ni0.8Co0.1Mn0.1(OH)2The morphology of the obtained precursor of the positive electrode material is shown in fig. 4, the precursor does not contain a coating layer, and the cross-sectional view shows that primary particles in the precursor of the positive electrode material grow disorderly and have no obvious radial shape.
Preparation of cathode material
And uniformly mixing the precursor of the positive electrode material and a lithium source according to the molar ratio of 1:1.1, then roasting in a muffle furnace for multiple stages, and raising the roasting temperature to 920 ℃ at the temperature rise speed of 2 ℃/min. The roasting time is 16H, and the nickel cobalt lithium manganate positive electrode material is obtained by cooling, crushing and sieving after multi-stage roasting.
Comparative example 2
Preparation of positive electrode material precursor
1) Mixing nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of 8:1:1 to obtain a mixed salt solution with the total concentration of 2 mol/L; preparing a sodium hydroxide solution with the concentration of 5 mol/L; preparing an ammonia water solution with the concentration of 5 mol/L;
2) adding 5L of water into a reaction kettle to serve as reaction base liquid, heating in a water bath to control the constant temperature of the base liquid to be 55 ℃, dropwise adding the sodium hydroxide solution and the ammonia water solution prepared in the step 1) into the aqueous solution, and stirring to obtain the reaction base liquid with the pH value of 12.3 and the ammonia concentration of 0.5 mol/L;
3) continuously adding the mixed salt solution, the ammonia water solution and the sodium hydroxide solution in the step 1) into a reaction kettle with a stirrer, and in the first reaction stage, adjusting the ammonia concentration to be 0.5mol/L, the pH value to be 12.3, the temperature to be 55 ℃ and the reaction time to be 2 hours; adjusting the flow rates of the ammonia water solution and the sodium hydroxide solution, and entering a second reaction stage, wherein the ammonia concentration is 0.5mol/L, the pH value is 11.2, the temperature is 55 ℃, and the reaction time is 28 hours;
4) aging for 2 hours, separating and washing the reactant to obtain the metal hydroxide Ni0.8Co0.1Mn0.1(OH)2The shape of the obtained precursor of the cathode material is shown in fig. 5, the number of the coating layers is one, and the difference between the particle size of the primary particles in the core and the particle size of the primary particles in the coating layers is large.
Preparation of cathode material
And uniformly mixing the precursor of the positive electrode material and a lithium source according to the molar ratio of 1:1.1, then roasting in a muffle furnace for multiple stages, and raising the roasting temperature to 920 ℃ at the temperature rise speed of 2 ℃/min. The roasting time is 16H, and the nickel cobalt lithium manganate positive electrode material is obtained by cooling, crushing and sieving after multi-stage roasting.
Test method
1) Testing of positive electrode Material precursor
After the positive electrode material precursors obtained in examples 1 to 6 and comparative examples 1 to 2 are subjected to ion grinding, the cross section of the positive electrode material precursor is obtained, and SEM images are obtained by using a ZEISS GeminiSEM 300 field emission scanning electron microscope, respectively, to represent the micro-morphology of the cross section of the positive electrode material precursor, and the corresponding test results are shown in fig. 1 to 5.
And randomly selecting 30 secondary particles from the SEM image, and carrying out measurement statistics on the distribution intervals of the particle sizes of the primary particles of the core and the coating in the cross section of the precursor of the positive electrode material by using SmileView software, wherein the corresponding test results are shown in Table 1.
The particle size of the precursor of the positive electrode material obtained in examples 1 to 6 and comparative examples 1 to 2 was measured by a malvern laser particle sizer MS3000 to obtain the average particle size (D50) of the precursor of the positive electrode material (secondary particles) and the uniformity of the particles of the precursor of the positive electrode material, the uniformity calculation formula was (D90-D10)/D50, and the smaller the calculated value, the better the uniformity of the particles of the precursor of the positive electrode material. The corresponding results are shown in table 1.
And randomly selecting 30 secondary particles from the SEM image, and carrying out measurement statistics on the thickness distribution intervals of the core and the coating layer in the cross section of the precursor of the positive electrode material by using SmileView software, wherein the corresponding test results are shown in Table 2.
TABLE 1
Figure 901531DEST_PATH_IMAGE002
Remarking: the particle size of the primary particles in the core and the coating layer of the positive electrode material precursor in table 1 does not mean an average particle size, but means a particle size distribution interval of the primary particles.
TABLE 2
Figure 382454DEST_PATH_IMAGE004
Remarking: the thickness in the core and the cladding of the precursor of the positive electrode material in table 2 does not mean the thickness of each layer in one precursor of the positive electrode material, nor an average value, but means the thickness distribution interval of each layer in 30 precursors of the positive electrode material.
2) Testing of positive electrode materials and batteries
The positive electrode materials in examples 1 to 6 and comparative examples 1 to 2 were assembled into 053450 pouch laminated cells: dissolving polyvinylidene fluoride (PVDF) binder in N-methyl pyrrolidone, adding the prepared positive electrode material and a conductive agent (SP), fully mixing, walking on an aluminum foil, and drying and rolling to prepare a positive electrode plate, wherein the mass ratio of the positive electrode active substance SP to PVDF is 95:3: 2; the negative pole piece is manufactured as the positive pole, and the mass ratio of graphite, SP, CMC and SBR is 95:1.5:1.5: 2.
The first discharge specific capacity of the battery at 0.1C, the capacity retention rate at 5C and the capacity retention rate after 500 cycles at 0.5C are respectively measured.
5C capacity retention% =5C first cycle capacity/0.2C first cycle capacity;
capacity retention ratio% after 500 cycles of 0.5C/capacity of 0.5C first cycle "= capacity after 500 cycles of 0.5C; the test results are shown in table 3.
Testing the consistency of the positive electrode material: the positive electrode materials obtained in examples 1 to 6 and comparative examples 1 to 2 were subjected to particle size measurement using a malvern laser particle sizer MS3000 to obtain the average particle size (D50) of the positive electrode material (secondary particles) and the uniformity of the positive electrode material, the uniformity calculation formula being (D90-D10)/D50. The smaller the calculated value, the better the uniformity of the positive electrode material. The test results are shown in table 3, and the results show that the positive electrode material prepared from the positive electrode material precursor with the multilayer structure has better consistency than the positive electrode material prepared from the positive electrode material precursor without the coating layer (comparative example 1).
Cracking test of the positive electrode material: the positive electrode material obtained in the soft-package laminated battery obtained in the embodiment 1-the embodiment 6 and the comparative example 1-the comparative example 2 is peeled after being cycled for 500 times, the micro-morphology of the positive electrode material after charging and discharging is represented by a ZEISS GeminiSEM 300 field emission scanning electron microscope, and 1500 positive electrode material particles are randomly selected to count the particle cracking ratio. The test results are shown in table 3. The positive electrode material prepared from the positive electrode material precursor in which the coating layer is of the multilayer structure in the examples has less cracking than the positive electrode material prepared from the positive electrode material precursor in which the coating layer is not present (comparative example 1) and the coating layer is of the single-layer structure (comparative example 2).
TABLE 3
Figure DEST_PATH_IMAGE005
As can be seen from fig. 1 to fig. 3, the positive electrode material precursor prepared in the embodiment of the present application has a multilayer structure, the primary particles in any two adjacent layers have different particle sizes and different thicknesses, the positive electrode material precursor with high compactness is formed by alternately coating the primary particle layer with a smaller particle size and the primary particle layer with a larger particle size layer by layer, and meanwhile, in the transition region where the two adjacent layers are in contact, the primary particles with a smaller particle size have a larger number of particles, and the primary particles with a larger particle size are not consistent and are more disordered in arrangement and growth directions, which is beneficial to stress release in the charge-discharge process of the sintered positive electrode material.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. The precursor of the cathode material is characterized by comprising a core and a coating layer for coating the core, wherein the number n of the coating layer is more than or equal to 3; the coating layers comprise a 1 st coating layer and a 2 nd coating layer … …, wherein m is a positive integer, 1+ m is less than or equal to n, and the particle size of primary particles in the coating layer with the odd number in any two adjacent layers is more than or equal to that of primary particles in the coating layer with the even number; the 1 st coating layer is in contact with the core, and the particle size of primary particles in the core is smaller than that of the 1 st coating layer; the core and the coating layer contain metal hydroxide, and the metal hydroxide is NixCoyMn1-x-y(OH)2Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.2.
2. The positive electrode material precursor according to claim 1, wherein the clad layer comprises a 1 st clad layer, a 2 nd clad layer and a 3 rd clad layer, the 1 st clad layer, the 2 nd clad layer and the 3 rd clad layer sequentially clad the core, and the 1 st clad layer is in contact with the core; the particle size of the primary particles in the core is 0.05-0.2 micrometer, the particle size of the primary particles in the 1 st coating layer is 0.4-1.5 micrometer, the particle size of the primary particles in the 2 nd coating layer is 0.05-0.2 micrometer, and the particle size of the primary particles in the 3 rd coating layer is 0.2-1.1 micrometer.
3. The positive electrode material precursor according to claim 1, wherein the clad layer comprises a 1 st clad layer, a 2 nd clad layer, a 3 rd clad layer, a 4 th clad layer and a 5 th clad layer, the 1 st clad layer, the 2 nd clad layer, the 3 rd clad layer, the 4 th clad layer and the 5 th clad layer are clad on the core in this order, and the 1 st clad layer is in contact with the core; the particle size of the primary particles in the core is 0.05-0.2 micrometer, the particle size of the primary particles in the 1 st coating layer is 0.6-1.5 micrometer, the particle size of the primary particles in the 2 nd coating layer is 0.05-0.2 micrometer, the particle size of the primary particles in the 3 rd coating layer is 0.3-1 micrometer, the particle size of the primary particles in the 4 th coating layer is 0.05-0.2 micrometer, and the particle size of the primary particles in the 5 th coating layer is 0.4-2 micrometer.
4. The positive electrode material precursor according to claim 1, wherein the average particle diameter of the positive electrode material precursor is 3 to 18 μm.
5. The cathode material precursor according to claim 2 or 4, wherein the core has a diameter of 0.5 to 2 micrometers, the 1 st clad layer has a thickness of 0.4 to 1.5 micrometers, the 2 nd clad layer has a thickness of 0.2 to 1.1 micrometers, and the 3 rd clad layer has a thickness of 0.2 to 1.1 micrometers.
6. The cathode material precursor according to claim 3 or 4, wherein the core has a diameter of 0.5 to 2 micrometers, the 1 st clad layer has a thickness of 0.6 to 1.5 micrometers, the 2 nd clad layer has a thickness of 0.2 to 0.5 micrometers, the 3 rd clad layer has a thickness of 0.3 to 1 micrometer, the 4 th clad layer has a thickness of 0.3 to 0.7 micrometers, and the 5 th clad layer has a thickness of 0.3 to 1.1 micrometers.
7. The preparation method of the precursor of the cathode material is characterized by comprising the following steps
1) Mixing nickel salt, cobalt salt and manganese salt according to the molar ratio of x to y to 1-x-y to obtain mixed salt solution with the total concentration of 1-3 mol/L; preparing ammonia water solution with the concentration of 4-13 mol/L; preparing a sodium hydroxide solution with the concentration of 2-8 mol/L;
2) adding water into a reaction container as reaction base liquid, dropwise adding the ammonia water solution and the sodium hydroxide solution in the step 1) into the water at a constant temperature of 45-60 ℃, and stirring to obtain the reaction base liquid with the pH of 12-13 and the ammonia concentration of 0.3-0.8 mol/L;
3) continuously adding the mixed salt solution, the ammonia water solution and the sodium hydroxide solution in the step 1) into a reaction container, and stirring; in the first reaction stage, the ammonia concentration is adjusted to be 0.3-0.8mol/L, the pH is adjusted to be 12-13, the temperature is 45-60 ℃, and the reaction time is 1-15 hours; in the second reaction stage, the ammonia concentration is adjusted to be 0.3-0.8mol/L, the pH is adjusted to be 11-12, the temperature is 45-60 ℃, and the reaction time is 1-30 hours; repeating the first reaction stage and the second reaction stage; in this order, the reaction times in each of the first reaction stages are the same or different; the reaction time in each second reaction stage is the same or different;
5) aging, separating and washing the reactant to obtain the metal hydroxide NixCoyMn1-x-y(OH)2Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.2.
8. The preparation method according to claim 7, wherein the molar ratio of the nickel salt, the cobalt salt and the manganese salt in the mixed salt solution is one of 8:1:1, 6:2:2, 5:2:3, 2:1:1 and 1:1: 1.
9. A positive electrode material produced from the positive electrode precursor according to any one of claims 1 to 6.
10. A battery comprising a positive electrode, a negative electrode, and an electrolytic solution or a solid electrolyte, wherein the positive electrode contains the positive electrode material according to claim 9.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113651371A (en) * 2021-08-18 2021-11-16 宁波容百新能源科技股份有限公司 High-nickel ternary precursor material, preparation method thereof and high-nickel ternary cathode material
CN114195202A (en) * 2021-12-28 2022-03-18 中伟新材料股份有限公司 Binary precursor and preparation method thereof, lithium ion battery anode material, lithium ion battery and power utilization equipment
CN114644368A (en) * 2020-12-18 2022-06-21 中国石油化工股份有限公司 Positive electrode material precursor and preparation method thereof, and positive electrode material and application thereof
CN115043440A (en) * 2022-06-27 2022-09-13 北京当升材料科技股份有限公司 Lithium ion battery positive electrode material precursor, preparation method and application thereof, lithium ion battery positive electrode material, preparation method and application thereof
WO2022242596A1 (en) * 2021-05-19 2022-11-24 中国石油化工股份有限公司 Lithium battery positive electrode material precursor, preparation method therefor and application thereof
WO2024066809A1 (en) * 2022-09-27 2024-04-04 天津巴莫科技有限责任公司 Positive electrode material, preparation method therefor, positive electrode sheet, secondary battery, and electronic device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101997113A (en) * 2009-08-17 2011-03-30 北京当升材料科技股份有限公司 Multicomponent material with multilayer coating structure for lithium ion battery and preparation method thereof
US20130295469A1 (en) * 2012-05-03 2013-11-07 Ut-Battelle, Llc Lithium sulfide compositions for battery electrolyte and battery electrode coatings
CN105355907A (en) * 2015-12-10 2016-02-24 哈尔滨工业大学 Lithium metallic oxide precursor material with annual ring type structure, anode material prepared by lithium metallic oxide precursor material, and preparation method and application
WO2018097136A1 (en) * 2016-11-22 2018-05-31 住友金属鉱山株式会社 Transition metal-containing composite hydroxide and production method thereof, and production method of positive electrode active substance for non-aqueous electrolyte secondary battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101997113A (en) * 2009-08-17 2011-03-30 北京当升材料科技股份有限公司 Multicomponent material with multilayer coating structure for lithium ion battery and preparation method thereof
US20130295469A1 (en) * 2012-05-03 2013-11-07 Ut-Battelle, Llc Lithium sulfide compositions for battery electrolyte and battery electrode coatings
CN105355907A (en) * 2015-12-10 2016-02-24 哈尔滨工业大学 Lithium metallic oxide precursor material with annual ring type structure, anode material prepared by lithium metallic oxide precursor material, and preparation method and application
WO2018097136A1 (en) * 2016-11-22 2018-05-31 住友金属鉱山株式会社 Transition metal-containing composite hydroxide and production method thereof, and production method of positive electrode active substance for non-aqueous electrolyte secondary battery

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114644368A (en) * 2020-12-18 2022-06-21 中国石油化工股份有限公司 Positive electrode material precursor and preparation method thereof, and positive electrode material and application thereof
CN114644368B (en) * 2020-12-18 2024-03-26 中国石油化工股份有限公司 Positive electrode material precursor, preparation method thereof, positive electrode material and application thereof
WO2022242596A1 (en) * 2021-05-19 2022-11-24 中国石油化工股份有限公司 Lithium battery positive electrode material precursor, preparation method therefor and application thereof
CN113651371A (en) * 2021-08-18 2021-11-16 宁波容百新能源科技股份有限公司 High-nickel ternary precursor material, preparation method thereof and high-nickel ternary cathode material
CN113651371B (en) * 2021-08-18 2023-10-20 宁波容百新能源科技股份有限公司 High-nickel ternary precursor material, preparation method thereof and high-nickel ternary cathode material
CN114195202A (en) * 2021-12-28 2022-03-18 中伟新材料股份有限公司 Binary precursor and preparation method thereof, lithium ion battery anode material, lithium ion battery and power utilization equipment
CN115043440A (en) * 2022-06-27 2022-09-13 北京当升材料科技股份有限公司 Lithium ion battery positive electrode material precursor, preparation method and application thereof, lithium ion battery positive electrode material, preparation method and application thereof
CN115043440B (en) * 2022-06-27 2024-03-15 当升科技(常州)新材料有限公司 Lithium ion battery positive electrode material precursor, preparation method and application thereof, lithium ion battery positive electrode material, preparation method and application thereof
WO2024066809A1 (en) * 2022-09-27 2024-04-04 天津巴莫科技有限责任公司 Positive electrode material, preparation method therefor, positive electrode sheet, secondary battery, and electronic device

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