CN114455644A - Lithium ion battery anode material, preparation method and application thereof, system and precursor preparation device - Google Patents

Lithium ion battery anode material, preparation method and application thereof, system and precursor preparation device Download PDF

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CN114455644A
CN114455644A CN202111681916.4A CN202111681916A CN114455644A CN 114455644 A CN114455644 A CN 114455644A CN 202111681916 A CN202111681916 A CN 202111681916A CN 114455644 A CN114455644 A CN 114455644A
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reaction
precursor
coating
lithium ion
ion battery
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张朋立
田鑫民
陈彦彬
宋顺林
刘亚飞
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Dangsheng Science And Technology Changzhou New Materials Co ltd
Beijing Easpring Material Technology Co Ltd
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Dangsheng Science And Technology Changzhou New Materials Co ltd
Beijing Easpring Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/40—Electric properties

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  • Manufacturing & Machinery (AREA)
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Abstract

The invention relates to the field of lithium ion batteries, and discloses a lithium ion battery anode material, a preparation method and application thereof, a system and a precursor preparation device, wherein the method comprises the following steps: (1) carrying out coprecipitation reaction on each component in the component A in the presence of a complexing agent and a first precipitator to obtain precursor slurry, wherein the component A contains manganese salt, cobalt salt and nickel salt; (2) in the presence of a second precipitator, carrying out coating reaction on the precursor slurry and a modifier so that the modifier is coated on the surface of precursor particles to obtain a coated precursor; (3) and carrying out sintering reaction on the coated precursor and lithium salt to obtain the doped and coated co-modified lithium ion battery anode material. By adopting the method, the doped and coated double-modified lithium ion battery anode material can be obtained, and the electrochemical performance of the material is effectively improved.

Description

Lithium ion battery anode material, preparation method and application thereof, system and precursor preparation device
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium ion battery anode material, a preparation method and application thereof, a system and a precursor preparation device.
Background
The lithium ion battery is a green secondary battery, has the outstanding advantages of high voltage, large energy density, good cycle performance, small self-discharge, no memory effect and the like, and is widely applied to a plurality of fields of electric tools, electric bicycles, electric motorcycles, electric automobiles, military equipment, aerospace and the like.
The positive electrode material is one of the most important components in the lithium ion battery, and the performance of the positive electrode material plays a decisive role in the performance of the lithium ion battery. The ternary cathode material combines LiCoO through the synergistic effect of three elements of Ni-Co-Mn2Good cycle performance, LiNiO2High specific capacity, LiMnO2The lithium ion battery anode material has the advantages of high safety, low cost and the like, and becomes the lithium ion battery anode material with the most development prospect at present. However, with the demand for high energy density, the ternary cathode material shows a trend towards high nickel content, and the increase of the nickel content leads to the rate capability, the cycle performance and the thermal stability of the material along with the increase of the nickel contentWhich in turn affects the life and safety of the battery.
At present, the means for modifying the lithium ion battery material is mainly to improve the surface interface structure of the material by doping or cladding, thereby improving the electrochemical performance of the material.
Doping is usually carried out in a sintering stage, and the precursor, a lithium source and a modified substance containing doping elements are uniformly mixed and then sintered at high temperature to obtain the doped modified cathode material. The method is easy to have the defect of uneven enrichment or deletion of doping elements, and can not effectively improve the electrochemical performance of the anode material. In order to improve the uniformity of the doped elements, the elements can be doped in the preparation of the precursor of the cathode material, and then the element can be sintered with a lithium source. Although the method can improve the uniformity of the doping elements, the method has the problems that the solubility product of the doping elements and the main elements of nickel, cobalt and manganese of the precursor is greatly different, so that the indexes of the particle size, distribution, density, crystallinity, primary particle morphology and the like of the precursor are influenced, the preparation difficulty of the precursor is higher, the selectable range of the doping elements is seriously limited, in addition, for doping modification, the capacity of the anode material can be influenced because the doping elements are generally inactive substances, and especially when the doping amount is large, the electrical property of the anode material cannot be really improved by single doping.
The coating is generally carried out in a sintering stage, the positive electrode material formed after lithium preparation and sintering is mixed with a coating, and then the mixture is sintered at a lower temperature, so that the coating element covers the surface layer of the positive electrode material, and the performance of the positive electrode material is improved by improving the surface structure. The process is easy to have the condition of uneven coating layer, so the improvement degree of the electrochemical performance of the material is limited, and the operation process of secondary or multiple sintering is complex, time-consuming and labor-consuming, and is not beneficial to industrial production.
Therefore, aiming at the defects existing in the existing modification means, the method for preparing the modified lithium ion battery cathode material is of great significance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a novel method for preparing a modified lithium ion battery cathode material.
Aiming at the defects existing in the doping and coating modification means commonly used for the anode material of the lithium ion battery at present, the inventor of the invention finds that the anode material with better electrochemical performance can be obtained by skillfully designing the preparation of the precursor and matching with the specific process conditions through a large amount of experimental researches, and also unexpectedly finds that the modification elements of the anode material obtained by the method can realize double modification of coating and doping simultaneously, thereby providing the invention.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a positive electrode material for a lithium ion battery, comprising:
(1) carrying out coprecipitation reaction on each component in the component A in the presence of a complexing agent and a first precipitator to obtain precursor slurry containing a precursor, wherein the component A contains manganese salt, cobalt salt and nickel salt;
(2) in the presence of a second precipitator, carrying out coating reaction on the precursor slurry and a modifier so that the modifier is coated on the particle surface of the precursor to obtain a coated precursor;
(3) and carrying out sintering reaction on the coated precursor and lithium salt to obtain the doped and coated co-modified lithium ion battery anode material.
The invention provides a lithium ion battery cathode material prepared by the method.
The invention also provides the application of the lithium ion battery cathode material in a lithium ion battery.
The invention provides a device for preparing a precursor of a lithium ion battery anode material, which comprises a reaction kettle and a coating kettle, wherein the coating kettle is communicated with the reaction kettle, so that precursor slurry prepared by the reaction kettle can enter the coating kettle to contact a modifier for coating reaction to obtain a coated precursor.
The invention provides a system for preparing a lithium ion battery cathode material, which comprises a precursor preparation device and a sintering furnace, wherein the precursor preparation device is the device for preparing the lithium ion battery cathode material precursor.
Compared with the prior art, the invention has at least the following advantages:
by adopting the method provided by the invention, the preparation of the precursor is divided into two steps through ingenious design, the slurry of the precursor of the lithium ion battery anode material with excellent physicochemical indexes is prepared firstly, then the wet coprecipitation technology is adopted, so that the modified elements are uniformly precipitated on the surface of the precursor to obtain the coated precursor, and then the coated precursor and a lithium source are sintered to obtain the doped and coated double-modified anode material, wherein the modified elements are gradually reduced from the surface to the inside of the material, the influence of the modified elements on the material body is reduced while the surface interface structure of the material is improved, and the electrochemical performance of the lithium ion battery anode material is effectively improved.
Other features and advantages of the present invention will be described in detail in the following detailed description.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for preparing a precursor of a positive electrode material of a lithium ion battery according to a preferred embodiment of the present invention;
FIG. 2 is an SEM image of the coated precursor prepared in example 3 at different magnification;
FIG. 3 is SEM images of doped precursors prepared in comparative example 1 at different magnification;
FIG. 4 is a comparative graph showing the results of Zr element content distribution of the positive electrode materials for lithium ion batteries prepared in example 3 and comparative example 1;
FIGS. 5 and 6 are the results of cycle performance tests of the lithium ion battery positive electrode materials obtained in example 3 and comparative example 1 under different test conditions, respectively, wherein the test conditions in FIG. 5 are 25 ℃, 1C/1C @ 4.5-3.0V; the test conditions of FIG. 6 were 45 ℃ and 1C/1C @ 4.3-3.0V;
FIGS. 7 and 8 are the results of cycle performance tests of the lithium ion battery positive electrode materials obtained in example 3 and comparative example 2 under different conditions, respectively, wherein the test conditions in FIG. 7 are 25 ℃, 1C/1C @ 4.5-3.0V; the test conditions in FIG. 8 were 45 ℃ and 1C/1C @ 4.3-3.0V.
Description of the reference numerals
1, a reaction kettle:
1-1 stirring motor, 1-2 feeding pipes, 1-3 stirring shafts, 1-4 overflow ports, 1-5 circulating water outlets, 1-6 overflow control valves, 1-7 baffle plates, 1-8 heating layers, 1-9 stirring paddles, 1-10 heat insulation layers, 1-11 circulating water inlets and 1-12 liquid discharge ports.
2 clear liquid discharge device:
2-1 clear liquid outlet, 2-2 liquid discharge control valve, 2-3 sight glass, 2-4 liquid discharge pump and 2-5 liquid discharge pipeline.
3, coating the kettle:
3-1 stirring motor, 3-2 feeding pipes, 3-3 liquid level meters, 3-4 heating layers, 3-5 circulating water outlets, 3-6 heat preservation layers, 3-7 stirring shafts, 3-8 stirring paddles, 3-9 liquid discharging ports, 3-10 circulating water inlets and 3-11 overflow liquid receiving ports.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
As previously mentioned, a first aspect of the present invention provides a method for preparing a positive electrode material for a lithium ion battery, comprising:
(1) carrying out coprecipitation reaction on each component in the component A in the presence of a complexing agent and a first precipitator to obtain precursor slurry containing a precursor, wherein the component A contains manganese salt, cobalt salt and nickel salt;
(2) in the presence of a second precipitator, carrying out coating reaction on the precursor slurry and a modifier so that the modifier is coated on the particle surface of the precursor to obtain a coated precursor;
(3) and carrying out sintering reaction on the coated precursor and lithium salt to obtain the doped and coated co-modified lithium ion battery anode material.
The inventor of the invention finds that by adopting the method provided by the invention, the preparation of the precursor is divided into two steps through ingenious design, the precursor slurry of the lithium ion battery anode material with excellent physicochemical indexes is prepared firstly, then the wet coprecipitation technology is adopted, so that the modified elements are uniformly precipitated on the surface of the precursor to obtain the coating precursor, then the coating precursor and a lithium source are mixed and sintered, part of the modified elements can permeate into the anode material to form the doping layer in the sintering process, and the rest of the modified elements form the coating layer on the surface of the anode material, so that the doped and coated double-modified anode material can be obtained, the modified elements are gradually reduced from the surface to the inside of the material, the influence on the material body can be reduced while the surface interface structure of the material is improved, and the electrochemical performance of the anode material is effectively improved.
Preferably, the modifier contains a modifying element M selected from at least one of Ni, Mn, Co, Al, Ti, Zr, W, B, Fe, La, Cr and Ce elements.
Preferably, the precursor has the chemical formula of Ni1-x-yCoxMny(OH)2(ii) a The chemical formula of the coating precursor is Ni1-x-yCoxMny(OH)2·MzE; the chemical formula of the lithium ion battery anode material is LiNi1-x-y-zCoxMnyMzO2(ii) a Wherein, 0<x<0.5，0<y<1.0，0.001<z<0.1. According to the invention, in the coating precursor, the modifying element M coats the surface of the precursor to form a coating layer. In addition, M is to be specifically mentionedzE represents a hydroxide or carbonate of a modifying element M, here represented in a form representing a coating precursor having, in terms of molar amounts of elements M/Ni + Co + Mn, 0.001-0.1: 1 modifying element content in Ni1-x-yCoxMny(OH)2·MzE in which E is according to MzThe valency of the ions formed is correspondingly established, MzE may be, for example, La0.01(CO3)0.015、Al0.02(OH)0.06、Zr0.005(OH)0.02. The chemical structural formula of the invention is calculated according to the raw material feeding amount,
preferably, D of the coating precursor50Is 3-20 um.
Preferably, in step (1), the conditions of the coprecipitation reaction include: the reaction temperature is 40-70 ℃, the pH value of the reaction system is 10.5-13, the ammonia content of the reaction system is 0.5-15g/L, the reaction time is 5-40h, and the stirring speed is 50-300 rpm.
Preferably, in step (1), the manganese salt, the cobalt salt and the nickel salt are each independently selected from at least one of sulfate, nitrate, chloride, acetate and citrate, for example, the manganese salt is selected from at least one of manganese sulfate, manganese cobaltate, manganese chloride, manganese acetate and manganese citrate; the cobalt salt is at least one selected from cobalt sulfate, cobalt cobaltate, cobalt chloride, cobalt acetate and cobalt citrate; the nickel salt is at least one selected from nickel sulfate, nickel cobaltate, nickel chloride, nickel acetate and nickel citrate. Preferably, the manganese salt, the cobalt salt and the nickel salt are added to the reaction system in the form of a mixed salt solution. Preferably, the concentration of the mixed salt solution is 1-2.5mol/L, and the concentration of the mixed salt solution refers to the total concentration of nickel salt, cobalt salt and manganese salt in the mixed salt solution.
Preferably, in step (1), the first precipitating agent is an alkali metal hydroxide, more preferably sodium hydroxide and/or potassium hydroxide. Preferably, the first precipitant is added to the reaction system in the form of a precipitant solution. Preferably, the concentration of the first precipitant solution is 1.0 to 12.0 mol/L. Preferably, the first precipitator is used in an amount such that the pH value of the reaction system in the step (1) is 10.5-13.
Preferably, in step (1), the complexing agent is selected from at least one of ammonia water, ammonium sulfate, ammonium chloride, ammonium nitrate and the like. Preferably, the complexing agent is added to the reaction system in the form of a complexing agent solution. Preferably, the concentration of the complexing agent solution is 0.5-15 mol/L. Preferably, the complexing agent is used in an amount such that the ammonia content of the reaction system of step (1) is 0.5 to 15 g/L.
The solvents for the salt solution (manganese salt solution, cobalt salt solution, nickel salt solution or mixed salt solution), the precipitant solution and the complexing agent solution are not particularly limited as long as the substances can be sufficiently dissolved.
According to a preferred embodiment of the present invention, step (1) is carried out in a reaction vessel.
According to a particularly preferred embodiment of the present invention, in step (1), in the presence of water, a part of the complexing agent and a part of the first precipitating agent are added into a reaction kettle to form a base solution, so that the environment in the reaction kettle is suitable for the coprecipitation reaction, and then the rest of the complexing agent and the rest of the first precipitating agent and the component A are added to carry out the coprecipitation reaction. With this preferred mode, the coprecipitation reaction can be made more stable. The amount of the complexing agent and the first precipitating agent added in advance is not particularly limited in the present invention, and can be reasonably adjusted by those skilled in the art according to actual needs.
Preferably, the solid content of the precursor slurry obtained in step (1) is 50-130g/L, more preferably 50-120 g/L.
Preferably, in step (2), the conditions of the coating reaction include: the temperature is 50-70 ℃, the pH value of the reaction system is 8.0-13.5, the reaction time is 1-10h, and the stirring speed is 150-400 rpm.
Preferably, in the step (2), the second precipitator is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and in the present invention, the second precipitator may be the same as or different from the first precipitator. Preferably, the second precipitant is added to the reaction system in the form of a precipitant solution. Preferably, the concentration of the second precipitant solution is 1.0 to 12.0 mol/L. Preferably, the second precipitator is used in an amount such that the pH value of the reaction system in the step (1) is 8.0-13.5.
According to the invention, in step (2), the modifying agent is chosen from at least one soluble (e.g. soluble in water) containing modifying elements. Preferably, the modifier is at least one selected from the group consisting of oxides, chlorides, sulfates, nitrates, phosphates, fluorides of the modifying element. Preferably, the modifier is present in solution at a concentration of 0.01 to 0.5 mol/L.
Preferably, in the step (2), the molar ratio of the precursor slurry to the modifier is 1: 0.1-0.001. The amount of the precursor slurry is calculated by the total mol amount of nickel element, cobalt element and manganese element contained in the precursor slurry, and the amount of the modifier is calculated by the mol amount of the modifying element contained in the precursor slurry.
According to a preferred embodiment of the present invention, the step (2) further comprises aging the reactant after the coating reaction to obtain the coating precursor. Preferably, the aging conditions include: the aging temperature is 50-70 ℃, and the aging time is 0.5-5 h.
According to a preferred embodiment of the present invention, step (2) further comprises, before performing the coating reaction, settling the precursor slurry, then discharging a clear solution, and performing the coating reaction on the slurry after discharging the clear solution and the modifying agent. Therefore, the solid content of the precursor slurry can be adjusted and controlled according to the process requirements, so that the process condition requirements of coating of multiple elements are met, the production efficiency is improved, and the practicability is high. Preferably, the settling time is 0.5 to 5 hours. Preferably, the solid content of the slurry after the clear liquid is discharged is 150-650 g/L.
Preferably, in step (3), the sintering reaction conditions include: the sintering temperature is 400-1000 ℃, and the sintering time is 4-20 h. Preferably, the sintering reaction is carried out in air or oxygen.
Preferably, in step (3), the lithium salt is selected from at least one of lithium nitrate, lithium chloride, lithium hydroxide and lithium carbonate. Preferably, the coating precursor and the lithium salt are used in amounts such that the obtained positive electrode material has a chemical formula of LiNi1-x-y-zCoxMnyMzO2，0<x<0.5，0<y<1.0，0.001<z<0.1。
The second aspect of the invention provides a lithium ion battery cathode material prepared by the method.
The invention also provides the application of the anode material of the lithium ion battery in the lithium ion battery.
The fourth aspect of the invention provides a device for preparing a precursor of a lithium ion battery anode material, which comprises a reaction kettle and a coating kettle, wherein the coating kettle is communicated with the reaction kettle, so that precursor slurry prepared by the reaction kettle can enter the coating kettle to contact with a modifier for coating reaction, and a coated precursor is obtained.
According to a preferred embodiment of the invention, in the device, at least two coating kettles are provided, and each coating kettle is in controllable communication with the reaction kettle, so that the precursor slurry can overflow into each coating kettle alternately to contact with the modifier for the coating reaction, thereby realizing continuous coating operation.
According to the invention, the structures of the reaction kettle and the coating kettle are not particularly limited, as long as the devices can continuously react with each other to obtain the modified lithium ion battery cathode material. According to a preferred embodiment of the invention, as shown in fig. 1, a stirring motor 1-1, a stirring shaft 1-3 and a stirring paddle 1-9 are arranged inside a cylinder of a reaction kettle 1, and a baffle plate 1-7 is further arranged on the inner wall of the cylinder; the top of the cylinder body is provided with a feeding pipe 1-2, and the bottom is provided with a liquid discharge port 1-12; the side part of the cylinder body is provided with overflow ports 1-4, overflow control valves 1-6, circulating water outlets 1-5 and circulating water inlets 1-11; the outer part of the cylinder body is provided with a heating layer 1-8 and a heat preservation layer 1-10. According to the invention, the number of the overflow ports of the reaction kettle is correspondingly set according to the number of the coating kettles, and preferably, the overflow ports are distributed at intervals along the section circle of the kettle body of the reaction kettle and can be on the same plane or not. Preferably, the overflow ports are uniformly distributed on the same plane at intervals along the cross-sectional circle of the kettle body.
According to a preferred embodiment of the invention, as shown in fig. 1, a stirring motor 3-1, a stirring shaft 3-7 and a stirring paddle 3-8 are arranged inside a cylinder of the coating kettle 3; the top of the cylinder body is provided with a feeding pipe 3-2 and a liquid level meter 3-3, and the bottom of the cylinder body is provided with a liquid outlet 3-9; the side part of the cylinder body is provided with an overflow liquid receiving port 3-11, a circulating water outlet 3-5 and a circulating water inlet 3-10; and a heating layer 3-4 and a heat-insulating layer 3-6 are arranged outside the cylinder body to control the temperature required by the coating reaction.
According to another preferred embodiment of the present invention, as shown in fig. 1, the apparatus further comprises a clear liquid discharge device 2, the clear liquid discharge device 2 comprises a liquid discharge pump 2-4 and a clear liquid discharge pipeline 2-5, and the coating kettle is in controllable communication with the liquid discharge pump, so that before the coating reaction, the precursor slurry entering the coating kettle can be settled and then subjected to the coating reaction after being discharged with clear liquid through the clear liquid discharge device. Therefore, the system can flexibly adjust the solid content of the precursor slurry in the coating kettle, control the effective volume and the reaction time in the coating kettle, meet the technological condition requirements of coating of various elements, improve the production efficiency and have strong practicability. Preferably, the clear liquid discharging device 2 further comprises a clear liquid discharging port 2-1, a liquid discharging control valve 2-2 and a sight glass 2-3. Preferably, the clear liquid outlet 2-1 is disposed below 1/2 of the coating kettle.
According to the invention, parameters such as the inner diameter, height, volume, length-diameter ratio and the like of the reaction kettle, each coating kettle and the sintering furnace are not particularly limited, and can be reasonably selected or designed by a person skilled in the art according to actual requirements.
The invention provides a system for preparing a lithium ion battery cathode material, which comprises a precursor preparation device and a sintering furnace, wherein the precursor preparation device is the device for preparing the lithium ion battery cathode material precursor.
The structure and arrangement of the precursor preparation device according to the present invention are as described above, and the present invention is not described herein again.
According to the invention, the structure of the sintering furnace is not particularly limited as long as the coating precursor and the lithium salt can be sintered in the sintering furnace to obtain the lithium ion battery cathode material with the modification effect of the invention.
The system provided by the invention can be used for preparing the precursor step by step, and then sintering the coated precursor and the lithium source in a sintering furnace to obtain the doped and coated double-modified cathode material, thereby effectively improving the electrochemical performance of the cathode material. In addition, under the preferable condition, one reaction kettle is matched with two or more coating kettles, the continuous liquid feeding coating kettles of the reaction kettles alternately coat, the production efficiency is high, the whole reaction process is easy to control, the product stability is good, and the method is suitable for large-scale production. Meanwhile, under the preferable condition, different clear liquid discharge amounts can be adjusted according to the process requirements by configuring clear liquid discharge equipment, the solid content in the coating kettle, the effective volume in the coating kettle, the reaction time and the like are controlled, the process condition requirements of multi-element coating are met, and the practicability is high.
The present invention will be described in detail below by way of examples and comparative examples.
In the following examples, all the raw materials used are commercially available ones unless otherwise specified.
The following examples, unless otherwise specified, were carried out in the apparatus shown in fig. 1, which includes a reaction vessel 1, a clear liquid discharge apparatus 2, and a coating vessel 3; the number of the coating kettles is 2, and the 2 coating kettles are all in controllable communication with the reaction kettle 1, so that the precursor slurry can alternately overflow into each coating kettle to contact with the modifier for the coating reaction; the clear liquid discharge equipment 2 comprises a liquid discharge pump and a clear liquid discharge pipeline, and the coating kettle 3 is in controllable communication with the liquid discharge pump, so that the precursor slurry entering the coating kettle can be settled before the coating reaction, and then the coating reaction is carried out after the clear liquid is discharged through the clear liquid discharge equipment.
Example 1
The following solutions were prepared for use:
and (2) component A: a mixed salt solution with the concentration of 2.0mol/L (the molar ratio of nickel, cobalt and manganese elements is 5:2: 3);
complexing agent: aqueous ammonia solution with concentration of 10mol/L
A first precipitant: sodium hydroxide solution with the concentration of 10 mol/L;
a second precipitant: sodium carbonate solution with the concentration of 1.5 mol/L;
modifying agent: lanthanum sulfate solution with concentration of 0.04moL L/L;
(1) adding pure water, part of ammonia water and part of sodium hydroxide solution into a reaction kettle to prepare a base solution, adding mixed salt, the rest of sodium hydroxide and the rest of ammonia water into the reaction kettle to carry out coprecipitation reaction, wherein the coprecipitation reaction conditions comprise: the temperature of the reaction kettle is 50 ℃, the pH value of the reaction system is 11.6, the ammonia content of the reaction system is 4g/L, the reaction retention time is 10h, the stirring speed is 75rpm, and precursor slurry with the solid content of about 120g/L is obtained;
(2) enabling the precursor slurry to flow into one coating kettle through an overflow port and an overflow liquid receiving port, closing an overflow control valve of the coating kettle after the coating kettle is full, opening an overflow control valve of the other coating kettle, and enabling the precursor slurry to overflow to the other coating kettle;
closing the coating kettle filled with the slurry, settling the slurry in the coating kettle for 5 hours, discharging supernatant through a clear liquid discharge device, observing the condition of discharging the clear liquid through a sight glass on a clear liquid discharge pipeline, and closing a clear liquid control valve when the liquid level of the coating kettle drops to the height 1/4 of the coating kettle, wherein the solid content of the slurry after discharging the clear liquid is about 450 g/L; then the coating kettle is started to stir, and the ratio of the total mole amount of the nickel, cobalt and manganese elements to the lanthanum element is 1: 0.01, slowly adding a lanthanum sulfate solution and a sodium carbonate solution into a coating kettle for coating reaction, wherein the conditions of the coating reaction comprise: controlling the pH value of a reaction system to be about 9.0 by sodium carbonate, controlling the reaction time to be 5h, the reaction temperature to be 50 ℃, the stirring rotation speed to be 200rpm, continuously stirring and aging in a coating kettle after coating reaction, wherein the aging conditions comprise: aging at 50 deg.C for 5h, discharging the aged material through material outlet, filtering, washing, and oven drying to obtain D50A coating precursor of 3.5 um; repeating the reaction process after the other coating kettles are full;
(3) mixing the coating precursor with lithium carbonate in an air atmosphere to carry out a sintering reaction, wherein the sintering reaction conditions comprise: the sintering temperature is 980 ℃, the sintering time is 20h, and the doped and coated co-modified lithium ion battery anode material is obtained.
The chemical formula of the precursor is Ni0.5Co0.2Mn0.3(OH)2(ii) a The chemical formula of the coating precursor is Ni0.5Co0.2Mn0.3(OH)2·La0.01(CO3)0.015(ii) a The chemical formula of the lithium ion battery anode material is LiNi0.4951Co0.198Mn0.297La0.0099O2。
Example 2
The following solutions were prepared for use:
and (2) component A: a mixed salt solution with the concentration of 1.5mol/L (the molar ratio of nickel, cobalt and manganese elements is 6:2: 2);
complexing agent: ammonia water solution with the concentration of 5 mol/L;
first and second precipitating agents: sodium hydroxide solution with concentration of 5mol/L
Modifying agent: aluminum sulfate solution with the concentration of 0.2 moL/L;
(1) adding pure water, part of ammonia water and part of sodium hydroxide solution into a reaction kettle to prepare base solution, adding mixed salt solution, residual sodium hydroxide and residual ammonia water into the reaction kettle to carry out coprecipitation reaction, wherein the coprecipitation reaction conditions comprise: controlling the temperature of the reaction kettle to be 60 ℃, the pH value of the reaction system to be 12.2, the ammonia content of the reaction system to be 6g/L, the reaction retention time to be 15h, and the stirring speed to be 95rpm to obtain precursor slurry with the solid content of about 92 g/L;
(2) enabling the precursor slurry to flow into one coating kettle through an overflow port, an overflow pipeline and an overflow liquid receiving port, closing an overflow control valve after the coating kettle is full, opening an overflow control valve of the other coating kettle, and enabling the precursor slurry to overflow to the other coating kettle so as to alternatively overflow;
closing the coating kettle filled with the slurry, settling the slurry in the coating kettle for 2 hours, opening a clear liquid discharge device to discharge a clear liquid, observing the condition of discharging the clear liquid through a sight glass on a clear liquid discharge pipeline, and closing a clear liquid control valve when the liquid level of the coating kettle drops to the height 1/3 of the coating kettle, wherein the solid content of the slurry after the clear liquid is discharged is about 280 g/L; then the coating kettle is started to stir, and the ratio of the total mole amount of the nickel, cobalt and manganese elements to the aluminum element is 1: 0.02, slowly adding an aluminum sulfate solution and a sodium hydroxide solution into a coating kettle for coating reaction, wherein the conditions of the coating reaction comprise: controlling the pH value to be 12.6 by sodium hydroxide, the reaction time to be 3h and the reaction temperature to be 55Stirring at 150rpm, continuously stirring and aging in the coating after the coating reaction, wherein the aging conditions comprise: aging for 2h at 55 deg.C, discharging the aged material through material outlet, filtering, washing and drying to obtain D50Is a coated precursor of 8.0 um. Repeating the reaction process after the other coating kettles are full;
(3) and mixing the coated precursor with lithium carbonate, and then carrying out sintering reaction in an oxygen atmosphere, wherein the sintering reaction conditions comprise: the sintering temperature is 900 ℃, the sintering time is 14h, and the doped and coated co-modified lithium ion battery anode material is obtained.
The chemical formula of the precursor is Ni0.6Co0.2Mn0.2(OH)2(ii) a The chemical formula of the coating precursor is Ni0.6Co0.2Mn0.2(OH)2·Al0.02(OH)0.06(ii) a The chemical formula of the lithium ion battery anode material is LiNi0.5882Co0.196 1Mn0.1961Al0.0196O2。
Example 3
The following solutions were prepared for use:
and (2) component A: a mixed salt solution with the concentration of 1.5mol/L (the molar ratio of nickel, cobalt and manganese elements is 8:1: 1);
complexing agent: 5mol/L ammonia water solution
First and second precipitating agents: sodium hydroxide solution with the concentration of 10 mol/L;
modifying agent: zirconium nitrate solution with concentration of 0.01 moL/L;
(1) adding pure water, part of ammonia water and part of sodium hydroxide solution into a reaction kettle to prepare a base solution, adding mixed salt, the rest of sodium hydroxide and the rest of ammonia water into the reaction kettle to carry out coprecipitation reaction, wherein the coprecipitation reaction conditions comprise: the temperature of the reaction kettle is 65 ℃, the pH value of the reaction system is 12.7, the ammonia content of the reaction system is 9g/L, the reaction retention time is 20h, and the stirring speed is 120rpm, so that precursor slurry with the solid content of about 98g/L is obtained;
(2) enabling the precursor slurry to flow into one coating kettle through an overflow port, an overflow pipeline and an overflow liquid receiving port, closing an overflow control valve of the coating kettle after the coating kettle is full, opening an overflow control valve of the other coating kettle, and enabling the precursor slurry to overflow to the other coating kettle;
closing the coating kettle filled with the slurry, settling the slurry in the coating kettle for 1 hour, then opening a control valve of connected clear liquid discharge equipment to discharge clear liquid, observing the condition of discharging the clear liquid through a sight glass on a clear liquid discharge pipeline, closing a clear liquid automatic control valve when the liquid level of the coating kettle drops to the height of 1/2 of the kettle, and discharging the clear liquid to obtain the slurry with the solid content of about 190 g/L; then the coating kettle is started to stir, and the ratio of the total mole amount of the nickel element, the cobalt element and the manganese element to the zirconium element is 1: 0.005, adding zirconium nitrate solution and sodium hydroxide into a coating kettle for coating reaction, wherein the conditions of the coating reaction comprise: controlling the pH value to be 13.0 by sodium hydroxide, adding liquid for reaction for 1h, the reaction temperature is 65 ℃, the stirring speed is 150rpm, continuously stirring and aging in a coating after coating reaction, wherein the aging conditions comprise: aging for 2h at 65 deg.C, discharging the aged material through material outlet, filtering, washing, and oven drying to obtain D50Is a 10.5um coated precursor. Repeating the process after the other coating kettles are full;
5) mixing the coated precursor with lithium hydroxide, and then carrying out sintering reaction in an oxygen atmosphere, wherein the conditions of the sintering reaction comprise: the sintering temperature is 780 ℃ and the sintering time is 10h, so as to obtain the doped and coated co-modified lithium ion battery anode material.
The chemical formula of the precursor is Ni0.8Co0.1Mn0.1(OH)2(ii) a The chemical formula of the coating precursor is Ni0.8Co0.1Mn0.1(OH)2·Zr0.005(OH)0.02(ii) a The chemical formula of the lithium ion battery anode material is LiNi0.796Co0.099 5Mn0.0995Zr0.005O2。
Comparative example 1
A positive electrode material was prepared in a similar manner to example 3, except that: step (1) is carried out without carrying out step (2)According to the ratio of the mol sum of nickel, cobalt and manganese to the zirconium element of 1: 0.005, adding the mixed salt, sodium hydroxide, ammonia water and zirconium nitrate solution into a reaction kettle for coprecipitation reaction, doping the zirconium element solution into the precursor in the preparation process of the precursor to prepare the doped precursor Ni0.8Co0.1Mn0.1·Zr0.005(OH)2+0.02Then preparing a positive electrode material LiNi by adopting the same sintering conditions as the example 30.796Co0.0995Mn0.0995Zr0.005O2。
Comparative example 2
(1) Obtaining precursor slurry in the same step (1) as the step (3), and filtering, washing and drying the precursor slurry to obtain a precursor;
(2) and carrying out primary sintering on the obtained precursor and the mixed material of lithium hydroxide in an oxygen atmosphere to obtain a primary sintered material, wherein the primary sintering conditions comprise: the sintering temperature is 780 ℃ and the sintering time is 10 h;
(3) according to the ratio of the molar total amount of nickel, cobalt and manganese to the zirconium element of 1: 0.005, mixing and coating the primary sintering material and zirconia, and sintering again at 450 ℃ to obtain the coated and modified lithium ion battery cathode material LiNi0.796Co0.099 5Mn0.0995Zr0.005O2。
Test example
1. SEM test
The present inventors tested SEM images of the coated precursors prepared in the above examples and comparative examples at different magnification.
The invention exemplarily provides SEM images of the coated precursor obtained in example 3 and the doped precursor obtained in comparative example 1 under different multiples, as shown in fig. 2 and fig. 3, respectively, and a comparison between fig. 2 and fig. 3 shows that the coated precursor obtained in example 3 has an obvious coating layer on the surface, while the doped precursor obtained in comparative example 1 has a cleaner surface, which indicates that the zirconium element in the coated precursor obtained in example 3 is uniformly coated on the surface of the precursor, while the zirconium element in comparative example 1 is doped into the precursor to form the doped precursor.
2. Zr element distribution test
According to the invention, the distribution of Zr element in the lithium ion battery anode material particles prepared in the above examples and comparative examples is tested by EDS energy spectrum.
The present invention exemplarily provides the test results of example 3 and comparative example 1, as shown in fig. 4 (the abscissa represents the distance from the particle core, and the larger the number represents the farther away from the particle core, i.e., the closer to the particle surface), it can be seen from fig. 4 that both the inside and the surface of the particles of the positive electrode material prepared by the present invention contain Zr element, and also, in combination with the SEM picture, it can be seen that the positive electrode material obtained by the preparation method of the present invention has the double modification effect of coating and doping with the modification element, and also, as can be seen from fig. 4, the modification element (e.g., Zr) of the positive electrode material obtained by the present invention gradually decreases from the particle surface to the inside.
3. Cell electrochemical performance testing
According to the invention, the button type half cell is prepared from the lithium ion battery anode materials prepared in the above examples and comparative examples, and the electrochemical performance of the button type half cell is tested.
The invention exemplarily provides the cycle performance of the cathode materials of the embodiment 3 and the comparative example 1 under different conditions, as shown in fig. 5 (the test conditions are 25 ℃, 1C/1C @4.5-3.0V) and fig. 6 (the test conditions are 45 ℃, 1C/1C @4.3-3.0V), respectively, it can be seen from both fig. 5 and fig. 6 that the initial capacity of the cathode material prepared by the invention is relatively higher, and the capacity retention rate of the cathode material obtained by the invention is obviously higher under the charging and discharging conditions of 25 ℃ and 45 ℃, and the cycle performance is better, thus it can be seen that the cathode material obtained by the invention has more excellent electrochemical performance compared with the cathode material obtained by the existing doping modification method.
In addition, the invention also exemplarily provides the cycle performance of the cathode materials of the embodiment 3 and the comparative example 2 under different conditions, as shown in fig. 7 (the test conditions are 25 ℃, 1C/1C @4.5-3.0V) and fig. 8 (the test conditions are 45 ℃, 1C/1C @4.3-3.0V), respectively, through fig. 7 and fig. 8, the capacity retention rate of the cathode material prepared by the invention is obviously higher under the charge and discharge conditions of 25 ℃ and 45 ℃ and the cycle performance is better than that of the cathode material prepared by the comparative example 2, and it can be seen that the cathode material obtained by the invention also has more excellent electrochemical performance than that of the cathode material obtained by the existing coating modification method.
In conclusion, the doped and coated double-modified cathode material can be prepared by adopting the method provided by the invention, and the electrochemical performance of the cathode material is effectively improved.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, numerous simple modifications can be made to the technical solution of the invention, including combinations of the individual specific technical features in any suitable way. The invention is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.

Claims (10)

1. A method for preparing a positive electrode material of a lithium ion battery is characterized by comprising the following steps:
(1) carrying out coprecipitation reaction on each component in the component A in the presence of a complexing agent and a first precipitator to obtain precursor slurry containing a precursor, wherein the component A contains manganese salt, cobalt salt and nickel salt;
(2) in the presence of a second precipitator, carrying out coating reaction on the precursor slurry and a modifier so that the modifier is coated on the particle surface of the precursor to obtain a coated precursor;
(3) and carrying out sintering reaction on the coated precursor and lithium salt to obtain the doped and coated co-modified lithium ion battery anode material.
2. The method according to claim 1, wherein the modifier contains a modifying element M selected from at least one of Ni, Mn, Co, Al, Ti, Zr, W, B, Fe, La, Cr and Ce elements;
preferably, the chemical formula of the precursor is Ni1-x-yCoxMny(OH)2(ii) a The chemical formula of the coating precursor is Ni1-x- yCoxMny(OH)2·MzE; the chemical formula of the lithium ion battery anode material is LiNi1-x-y-zCoxMnyMzO2(ii) a Wherein, 0<x<0.5，0<y<1，0.001<z<0.1，MzE is hydroxide or carbonate of the modifying element M;
preferably, in the lithium ion battery cathode material, the modification element M gradually decreases from the surface to the inside of the material particles.
3. The process according to claim 1, wherein, in step (1), the first precipitating agent is a hydroxide of an alkali metal, preferably sodium hydroxide and/or potassium hydroxide;
preferably, in the step (1), the complexing agent is selected from at least one of ammonia water, ammonium sulfate, ammonium chloride, ammonium nitrate and the like;
preferably, in step (1), the conditions of the coprecipitation reaction include: the reaction temperature is 40-70 ℃, the pH value of the reaction system is 10.5-13, the ammonia content of the reaction system is 0.5-15g/L, the reaction time is 5-40h, and the stirring speed is 50-300 rpm.
4. The method of claim 1 or 2, wherein in step (2), the conditions of the coating reaction comprise: the reaction temperature is 50-70 ℃, the reaction time is 1-10h, the pH value of the reaction system is 8.0-13.5, and the stirring speed is 150-400 rpm;
preferably, in the step (2), the second precipitant is selected from at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate;
preferably, the step (2) further comprises, before the coating reaction, settling the precursor slurry, then discharging a clear liquid, and then performing the coating reaction on the slurry after the clear liquid is discharged and the modifying agent;
preferably, the step (2) further comprises aging the reaction material subjected to the coating reaction to obtain the coating precursor;
preferably, the aging conditions include: the aging temperature is 50-70 ℃, and the aging time is 0.5-5 h.
5. The method according to any one of claims 1 to 4, wherein in step (3), the conditions of the sintering reaction comprise: the sintering temperature is 400-1000 ℃, and the sintering time is 4-20 h;
preferably, in step (3), the lithium salt is selected from at least one of lithium nitrate, lithium chloride, lithium hydroxide and lithium carbonate.
6. A lithium ion battery positive electrode material made by the method of any one of claims 1-5.
7. The use of the lithium ion battery positive electrode material of claim 6 in a lithium ion battery.
8. The device for preparing the precursor of the lithium ion battery anode material is characterized by comprising a reaction kettle and a coating kettle, wherein the coating kettle is communicated with the reaction kettle, so that precursor slurry prepared by the reaction kettle can enter the coating kettle to contact with a modifier for coating reaction to obtain a coated precursor.
9. The apparatus of claim 8, wherein there are at least two coating kettles, and each coating kettle is in controllable communication with the reaction kettle, so that the precursor slurry can alternately overflow into each coating kettle to contact with the modifier for the coating reaction;
preferably, the device further comprises a clear liquid discharging device, the clear liquid discharging device comprises a liquid discharging pump, and the coating kettle is in controllable communication with the liquid discharging pump, so that the precursor slurry entering the coating kettle can be settled and then subjected to the coating reaction after the clear liquid is discharged through the liquid discharging pump.
10. A system for preparing a lithium ion battery cathode material, which is characterized by comprising a precursor preparation device and a sintering furnace, wherein the precursor preparation device is the device for preparing the lithium ion battery cathode material precursor according to claim 8 or 9.
CN202111681916.4A 2020-12-31 2021-12-31 Lithium ion battery anode material, preparation method and application thereof, system and precursor preparation device Pending CN114455644A (en)

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