CN117088426B - Lithium ion battery, positive electrode material and modified precursor thereof and preparation method - Google Patents

Lithium ion battery, positive electrode material and modified precursor thereof and preparation method Download PDF

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CN117088426B
CN117088426B CN202311360495.4A CN202311360495A CN117088426B CN 117088426 B CN117088426 B CN 117088426B CN 202311360495 A CN202311360495 A CN 202311360495A CN 117088426 B CN117088426 B CN 117088426B
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precursor
lithium ion
ion battery
modified
lithium
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CN117088426A (en
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周宇环
张萍
李成
侯世林
龚仕洪
范未峰
张彬
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Yibin Libao New Materials Co Ltd
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • 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
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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Abstract

The invention discloses a lithium ion battery, a positive electrode material, a modified precursor and a preparation method thereof, and belongs to the technical field of lithium ion batteries. The preparation of the modified precursor comprises the following steps: the nickel-containing binary precursor or the nickel-containing ternary precursor is subjected to heat treatment, and then mixed with a solution containing a modified raw material, and the solvent is removed. The method can be used for pore-forming the precursor primary particles and increasing the specific surface area of the precursor primary particles; after pore formation, the whole agglomerate grains are distributed with tiny holes from inside to outside to form communicating pore channels. The solution containing the modified raw material permeates into the agglomerate grains along the micro pore canals under the action of capillary effect, so that the doping or coating of primary grains is realized, and the cycle performance of the anode material and the lithium ion battery further prepared from the modified precursor is improved.

Description

Lithium ion battery, positive electrode material and modified precursor thereof and preparation method
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery, a positive electrode material, a modified precursor and a preparation method thereof.
Background
The modification of the precursor of the positive electrode material is usually performed by wet chemical methods. The method comprises the steps of dissolving a modified raw material in a solvent to form a uniform solution, adding a precursor of a positive electrode material into the solution to form a suspension, heating and evaporating the solvent to dryness to precipitate and uniformly attach the solute of the modified raw material on the surfaces of precursor particles, realizing uniform coating, and carrying out heat treatment to coat or dope the modifier into the material.
However, the following problems may exist with this approach for polycrystalline agglomerated particles: the appearance of some polycrystal secondary particles is compact, and the viscosity of the coating solution is high, so that the solution cannot permeate into the secondary particles, coating of the inner primary particles is realized, modification can only be stopped on the surfaces of the secondary particles, and the effect is greatly reduced.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a modified precursor of a lithium ion battery, wherein pores are formed in the modified precursor, the specific surface area is large, and a modifying element can enter secondary particles, so that the effect of the modifying element is improved.
The second purpose of the invention is to provide a preparation method of the lithium ion battery modified precursor.
The invention further provides a lithium ion battery anode material prepared from the modified precursor.
The fourth object of the invention is to provide a preparation method of the positive electrode material of the lithium ion battery.
The fifth object of the present invention is to provide a lithium ion battery containing the above positive electrode material.
The application can be realized as follows:
in a first aspect, the present application provides a method for preparing a modified precursor of a lithium ion battery, comprising the steps of: carrying out heat treatment on a nickel-containing binary precursor or a nickel-containing ternary precursor, then mixing the nickel-containing binary precursor or the nickel-containing ternary precursor with a solution containing a modified raw material, and removing a solvent to obtain a lithium ion battery modified precursor;
the molecular formula of the nickel-containing binary precursor is: ni (Ni) x M y (OH) 2 Wherein M is any one of Mn, al and Co, x is more than or equal to 0.8 and less than or equal to 1, and x+y=1; the molecular formula of the ternary precursor containing nickel isNi x Co y N 1-x-y (OH) 2 Wherein, N is any one of Al or Co, x is more than or equal to 0.8 and less than 1, and y is more than or equal to 0 and less than 0.2.
In an alternative embodiment, the heat treatment is carried out at a temperature of 250 ℃ to 550 ℃ for 4 hours to 6 hours.
In an alternative embodiment, the modifying element of the modifying feedstock comprises at least one of Mg, sc, V, zr, fe, ti, Y, la, cu, zn, ba and Ca elements; the amount of each modifying element is independently 0.1wt% to 0.4wt% of the precursor before modification.
In an alternative embodiment, the solvent used in the solution comprising the modifying feedstock comprises at least one of absolute ethanol and water; the solvent is used in an amount of 1 to 1.5 times the mass of the precursor before modification.
In an alternative embodiment, the mixing is performed at 1800rpm to 2200 rpm.
In an alternative embodiment, the solvent removal is performed at a temperature of 70 ℃ to 80 ℃.
In a second aspect, the present application provides a lithium ion battery modified precursor, prepared by the preparation method of any one of the foregoing embodiments.
In a third aspect, the present application provides a lithium ion battery cathode material, which is obtained by mixing and sintering the lithium ion battery modified precursor and the lithium source in the foregoing embodiment.
In a fourth aspect, the present application provides a method for preparing a positive electrode material of a lithium ion battery according to the foregoing embodiment, including the following steps: mixing the lithium ion battery modified precursor of the previous embodiment with a lithium source, and sintering;
wherein the lithium source comprises lithium hydroxide;
the molar ratio of the total amount of transition metal in the lithium ion battery modified precursor to lithium element in the lithium source is 1:1 to 1:1.06;
the sintering is carried out by preserving heat for 2-4 h at 480-520 ℃ and then preserving heat for 8-12 h at 760-800 ℃.
In a fifth aspect, the present application provides a lithium ion battery comprising the lithium ion battery cathode material of the foregoing embodiment.
The beneficial effects of this application include:
the application is that a nickel-containing precursor with a specific molecular formula is subjected to heat treatment, hydroxide in the hydroxide precursor is decomposed into water and oxide, and the generated water is evaporated at high temperature, so that holes are left on precursor particles. On the whole, after pore formation, the whole agglomerate grains are fully distributed with tiny holes from inside to outside to form communicated pore channels, and the specific surface area of the precursor is greatly improved. The holes can enable the solution containing the modified raw material to permeate into the agglomerate grains under the action of capillary effect, so that the primary grains are coated or doped, and the cycle performance of the positive electrode material and the lithium ion battery prepared from the modified precursor is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is Ni 0.96 Co 0.03 Mn 0.01 (OH) 2 A specific surface area change chart of the precursor along with the heat treatment temperature;
FIG. 2 is a diagram of the LiNi of example 2 0.96 Co 0.03 Mn 0.01 O 2 An XRD pattern of (b);
FIG. 3 is a diagram of the LiNi of example 2 0.96 Co 0.03 Mn 0.01 O 2 SEM images of (a).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The lithium ion battery, the anode material, the modified precursor and the preparation method thereof provided by the application are specifically described below.
The application provides a preparation method of a lithium ion battery modified precursor, which comprises the following steps: and carrying out heat treatment on the nickel-containing binary precursor or the nickel-containing ternary precursor, then mixing with a solution containing a modified raw material, and removing the solvent to obtain the modified precursor of the lithium ion battery.
The molecular formula of the nickel-containing binary precursor is as follows: ni (Ni) x M y (OH) 2 Wherein M is any one of Mn, al and Co, x is more than or equal to 0.8 and less than or equal to 1, and x+y=1. The molecular formula of the ternary precursor containing nickel is Ni x Co y N 1-x-y (OH) 2 Wherein, N is any one of Al or Co, x is more than or equal to 0.8 and less than 1, and y is more than or equal to 0 and less than 0.2.
The heat treatment is carried out at the temperature of 250-550 ℃ for 4-6 h. The heat treatment temperature may be 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, or the like, or may be any other value in the range of 250 to 550 ℃. The heat treatment time may be 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, etc., or any other value within the range of 4 to 6 hours.
In some preferred embodiments, the heat treatment is performed at a temperature of 350 ℃ to 450 ℃ for 5 hours.
Preferably, the heat treatment process is performed under an oxygen atmosphere.
By heat treating the nickel-containing precursor of the above formula at a temperature of 250-550 ℃, the hydroxide in the hydroxide precursor is decomposed into water and oxide, and the resulting water evaporates at high temperature, leaving behind pores in the precursor particles. On the whole, after pore formation, the whole agglomerate grains are fully distributed with tiny holes from inside to outside to form communicating pore channels, which is shown by the great increase of the specific surface area of the precursor (Ni is used 0.96 Co 0.03 Mn 0.01 (OH) 2 The precursor is exemplified by the specific surface area change with the heat treatment temperature shown in fig. 1). The holes can enable the solution containing the modified raw materials to permeate into the agglomerate grains under the action of capillary effect,the coating or doping of the primary particles is realized, and the cycle performance of the anode material and the lithium ion battery further prepared from the modified precursor is improved.
If the heat treatment temperature is lower than 250 ℃, the hydroxide is incompletely acidified and cannot be completely decomposed into oxide and water, and the pore-forming effect is poor; if the heat treatment temperature is higher than 550 ℃, the specific surface area of the precursor obtained by modification is rather smaller, which may be due to other changes of the precursor primary particles under the temperature conditions.
In the present application, the solvent used in the solution containing the modified raw material may include, for example, at least one of absolute ethanol and water. The solvent may be used in an amount of 1 to 1.5 times, such as 1, 1.1, 1.2, 1.3, 1.4, or 1.5 times the mass of the precursor before modification.
The modifying element of the modifying raw material may include at least one of Mg, sc, V, zr, fe, ti, Y, la, cu, zn, ba and Ca elements, and accordingly, the modifying raw material may include at least one of magnesium acetate, scandium nitrate, vanadium nitrate, zirconium nitrate, iron nitrate, titanium nitrate, yttrium nitrate, lanthanum nitrate, copper nitrate, zinc nitrate, calcium nitrate, and barium nitrate. The amount of each modifying element is independently 0.1wt% to 0.4wt% of the precursor before modification, such as 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt% or 0.4wt%, etc.
In some preferred embodiments, the modified raw material contains 3 modified elements, specifically Zr, Y and Mg, and the amount of each modified element is 0.2wt% of the precursor before modification, so that the corresponding lithium ion battery can have better gram capacity and capacity retention rate at the same time under the preferred scheme.
In this application, the heat-treated precursor and the modified raw material-containing solution may be mixed under stirring conditions, and the stirring speed may be, for example, 1800rpm to 2200rpm, such as 1800rpm, 1900rpm, 2000rpm, 2100rpm, 2200rpm, or the like.
Through the mixing mode, the precursor after heat treatment is uniformly infiltrated by the solution containing the modified raw material, so that the modified raw material can uniformly enter holes formed after heat treatment of the precursor while acting on the surface of the agglomerated particles (secondary particles) and infiltrate into the inside of the agglomerated particles (secondary particles) to act on the primary particles.
The solvent removal can be carried out, for example, under conditions of 70℃to 80℃such as 70℃and 75℃or 80 ℃. The primary particles or secondary particles are coated or doped in situ by removing the solvent from the modified feedstock.
Correspondingly, the application also provides a lithium ion battery modified precursor which is prepared by the preparation method.
The specific surface area of the modified precursor of the lithium ion battery is obviously improved compared with that of the modified precursor, and the modified precursor is favorable for improving the cycle performance of the positive electrode material prepared from the modified precursor and the lithium ion battery.
In addition, the application also provides a lithium ion battery anode material which is obtained by mixing and sintering the lithium ion battery modified precursor and a lithium source.
Correspondingly, the application also provides a preparation method of the lithium ion battery anode material, which comprises the following steps: mixing the modified precursor of the lithium ion battery with a lithium source, and sintering.
Wherein the lithium source comprises lithium hydroxide.
The molar ratio of the total amount of transition metal in the lithium ion battery modified precursor to lithium element in the lithium source is 1:1 to 1:1.06, such as 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, etc.
Sintering may be performed at 480-520℃ (e.g., 480℃, 490℃, 500℃, 510℃, 520℃, etc.) for 2h-4h (e.g., 2h, 2.5h, 3h, 3.5h, 4h, etc.), followed by 8h-12h (e.g., 8h, 9h, 10h, 11h, 12h, etc.) at 760-800℃ (e.g., 760℃, 770℃, 780℃ 790℃, 800℃, etc.).
Further, the application also provides a lithium ion battery, which contains the positive electrode material of the lithium ion battery. The corresponding lithium ion battery has higher gram capacity and capacity retention rate.
It should be noted that, the specific preparation method and conditions of the lithium ion battery can refer to the related prior art, and are not repeated and limited herein.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a lithium ion battery anode material, which is prepared by the following method:
s1: and adding the precursor after pore formation into the modified solution, stirring at 2000rpm, and evaporating the solvent at 75 ℃ to obtain the modified precursor.
The precursor after pore formation is obtained by the following method: by mixing Ni with molecular formula 0.96 Co 0.03 Mn 0.01 (OH) 2 And (3) carrying out heat treatment on the hydroxide ternary precursor for 5 hours in an oxygen atmosphere at the temperature of 250 ℃ to obtain the precursor after pore formation.
The uniform transparent modified solution is obtained by the following method: adding solute into solvent, mixing well. The solvent is absolute ethyl alcohol, and the solute is zirconium nitrate, aluminum nitrate and magnesium acetate. The solvent amount is 1.2 times of the mass of the precursor after pore formation, and the amount of each doping element (Zr, Y and Mg) is 0.2wt% of the precursor after pore formation.
S2: and uniformly mixing lithium hydroxide with the modified precursor, and sintering in an oxygen atmosphere to obtain the lithium ion battery anode material.
Wherein the molar ratio of the total amount of transition metal in the modified precursor to lithium element in lithium hydroxide is 1:1.06. The sintering is carried out at 500 ℃ for 3 hours, and then at 780 ℃ for 10 hours.
Example 2
This embodiment differs from embodiment 1 in that: in S1, the heat treatment temperature of the hydroxide ternary precursor is 350 ℃.
LiNi prepared in this example 0.96 Co 0.03 Mn 0.01 O 2 The XRD patterns and SEM patterns of (a) are shown in fig. 2 and 3, respectively.
As can be seen from fig. 2: synthesized positive electrode material and alpha-NaFeO 2 In the same structure as that of the plastic bag,the transition metal cations and alkaline earth metal cations are alternately arranged and are typically layered oxides.
As can be seen from fig. 3: the synthesized secondary particles of the positive electrode material have spherical morphology, the particle size is about 4 mu m, and the particle size of the primary particles is about 100nm to 200nm.
Example 3
This embodiment differs from embodiment 1 in that: in S1, the heat treatment temperature of the hydroxide ternary precursor is 450 ℃.
Example 4
This embodiment differs from embodiment 1 in that: in S1, the heat treatment temperature of the hydroxide ternary precursor is 550 ℃.
Example 5
The embodiment provides a lithium ion battery anode material, which is prepared by the following method:
s1: adding the precursor after pore formation into the modified solution, stirring at 1800rpm, and evaporating the solvent at 70 ℃ to obtain the modified precursor.
The precursor after pore formation is obtained by the following method: the same hydroxide ternary precursor as in example 1 was heat treated under an oxygen atmosphere at 250 ℃ for 6 hours to obtain a precursor after pore formation.
The uniform transparent modified solution is obtained by the following method: adding solute into solvent, mixing well. The solvent is deionized water, and the solute is manganese acetate and ferric nitrate. The solvent amount is 1 time of the mass of the precursor after pore-forming, and the amount of each doping element (Ba and Fe) is 0.1wt% of the precursor after pore-forming.
S2: and uniformly mixing lithium hydroxide with the modified precursor, and sintering in an oxygen atmosphere to obtain the lithium ion battery anode material.
Wherein the molar ratio of the total amount of transition metal in the modified precursor to lithium element in lithium hydroxide is 1:1.04. Sintering is carried out for 4 hours at 480 ℃ and then 12 hours at 760 ℃.
Example 6
The embodiment provides a lithium ion battery anode material, which is prepared by the following method:
s1: adding the precursor after pore formation into the modification solution, stirring at 2200rpm, and evaporating the solvent at 80 ℃ to obtain the modified precursor.
The precursor after pore formation is obtained by the following method: the same hydroxide ternary precursor as in example 1 was heat treated under an oxygen atmosphere at 550 ℃ for 4 hours to obtain a precursor after pore formation.
The uniform transparent modified solution is obtained by the following method: adding solute into solvent, mixing well. The solvent is absolute ethyl alcohol, and the solute is titanium nitrate. The solvent amount is 1.2 times of the mass of the precursor after pore formation, and the doping element (Ti) amount is 0.4wt% of the precursor after pore formation.
S2: and uniformly mixing lithium hydroxide with the modified precursor, and sintering in an oxygen atmosphere to obtain the lithium ion battery anode material.
Wherein the molar ratio of the total amount of transition metal in the modified precursor to lithium element in lithium hydroxide is 1:1. Sintering is carried out by preserving heat for 2 hours at 520 ℃ and then preserving heat for 8 hours at 800 ℃.
Example 7
This embodiment differs from embodiment 2 in that: the precursor is a binary precursor containing nickel, and the molecular formula is as follows: ni (Ni) 0.95 Mn 0.05 (OH) 2 。
Comparative example 1
The difference between this comparative example and example 2 is that: in S1, the precursor is directly mixed with the modifying solution without pore-forming treatment, and the rest steps and conditions are the same as in example 2.
Comparative example 2
The difference between this comparative example and example 2 is that: only the precursor after pore formation was treated with no modifying solution, and the rest of the procedure and conditions were the same as in example 2.
Comparative example 3
The difference between this comparative example and example 2 is that: neither pore-forming treatment nor modification solution treatment is performed on the precursor, i.e. the hydroxide ternary precursor is directly subjected to step S2.
Comparative example 4
The difference between this comparative example and example 2 is that: in S1, the heat treatment temperature of the hydroxide ternary precursor is 200 ℃.
Comparative example 5
The difference between this comparative example and example 2 is that: in S1, the heat treatment temperature of the hydroxide ternary precursor is 650 ℃.
Comparative example 6
The difference between this comparative example and example 2 is that: in S1, the heat treatment time of the hydroxide ternary precursor is 3.5h.
Comparative example 7
The difference between this comparative example and example 2 is that: in S1, the heat treatment time of the hydroxide ternary precursor is 8h.
Comparative example 8
The difference between this comparative example and example 2 is that: in S1, the amount of each doping element (Zr, Y and Mg) is 0.05wt% of the precursor after pore formation.
Comparative example 9
The difference between this comparative example and example 1 is that: in S1, the amount of each doping element (Zr, Y and Mg) was 0.45wt% of the precursor after pore formation.
Comparative example 10
The difference between this comparative example and example 2 is that: in S1, solutes in the modification solution are zirconium nitrate and aluminum nitrate, and the dosage of each doping element is 0.3wt% of the precursor after pore forming.
Comparative example 11
The difference between this comparative example and example 2 is that: in S1, zinc nitrate is used for replacing magnesium acetate with equal amount.
Test examples
The positive electrode materials of the lithium ion batteries obtained in examples 1-7 and comparative examples 1-11 are prepared into electrode plates, and the electrode plates are assembled into button half batteries respectively, specifically, after 0.9g of positive electrode powder, 0.05g of PVDF and 0.05g of Super P are uniformly mixed, 2.9g of NMP is added to form a viscous suspension, the suspension is stirred to form uniform viscous slurry, the slurry fluidity is observed in the stirring process, the viscosity is controlled to be 2000-5000 mPas, and NMP is properly added. And uniformly coating the prepared slurry on aluminum foil by using a scraper with the height of 250 mu m, then placing the coated pole piece into a vacuum drying oven, vacuumizing and drying for 8 hours at 120 ℃, and finally compacting the pole piece by using a pair roller (the distance between the pair rollers is 10 mu m) to obtain the positive pole piece. And (3) respectively taking lithium metal as a counter electrode for the prepared pole pieces, and assembling the button half battery for testing.
(1) The specific surface areas of the modified precursors or precursors for mixing with lithium hydroxide in each of the examples and comparative examples were measured, and the results are shown in table 1.
(2) The unit cell parameters of the positive electrode materials for lithium ion batteries obtained in each example and comparative example were measured, and the results are shown in table 1.
(3) The button half-cells obtained by assembling each example and comparative example were subjected to comparison of gram capacity and capacity retention (50 cycles at 1C and 45℃), and the results are shown in table 1.
Table 1 test results
As can be seen from table 1, the button half cell prepared from the positive electrode material provided in the embodiment of the present application can have both higher gram capacity and cycle retention rate.
In summary, the preparation method provided by the application can be used for pore-forming of the precursor primary particles and increasing the specific surface area of the precursor primary particles; after pore formation, the whole agglomerate grains are distributed with tiny holes from inside to outside to form communicating pore channels. The solution containing the modified raw material permeates into the agglomerate grains along the micro pore canals under the action of capillary effect, so that the doping or coating of primary grains is realized, and the cycle performance of the anode material and the lithium ion battery further prepared from the modified precursor is improved.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. The preparation method of the lithium ion battery modified precursor is characterized by comprising the following steps of: carrying out heat treatment on a nickel-containing binary precursor or a nickel-containing ternary precursor, then mixing the nickel-containing binary precursor or the nickel-containing ternary precursor with a solution containing a modified raw material, and removing a solvent to obtain a lithium ion battery modified precursor;
the molecular formula of the nickel-containing binary precursor is as follows: ni (Ni) 0.95 Mn 0.05 (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the The molecular formula of the ternary precursor containing nickel is Ni 0.96 Co 0.03 Mn 0.01 (OH) 2 ；
The heat treatment is carried out for 4 to 6 hours at the temperature of 250 to 550 ℃;
the modifying elements of the modifying raw material are Zr, Y and Mg, and the dosage of each modifying element is 0.1-0.4 wt% of the precursor before modification independently;
the mixing is performed under stirring at 1800rpm to 2200 rpm.
2. The method according to claim 1, wherein the solvent used in the solution containing the modified raw material comprises at least one of absolute ethanol and water;
the dosage of the solvent is 1 to 1.5 times of the mass of the precursor before modification.
3. The process according to claim 1, wherein the removal of the solvent is carried out at a temperature of 70 ℃ to 80 ℃.
4. A lithium ion battery modified precursor, characterized in that it is prepared by the preparation method of any one of claims 1 to 3.
5. A lithium ion battery anode material is characterized in that the lithium ion battery anode material is obtained by mixing and sintering the lithium ion battery modified precursor and a lithium source.
6. A method for preparing the positive electrode material of the lithium ion battery according to claim 5, comprising the following steps: mixing the lithium ion battery modified precursor of claim 5 with a lithium source, and sintering;
wherein the lithium source comprises lithium hydroxide;
the molar ratio of the total amount of transition metal in the lithium ion battery modified precursor to lithium element in the lithium source is 1:1 to 1:1.06;
the sintering is carried out for 2-4 h under the condition of 480-520 ℃ and then 8-12 h under the condition of 760-800 ℃.
7. A lithium ion battery comprising the positive electrode material of the lithium ion battery of claim 6.
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