CN115881944B - Layered oxide positive electrode material with transition metal layer superlattice structure and preparation method thereof - Google Patents
Layered oxide positive electrode material with transition metal layer superlattice structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a layered oxide positive electrode material with a transition metal layer superlattice structure and a preparation method thereof. The chemical formula of the layered oxide positive electrode material is LiNi x M 1‑x O 2 Wherein M is a high-valence transition metal element with an atomic number greater than 40 and less than 84, at least one set of minimum super-structural units of-M-Ni-Ni-M-is contained in a single transition metal layer, a superlattice structure is formed between Ni and M through electrostatic interaction, and the valence state of M and the valence state of Ni keep a specific corresponding relation: ni (Ni) 2+ Corresponds to M 4+ While Ni 3+ Then corresponds to M 6+ Or M 5+ The method comprises the steps of carrying out a first treatment on the surface of the The atomic ratio between Ni and M is 2:1-1:0.01. From the aspect of structural design, the invention designs and synthesizes the layered oxide anode material with the transition metal superlattice structure, improves the cycling stability of the material, obtains the lithium ion battery anode material with excellent electrochemical performance through a simple and easy coprecipitation preparation process, is easy for industrial amplification application, and generates large-scale economic benefit.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials and electrochemistry, and particularly relates to a layered oxide positive electrode material of a lithium ion battery with a transition metal layer superlattice structure and a preparation method thereof.
Background
In modern innovative energy networks, to facilitate carbon neutralization to cope with 21 st century climate change and future energy infrastructure, higher energy density and higher safety energy storage devices are needed. Ternary LiNi x Co y Mn 1-x-y O 2 Positive electrode materials due to their high energy density and relative to LiCoO 2 The characteristics of lower cost and the like are applied to the field of power batteries represented by electric vehicles. Nickel-based ternary batteries have been found to occupy more than 40% of the power cell market share. With the expansion of the market and the demand for high energy density and endurance mileage, high-nickel cathode materials in the field of power batteries are gradually advancing to material systems with higher nickel content. However, for nickel-based materials with Ni contents higher than 0.75, there are several disadvantages: structural defects such as disorder of cations, formation of oxygen and lithium vacancies and further irreversible phase change, narrower electrochemical stability window of electrolyte solvent, interfacial reaction and Transition Metal (TMs) dissolutionSolution, anisotropic volume changes and cyclically generated microcracks, surface wet/air reactive lithium residues, and the like. The unsteady state of the structure during cycling and the high reactivity of the interface are the main causes of the above-mentioned disadvantages of the high nickel materials.
At present, the modification of the high nickel material mainly comprises two technical means of doping and cladding. The main purpose of doping is to stabilize the irreversible structural phase change of the material during the cycling process by utilizing the strong binding energy between the doping element and oxygen, such as the doping of elements such as Mg, al, ti and the like. However, the introduction of inactive elements reduces the reversible capacity of the material, and this modification mode, which sacrifices the reversible capacity of the material, is one of the current mainstream means. In addition, the high-nickel positive electrode material can improve the stability of a solid-liquid interface in a surface coating mode. The coating material is generally selected from the group consisting of structurally stable Al that does not react with the electrolyte 2 O 3 、ZnO、AlF 3 Etc. However, the coating on the surface of the particles is not effective in preventing the problem of particle pulverization due to the anisotropic phase transition of the internal structure of the high nickel material in the 4.2V high voltage region/high release state. It is generally necessary to combine two technical means of cladding and doping, so as to improve the overall performance of the material from inside to outside.
Therefore, in order to solve the disadvantage of deterioration of performance of the high nickel layered cathode material due to the structure, it is necessary to provide a new view to electrochemical performance of the layered oxide cathode material including high nickel from the viewpoint of structural design.
Disclosure of Invention
The invention mainly aims to solve the problem of structural stability of the layered oxide cathode material of the lithium ion battery from the aspect of structural design, and utilizes the transition metal elements with high valence state and heavy mass to form a stable superlattice structure with low valence state metals such as Ni, co and the like through electrostatic interaction, thereby improving the structural stability of the material in circulation. The method improves the cycling stability of the oxide positive electrode material from the aspect of structural design in an innovative view angle.
In a first aspect of the present invention, a layered oxide cathode material for a lithium ion battery is provided that is structurally stableA customization strategy, wherein the chemical formula of the layered oxide positive electrode material is LiNi x M 1-x O 2 Wherein M is a high valence transition metal element having an atomic number greater than 40 and less than 84, characterized by the structure:
a. the designed and synthesized chemical formula is LiNi x M 1-x O 2 In the layered oxide positive electrode material, at least one set of minimum super-structural units of-M-Ni-Ni-M-is contained in a single transition metal layer, and a superlattice structure is formed between low-valence element Ni and high-valence element M with high atomic number through electrostatic interaction;
b. m in the chemical formula is a transition metal element with high valence, and the valence of M and the valence of Ni keep a specific corresponding relation, and the valence characteristics are as follows: ni (Ni) 2+ Corresponds to M 4+ While Ni 3+ Then corresponds to M 6+ Or M 5+ ；
c. The atomic ratio between Ni and M is 2:1-1:0.01, namely 0< x <1 and x/(1-x) is 2-100.
The layered oxide cathode material LiNi x M (1-x) O 2 In which M is preferably one or more of Te, W, nb, ta, mo, a layered oxide cathode material such as LiNi 0.99 Te 0.1 O 2 、LiNi 0.98 Te 0.02 O 2 、LiNi 0.95 Te 0.05 O 2 、LiNi 2/ 3 Te 1/3 O 2 、LiNi 0.99 W 0.1 O 2 、LiNi 0.98 W 0.02 O 2 、LiNi 0.95 W 0.05 O 2 、LiNi 0.99 Nb 0.01 O 2 、LiNi 0.6 Ta 0.4 O 2 、LiNi 0.8 Mo 0.2 O 2 、LiNi 0.7 Mo 0.3 O 2 Etc.
High nickel layered oxide cathode material LiNi x M (1-x) O 2 In which x is preferably 0.5 to 0.99.
In a second aspect of the present invention, there is provided a controllable preparation method for mass production of the above layered oxide cathode material, comprising the steps of:
step 1: weighing chemical LiNi x M 1-x O 2 The compound containing Ni and M transition metal elements in the stoichiometric ratio is prepared into a solution which is marked as solution A; weighing NaOH with the concentration of transition metal being 2 times of the stoichiometric ratio, adding ammonia water as a complexing agent, and marking the formed mixed solution as a solution B;
step 2: dropwise adding the solution A into a reaction kettle at a constant flow rate through a coprecipitation process, dropwise adding the solution B into the reaction kettle through a pH self-feedback regulating system in a variable frequency manner, controlling the pH value of the reaction system to be between 10 and 13, obtaining precipitate after reaction, washing, drying, and sieving the obtained dry powder to obtain a precursor;
step 3: uniformly mixing the precursor obtained in the step 2 with a lithium source, placing the mixed powder in a high-temperature reaction container, and sintering in an oxidizing atmosphere to obtain a layered oxide anode material LiNi x M 1-x O 2 。
In the above step 1, the Ni-containing compound used for preparing the solution A may be selected from NiSO 4 、NiCH 3 COOH、Ni(NO 3 ) 2 One or more of, etc.; the compound containing transition metal element M is soluble salt containing M, and can be selected from C 10 H 5 NbO 20 Ammonium molybdate, H 6 TeO 6 、RuCl 3 、SnCl 4 、Na 2 WO 4 One or more of, etc.; preparing a compound containing Ni and M into a solution A with the total concentration of transition metal of 1-5 mol/L;
in the step 1, the concentration of the precipitant NaOH in the solution B is 2-10 mol/L, wherein the concentration of the ammonia water is within 2 mol/L.
In the step 2, preferably, the flow rate of the solution A is controlled to be 10-500 mL/min, the pH value of the reaction system is controlled to be 10-13, the reaction temperature is controlled to be 40-80 ℃, and the reaction time is controlled to be 30-50 h. Washing the precipitate with deionized water for several times (generally 4-8 times), placing the precipitate in a blast oven, drying the precipitate for 10-30 hours at a temperature of generally 80-120 ℃, sieving the obtained dried powder, controlling the ratio of the particle size distribution (D90-D10)/D50 to be 0.8-1.2, and sieving powder particles with a particle size of 3-15 mu m.
In the step 3, the lithium source is one or more of an organic lithium compound and an inorganic lithium compound, and may be selected from Li 2 CO 3 、LiOH、LiOH·H 2 O、Li 2 O、Li 2 O 2 One or more of lithium acetate, lithium oxalate and lithium nitrate. The precursor and the lithium source are mixed according to the stoichiometric ratio of transition metal to lithium of 1:1-1:1.2, and the excess of lithium is generally 1-10%. The oxidation atmosphere is preferably an oxygen split flow of 1-10 m 3 An atmosphere of/min. During sintering, the temperature is raised to 200-600 ℃ at a heating rate of 2-10 ℃/min for presintering for 2-6 hours, and then the temperature is raised to 600-800 ℃ at a heating rate of 1-5 ℃/min for 10-30 hours.
Compared with the prior art, the invention has the beneficial effects that:
the current modification research on the layered oxide cathode material mainly improves the electrochemical performance of the material by two technical means of doping and surface coating. The structural stability of the positive electrode material in the circulation process is improved by doping the inert material with high stability, and the irreversible phase change of the material is delayed mainly by inhibiting the phase change reaction of the material in a 4.2V region, but the influence of the phase change of the anisotropic structure cannot be fundamentally eliminated. The surface coating is mainly realized by forming a coating layer on the surface of the particles, so that side reactions with electrolyte are avoided. However, it is difficult to obtain a thin and uniform surface coating, and thus this method cannot fundamentally avoid the occurrence of interfacial side reactions. In order to obtain an electrode material with more excellent electrochemical performance, the industry generally adopts a technical means of coating and doping to improve the electrochemical performance of the material, which results in complex synthesis process of the material, and consistency is difficult to be well ensured. From the aspect of structural design, the invention designs and synthesizes the lithium ion battery layered oxide positive electrode material with transition metal superlattice structure, and the electrode material with excellent electrochemical performance is obtained through a simple preparation process.
In summary, the obvious benefits of the present invention are the following two points:
1. the design of the synthesized layered anode material with the transition metal superlattice structure can break the technical barriers of foreign patents;
2. the coprecipitation preparation process is simple and easy to implement, is easy to industrialize and amplify, and generates large-scale economic benefit.
Drawings
Fig. 1. Scanning Electron Microscope (SEM) pictures of the positive electrode materials prepared in example 1 of the present invention, including four positive electrode materials numbered NC95, NC95-T05, NC95-T1 and NC9595-T2, are magnified 1000 times on the left side and 60000 times on the right side of each material.
Fig. 2 is an X-ray diffraction (XRD) pattern of four positive electrode materials prepared in example 1 of the present invention.
Fig. 3 is a high angle annular dark field scanning transmission electron microscope (HADDF-STEM) image (top) and atomic contrast image (bottom) of the intra-layer superlattice structure of the cathode material synthesized in example 1 of the present invention.
FIG. 4 shows the first charge and discharge curves of the positive electrode material synthesized in example 1 of the present invention in the voltage range of 2.7-4.4V at a current density of 20 mA/g.
FIG. 5 is a graph showing the cycle performance of the positive electrode material synthesized in example 1 of the present invention, which was cycled for 100 weeks at a voltage ranging from 2.7 to 4.4V and a current density of 100 mA/g.
FIG. 6 shows a 55℃high temperature cycle curve of the cathode material synthesized in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail below, but it should be understood by those skilled in the art that the scope of the present invention is not limited thereto. All modifications and equivalents of the technical scheme of the invention are included in the protection of the invention without departing from the spirit and scope of the technical scheme of the invention.
Example 1 Synthesis of Te as Positive electrode Material for transition intermetallic superstructure ions
Step 1, weighing a proper amount of nickel source NiSO according to the molar ratio of 100:0, 99:1, 98:2 and 95:5 according to the total ion concentration of transition metal of 1 mol/L 4 And Te source Compound Na 6 TeO 6 Completely dissolved in deionized water of 2LThe solution is marked as solution A; OH at 2 mol/L - The ionic concentration is weighed, naOH is added with a certain amount of ammonia water as a complexing agent, wherein the final concentration of the ammonia water is 1 mol/L, and the mixed solution is marked as B. Dropping the solution A into the reaction kettle at a constant rate of 30mL/h, and dropping the solution B into the reaction kettle through the frequency conversion of the pH self-feedback regulating system; the reaction temperature is controlled at 55 ℃; the pH of the reaction was 11.5, and the reaction was stirred at 700 rpm to synthesize the target precursor. The precipitate produced by the reaction was washed 5 times with water by suction filtration, dried in a forced air drying oven at 100 ℃ for 20 h, and sieved through a 400 mesh sieve to obtain the dried target precursor.
And 2, respectively weighing lithium hydroxide and the precursor obtained in the step 1 according to the molar ratio of 1.05:1 (lithium excess), and performing mixed sintering. The sintering temperature is raised to 500 ℃ at a heating rate of 10 ℃/min, presintering is carried out for 4 h, then the temperature is raised to 750 ℃ at a heating rate of 5 ℃/min, and the heat preservation and sintering are carried out for 12 h. Finally obtaining the target anode material LiNi x Te 1-x O 2 And are marked NC95, NC95-T05, NC95-T1, NC95-T2 in sequence according to x being 1, 0.95, 0.99 and 0.98.
And 3, mixing the target anode material with carbon black and PVDF (polyvinylidene fluoride) according to a mass ratio of 8:1:1, uniformly grinding by taking N-methyl pyrrolidone as a solvent, coating the mixture on aluminum foil, and placing the aluminum foil in a blast drying oven for drying at 100 ℃ for 12 h. After removal, the electrode wafer was cut after several rolls on a roller press. The lithium ion battery high-voltage electrolyte is prepared from lithium ion battery high-voltage electrolyte produced by Beijing chemical reagent research, and a button battery is arranged in a glove box and tested at the temperature of 25 ℃ and 55 ℃.
As shown in fig. 1, as the spherical small particles of 4 μm or less increase in Te content and the primary particles taper, the remarkable trend of change in particle surface is mainly associated with the introduction of Te in high valence state, and it is demonstrated from the side that Te element can be co-precipitated with Ni element by this synthesis process.
As shown in fig. 2, XRD showed a gradual decrease in the intensity of the main peak around 20 °, which suggests that the structure is transformed from a lamellar phase to a locally disordered phase as the Te content increases. Thus, too much high a valence Te would cause a difficulty in the effective oxidation of the local Ni element, resulting in a more serious Li/Ni mixed discharge.
The spherical aberration electron microscope result of fig. 3 intuitively gives the super structure information of the ordered arrangement of the transition metal layers Te-Ni-Te. As shown by the white dashed box in the upper graph of fig. 3, since Te has a larger atomic number than Ni, the dark field image of the spherical aberration is more sensitive to heavy elements, and thus the "two-bright-one-brighter" atomic arrangement is clearly shown in the transition metal layer. The contrast distribution results for the different elements can also be clearly seen from the results graph of the contrast distribution (lower graph in fig. 3). This result provides direct strong evidence for the existence of the transition metal layer superstructure.
As shown in fig. 4, the change in the first-turn charge-discharge curve reflects the effect of layered materials of different Te contents on the reversible deintercalation ability of Li. The appropriate Te content can effectively improve the coulomb efficiency (delithiation reversibility) of the material, and the introduction of 1% Te can improve the coulomb efficiency of the material from 89% to 92%.
As shown in fig. 5, the capacities of NC95, NC95-T05, NC95-T1, NC95-T2 materials in the long cycle of 100 cycles were maintained as: 63%, 89%, 94% and 99%. Fig. 2 shows that severe Ni/Li mixing due to the higher Te content is a major cause of the influence on capacity release. The past experimental results show that the Li/Ni mixed discharge can cause the continuous collapse of the layered structure in the circulation process, so that the reversibility of the material can be influenced by the Li/Ni mixed discharge. Unlike the previous results, the structural stability is greatly improved and the delithiation reversibility is improved by forming an ordered superstructure of Ni-Te-Te-Ni in the transition metal layer. The data of the cyclic stability show the superiority of the ordered super-structure design among the metal elements in the transition metal layer.
As shown in fig. 6, the effect of side reactions can be amplified due to temperature factors. The superiority of the structural design can be further demonstrated by conducting long-cycle testing at a high temperature of 55 ℃. The stability test of the material with the preferred Te content of 1% shows that the capacity retention rate of 83% after 200 cycles is still improved by 1.5 times compared with the retention rate of 33% of the original sample.
Example 2 Synthesis of W as Positive electrode Material for transition intermetallic superstructure ions
Step 1 (precursor preparation), weighing a proper amount of NiSO according to the mole ratio of 99:1, 98:2 and 95:5 with the total ion concentration of transition metal of 1 mol/L 4 And Na (Na) 2 WO 4 Completely dissolved in deionized water of 2L and designated as solution a; OH at 2 mol/L - The ion concentration is weighed, naOH is added with a certain amount of ammonia water as a complexing agent, wherein the concentration of the ammonia water is 1 mol/L, and the mixed solution is marked as B. Dropping the solution A into the reaction kettle at a constant rate of 30mL/h, and dropping the solution B into the reaction kettle through the frequency conversion of the pH self-feedback regulating system; the reaction temperature is controlled at 55 ℃; the pH of the reaction was 11.5, and the reaction was stirred at 700 rpm to synthesize the target precursor. The precipitate produced by the reaction was washed 5 times with water by suction filtration, dried in a forced air drying oven at 100 ℃ for 20 h, and sieved through a 400 mesh sieve to obtain the dried target precursor.
And 2 (sintering process) respectively weighing lithium hydroxide and the precursor obtained in the step 1 according to a molar ratio of 1.05:1 (lithium excess), and performing mixed sintering. The sintering temperature is raised to 500 ℃ at a heating rate of 10 ℃/min, presintering is carried out for 4 h, then the temperature is raised to 750 ℃ at a heating rate of 5 ℃/min, and the heat preservation and sintering are carried out for 12 h. Finally, the target anode material is obtained.
Step 3 (battery assembly), mixing the target positive electrode material with carbon black and PVDF according to a mass ratio of 8:1:1, uniformly grinding the mixture by taking N-methyl pyrrolidone as a solvent, then coating the mixture on an aluminum foil, and placing the aluminum foil in a blast drying oven for drying at 100 ℃ for 12 h. After removal, the electrode wafer was cut after several rolls on a roller press. The lithium ion battery high-voltage electrolyte is prepared from lithium ion battery high-voltage electrolyte produced by Beijing chemical reagent research, and a button battery is arranged in a glove box and tested at the temperature of 25 ℃ and 55 ℃.
The doped sample of W also has the "two-bright one-brighter" superstructure characteristics in the transition metal layer, but due to the larger atomic halves of WThe diameter is such that there are transitional vacancies in the material, either due to the dislocation defect of Li. Too much W will be concentrated on the surface and difficult to effectively enter the interior of the material. Surface enriched W is sintered with Li 2 WO 4 The ionic conductivity and the electronic conductivity of the material can be effectively improved. The long-cycle test data result shows that the 1% W-doped sample can improve the cycle retention rate of the material for 100 circles from 65% to 88%.
Example 3 Synthesis of Nb as Positive electrode Material for transition intermetallic superstructure ions
By niobium oxalate C 10 H 5 NbO 20 The procedure of synthesis was the same as in example 1, except that the Te source compound was replaced. The obtained positive electrode material is LiNi 0.99 Nb 0.01 O 2 。
The Nb doped samples also have a "two-bright one-brighter" superstructure characteristic in the transition metal layer. Nb (Nb) 5+ Has a chemical structure with Li + Similar ionic radii, thus apart from forming an ordered superstructure, a portion Nb 5+ Will also occupy Li in the Li layer + A site. Thus resulting in poor rate performance of the material. 2000 The discharge specific capacity of 100 mAh/g at the current density of mA/g is slightly inferior to that of the original material of 170 mAh/g (2000 mA/g). But the material has good cycle stability, and the long-cycle test data shows that the 1% Nb doped sample can improve the cycle retention rate of the material for 100 circles from 65% to 92%.
Example 4 Synthesis of Ta as Positive electrode Material for transition intermetallic superstructure ions
By TaCl 5 The procedure of synthesis was the same as in example 1, except that the Te source compound was replaced. The obtained positive electrode material is LiNi 0.6 Ta 0.4 O 2 。
The synthesized material transition metal layer has obvious Ta-Ni-Ni-Ta ordered super structure characteristic. The reversible capacity of the material can reach 150 mAh/g (20 mA/g current density), and the cycle retention rate of 100 circles is 98%.
Example 5 Synthesis of Mo as Positive electrode Material for transition intermetallic superstructure ions
By ammonium molybdate(NH 4 ) 2 MoO 4 The procedure of synthesis was the same as in example 1, except that the Te source compound was replaced. The obtained positive electrode material is LiNi 0.7 Mo 0.3 O 2 。
Macroscopically, the disorder is apparent, but the local transition metal layer also has the super-structural characteristics of Mo-Ni-Ni-Mo. The reversible specific capacity of the material is low and is only 100 mAh/g, but the circulation capacity of the material is hardly attenuated after 100 circles.
Claims (9)
1. A layered oxide positive electrode material with a chemical formula of LiNi x M 1-x O 2 Wherein M is a high valence transition metal element with an atomic number greater than 40 and less than 84, and is selected from one or more of Te, W, nb, ta; at least one set of minimum super-structural units of-M-Ni-Ni-M-is contained in a single transition metal layer, and a superlattice structure is formed between low-valence element Ni and high-valence element M with high atomic number through electrostatic interaction; and the valence state of M and the valence state of Ni keep a specific corresponding relation, and the valence state is characterized in that: ni (Ni) 2+ Corresponds to M 4+ While Ni 3+ Then corresponds to M 6+ Or M 5+ The method comprises the steps of carrying out a first treatment on the surface of the The atomic ratio between Ni and M is 2:1-1:0.01, namely 0<x<1 and x/(1-x) is 2 to 100.
2. The layered oxide cathode material of claim 1, wherein x is 0.5 to 0.99.
3. The layered oxide cathode material of claim 1, wherein the layered oxide cathode material has a chemical formula LiNi 0.99 Te 0.1 O 2 、LiNi 0.98 Te 0.02 O 2 、LiNi 0.95 Te 0.05 O 2 、LiNi 2/3 Te 1/3 O 2 、LiNi 0.99 W 0.1 O 2 、LiNi 0.98 W 0.02 O 2 、LiNi 0.95 W 0.05 O 2 、LiNi 0.99 Nb 0.01 O 2 Or LiNi 0.6 Ta 0.4 O 2 。
4. The method for preparing the layered oxide cathode material according to any one of claims 1 to 3, comprising the steps of:
1) Weighing chemical LiNi x M 1-x O 2 The compound containing Ni and M transition metal elements in the stoichiometric ratio is prepared into a solution which is marked as solution A; weighing NaOH with the concentration of transition metal being 2 times of the stoichiometric ratio, adding ammonia water as a complexing agent, and marking the formed mixed solution as a solution B;
2) Dropwise adding the solution A into a reaction kettle at a constant flow rate through a coprecipitation process, dropwise adding the solution B into the reaction kettle through a pH self-feedback regulating system in a variable frequency manner, controlling the pH value of the reaction system to be between 10 and 13, obtaining precipitate after reaction, washing, drying, and sieving the obtained dry powder to obtain a precursor;
3) Uniformly mixing the precursor obtained in the step 2) with a lithium source, placing the mixed powder into a high-temperature reaction vessel, sintering in an oxidizing atmosphere, heating to 200-600 ℃ at a heating rate of 2-10 ℃/min for presintering for 2-6 h, heating to 600-800 ℃ at a heating rate of 1-5 ℃/min for sintering for 10-30 h, and obtaining the layered oxide anode material LiNi x M 1-x O 2 。
5. The process according to claim 4, wherein the Ni-containing compound used for preparing solution A in step 1) is selected from NiSO 4 、NiCH 3 COOH、Ni(NO 3 ) 2 The compound containing M is soluble salt containing M, and the compound containing Ni and M is prepared into solution A with the total concentration of transition metal of 1-5 mol/L.
6. The preparation method of claim 4, wherein the concentration of NaOH in the solution B is 2-10 mol/L, and the concentration of ammonia water is within 2 mol/L.
7. The method according to claim 4, wherein the flow rate of the solution A in the step 2) is controlled to be 10-500 mL/min, the pH value of the reaction system is controlled to be 10-13, the reaction temperature is controlled to be 40-80 ℃, and the reaction time is controlled to be 30-50 h.
8. The method according to claim 4, wherein the precipitate is washed with deionized water several times in step 2), dried in a forced air oven at 80-120 ℃ for 10-30 hours, the obtained dried powder is sieved, the ratio of the particle size distribution (D90-D10)/D50 is controlled to be 0.8-1.2, and powder particles with the particle size of 3-15 μm are selected.
9. The method of claim 4, wherein the lithium source in step 3) is selected from the group consisting of Li 2 CO 3 、LiOH、LiOH·H 2 O、Li 2 O、Li 2 O 2 One or more of lithium acetate, lithium oxalate, and lithium nitrate; mixing the precursor and a lithium source according to the stoichiometric ratio of transition metal to lithium of 1:1-1:1.2; the oxygen shunt quantity in the oxidizing atmosphere is 1-10 m 3 An atmosphere of/min.
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