CN110970616B - Preparation method of NCM (negative carbon) ternary cathode material with high-density dislocation on surface - Google Patents

Preparation method of NCM (negative carbon) ternary cathode material with high-density dislocation on surface Download PDF

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CN110970616B
CN110970616B CN201911333077.XA CN201911333077A CN110970616B CN 110970616 B CN110970616 B CN 110970616B CN 201911333077 A CN201911333077 A CN 201911333077A CN 110970616 B CN110970616 B CN 110970616B
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dislocation
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ternary cathode
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苏岳锋
张其雨
陈来
卢赟
吴锋
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Beijing Institute of Technology BIT
Chongqing Innovation Center of Beijing University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • 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
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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
    • H01M4/52—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
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    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method of an NCM ternary cathode material with high-density dislocation on the surface. The method comprises the steps of firstly soaking the NCM ternary cathode material in an acidic buffer solution for a certain time, and regulating and controlling the calcination time and temperature during the subsequent annealing calcination in an inert gas atmosphere to finally form a large number of oxygen vacancies on the surface of the material. The formation of oxygen vacancies leads to a high density of dislocations in the layered structure of the material surface. The cross-cutting effect of the high-density dislocation can inhibit dislocation generated by mutual extrusion of material particles from moving to the interior of the material in the long-cycle charge and discharge process, so that the particle integrity of the material is maintained; meanwhile, the integrity of the particles reduces the exposure of the fresh surface of the material, reduces the corrosion of the electrolyte to the anode material, and simultaneously reduces the interface side reaction, thereby improving the cycling stability of the material in the cycling charge-discharge process. The raw materials used in the method disclosed by the invention are nontoxic and environment-friendly, meet the requirements of green chemistry, are simple to operate and convenient to implement, and have good industrial application prospects and economic benefits.

Description

Preparation method of NCM (negative carbon) ternary cathode material with high-density dislocation on surface
Technical Field
The invention relates to a preparation method of an NCM ternary cathode material with high-density dislocation on the surface, in particular to a method for preparing an NCM ternary material with a high-density dislocation structure on the surface by soaking in an acidic buffer solution and then annealing and calcining in inert gas, belonging to the field of chemical energy storage batteries.
Background
With the increasing severity of the problems of environmental pollution, energy exhaustion and the like, researchers in the field of energy have an intense interest in the development and research of novel clean energy. As a clean and green secondary energy source, electric energy is gradually replacing the traditional fossil energy source in daily life. Meanwhile, due to the wide use of electric automobiles and portable mobile electronic devices,the development of electrical energy storage devices is also becoming increasingly important. Lithium ion batteries have been studied in large quantities as the most interesting electric energy storage devices at present, and high energy density has become the main research direction of lithium ion batteries under the requirement of high cruising ability. As a main limiting factor of energy density of lithium ion batteries, research and development of positive electrode materials mainly focus on how to improve charge-discharge specific capacity of the positive electrode materials. Compared with other cathode materials, the NCM ternary cathode material (LiNi)xCoyMn1-x-yO2Wherein 0.6<x<1) Due to the advantages of the lithium ion battery in specific capacity, price and the like, the lithium ion battery is generally concerned in the field of research and development of positive electrode materials. With the increase of the nickel content, the specific discharge capacity of the NCM ternary cathode material is obviously increased, but the cycling stability of the material is also greatly reduced, and the service life of the battery is shortened.
The stability of the layered structure of the NCM ternary cathode material directly determines the cycling stability, and therefore, in order to improve the cycling stability of the NCM ternary cathode material, it is necessary to start with the aspect of enhancing the structural stability of the material. The specific capacity of the anode material under the same condition is only Li extracted/inserted from the anode material+Content-dependent, and therefore a large amount of Li is necessary to obtain a high charge-discharge capacity+Repeated deintercalation in the material lattice, and Li+Frequent changes in the material lattice size due to repeated deintercalation are the main cause of poor structural stability of the positive electrode material. Partial research is carried out on the NCM material surface layer doped with other transition metal elements (such as zirconium, titanium and the like) to stabilize the material surface layer structure, so as to achieve the purpose of relieving the internal phase change and the structure collapse of the material, but the method cannot fundamentally inhibit the negative influence caused by the lattice distortion process. The NCM ternary positive electrode material is generally synthesized by a coprecipitation method and a high-temperature solid-phase method, and the obtained secondary particles of the material are stacked by smaller primary particles. Li+The greater the degree of deintercalation from the crystal lattice, the more severe the distortion of the crystal lattice of the material, which leads to more pronounced squeezing phenomena between the primary particles. The extrusion process promotes the accumulation of internal stresses in the primary particles and the formation of dislocation structures, which migrate from the surface of the material to the interior and accelerate the occurrence of cracks in the grains. Internal crackingThe formation of the composite electrolyte provides a channel for the electrolyte to erode the anode material, thereby causing more interface side reactions, inducing the problems of material phase change, laminated structure collapse and the like, and causing the service life of the battery to be greatly reduced.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing an NCM ternary cathode material with high surface density dislocation; the method comprises the steps of firstly soaking an NCM ternary cathode material in an acidic buffer solution for a certain time, and regulating and controlling the calcination time and temperature during the subsequent annealing calcination in an inert gas atmosphere to finally form a large number of oxygen vacancies on the surface of the material. The formation of oxygen vacancies leads to a high density of dislocations in the layered structure of the material surface. The cross-cutting effect of the high-density dislocation can inhibit dislocation generated by mutual extrusion of material particles from moving to the interior of the material in the long-cycle charge and discharge process, so that the particle integrity of the material is maintained; meanwhile, the integrity of the particles reduces the exposure of the fresh surface of the material, reduces the corrosion of the electrolyte to the anode material, and simultaneously reduces the interface side reaction, thereby improving the cycling stability of the material in the cycling charge-discharge process.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an NCM ternary cathode material with high-density dislocation on the surface comprises the following steps:
mixing an acidic buffer solution with the pH value of 3-7 and volatile alcohols according to the volume ratio of 10: 1-1: 10, and stirring and mixing uniformly at the temperature of 30-60 ℃ for 10-60 min to obtain a mixed solution;
adding 20g of NCM ternary positive electrode material into the mixed solution obtained in the step (1), and continuously maintaining the stirring temperature of 30-60 ℃ for 1-30 min to obtain suspension;
step (3) filtering the suspension obtained in the step (2) under reduced pressure to obtain a solid filtering material;
and (4) placing the solid material in a tube furnace, and annealing for 1-10 h at 200-600 ℃ in an inert gas atmosphere to obtain the NCM ternary cathode material with high-density dislocation on the surface.
Preferably, the acidic buffer solution in step (1) is one or more of disodium hydrogen phosphate-citric acid buffer solution, citric acid-sodium hydroxide-hydrochloric acid buffer solution, citric acid-sodium citrate buffer solution, acetic acid-sodium acetate buffer solution, phthalic acid-hydrochloric acid buffer solution and barbiturate sodium-hydrochloric acid buffer solution.
Preferably, the volatile alcohol in step (1) is ethanol.
Preferably, the NCM ternary positive electrode material in the step (2) is Li (Ni)0.8Co0.1Mn0.1)O2。
Preferably, the inert atmosphere in step (4) is a nitrogen atmosphere.
Preferably, the NCM ternary positive electrode material is obtained by a hydroxide coprecipitation method and a high-temperature solid-phase method.
The invention relates to a lithium ion battery, wherein the positive electrode material of the battery adopts the NCM ternary positive electrode material with high-density dislocation on the surface.
Advantageous effects
The method comprises the steps of soaking an NCM ternary positive electrode material in an acidic buffer solution, destroying the strong ionic bonding effect of metal ions and oxygen anions on the surface of the NCM ternary material through a stable acidic pH environment in the acidic buffer solution, and simultaneously placing the filtered material in an inert atmosphere environment for annealing, wherein the oxygen anions on the surface of the material, which are reduced by the ionic bonding effect caused by the acidic environment, can be released in the form of oxygen due to the lower oxygen partial pressure in the inert atmosphere, so that a large number of oxygen vacancies are formed on the surface of the material. A large number of oxygen vacancies are connected with each other to finally form a dislocation structure with higher density. The high-density dislocations are subjected to a cross-cut action, and thus, they are mutually inhibited from migrating, and finally, they are deposited on the surface of the material to form a high-density dislocation layer. Stress accumulation and dislocation can be generated due to mutual extrusion of primary particles in the cyclic charge and discharge process of the material, and the dislocation can migrate to the interior of the material under the action of stress. The high-density dislocation layer structure can effectively play a role in the dislocation generated in the circulation process, so that the new dislocation generated in the circulation process is inhibited from moving to the interior of the material, and the possibility of the occurrence of primary particle cracks of the material is reduced. Because the method adopts the acidic buffer solution to soak the material, oxygen vacancies and high-density dislocations are formed in the inert atmosphere annealing process, the acidic buffer solution mainly plays an auxiliary role, and simultaneously the acidic buffer solution can maintain the balance of the surface reaction of the material, so the damage to the layered structure of the material is less compared with the direct acid treatment of the material.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the final product prepared in example 1.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description taken in conjunction with 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. Additionally, the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
For a better understanding of the present invention, the present invention is described in further detail below with reference to specific examples.
In the following examples 1 to 3, the material characterization and analysis methods used were as follows:
scanning Electron Microscope (SEM) testing: scanning electron microscope, instrument model: FEI Quanta, the netherlands.
Electron paramagnetic resonance spectroscopy (EPR) test: an electron paramagnetic resonance spectrometer, the instrument model is as follows: Bruker-A300-10/12, Germany.
Projection electron microscope (TEM) testing: projection electron microscope, instrument type: transmission electron microscope 2100F, japan.
Assembling and testing of CR2025 button cells: dividing NCM into threeThe method comprises the steps of preparing a raw cathode material (a final product prepared in an example), acetylene black and polyvinylidene fluoride (PVDF) into slurry according to the mass ratio of 8:1:1, coating the slurry on an aluminum foil, cutting the dried aluminum foil loaded with the slurry into small round pieces with the diameter of about 1cm by using a cutting machine to serve as a cathode, using a metal lithium piece as a cathode, using Celgard2500 as a diaphragm and using 1M carbonate solution as an electrolyte (wherein a solvent is a mixed solution of ethylene carbonate and dimethyl carbonate with the volume ratio of 1:1, and a solute is LiPF6) And assembling the button cell CR2025 in an argon atmosphere glove box.
NCM ternary cathode material (LiNi)0.8Co0.1Mn0.1O2) The catalyst is prepared by a hydroxide coprecipitation method:
step (1) NiSO4·6H2O solid, CoSO4·7H2O solids, MnSO4·H2210.28g, 28.11g and 16.9g of solid O were weighed out in a molar ratio of Ni to Co to Mn to 8 to 1. Adding three sulfates into 500mL of deionized water, dissolving to form metal ions with the total concentration of 2 mol.L-1A metal salt solution of (a); weighing 100g of sodium hydroxide, adding 500mL of deionized water to prepare 2 mol.L-1NaOH solution of (2); 50mL of 30% ammonia water solution is measured, and deionized water is added to prepare 2 mol.L-1Aqueous ammonia solution of (2).
Adding 1000mL of deionized water into a reaction kettle to serve as a coprecipitation reaction base solution, wherein stirring and water bath processes are required in the whole reaction stage, the temperature of the water bath is controlled to be about 55 ℃, the stirring speed is stabilized at 800r/min, argon protective gas is introduced before the reaction is started to ensure that the whole reaction is carried out in an argon atmosphere, pumping 30% ammonia water solution to control the pH value of the base solution to 11, pumping the metal salt solution, NaOH solution and ammonia water solution into a reaction kettle by a peristaltic pump, controlling the feeding speed of the metal salt solution and the ammonia water solution at 1mL/min, adjusting the feeding speed of the NaOH solution to stabilize the pH value of the reaction at 11, entering an aging stage after the feeding is finished, keeping the original temperature and the original rotating speed, continuously stirring for 2 hours, after the aging is finished, filtering and washing the hot solution, and then putting the precipitate into a vacuum drying oven at 80 ℃ for drying for 24h to finally obtain Ni.0.8Co0.1Mn0.1(OH)2And (3) precursor.
Step (3) weighing 10g of precursor Ni0.8Co0.1Mn0.1(OH)2Weighing LiOH. H24.771g of O solid, mixing the two with absolute ethyl alcohol, grinding the mixture in a mortar for 30min, putting the material into a muffle furnace for calcination after the absolute ethyl alcohol is completely volatilized, controlling the heating rate to be 2 ℃/min and heating to be 550 ℃, preserving heat for 5h, controlling the heating rate to be 5 ℃/min and heating to be 750 ℃, preserving heat for 15h, and cooling the calcined material to obtain the NCM ternary cathode material (LiNi)0.8Co0.1Mn0.1O2)。
Example 1
Mixing a disodium hydrogen phosphate-citric acid buffer solution with the pH value of 4.6 and ethanol according to the volume ratio of 10:1, and stirring and mixing uniformly at 40 ℃ for 20min to obtain a mixed solution;
step (2) adding 20g of NCM ternary positive electrode material into the mixed solution obtained in the step (1), and continuously maintaining the stirring temperature of 40 ℃ for 10min to obtain suspension;
step (3) filtering the suspension obtained in the step (2) under reduced pressure to obtain a solid filtering material;
and (4) placing the solid material in a tube furnace, and annealing for 3h at 300 ℃ under the control of the temperature in a nitrogen atmosphere to obtain the NCM ternary cathode material with high-density dislocation on the surface.
The scanning electron microscope result of the final product is shown in fig. 1, and it can be seen from the figure that the final product is secondary particles, the secondary particles are mainly formed by stacking primary particles, and the surface of the primary particles has tiny defects, which are mainly caused by soaking in an acidic buffer solution.
The electron paramagnetic resonance spectrum result of the final product shows that the structure with oxygen vacancies at the position with the g factor of 2.0004 proves that a large number of oxygen vacancies exist on the surface of the material.
The observation result of the final product by using a transmission electron microscope shows that a large number of obvious dislocation structures exist on the surface of the primary particles before the final product circulates, certain disorder occurs in the lamellar structures, the main form of dislocation is edge dislocation, the dislocation density is high, and the stacking is obvious.
The observation result of the transmission electron microscope after the final product assembled battery is tested shows that the phase change process of the material surface is weaker due to the existence of high-density dislocation after circulation, and meanwhile, no intragranular crack occurs in the primary particles of the material.
According to the electrochemical test result of the final product, after the assembled battery is cycled for 100 weeks at a cut-off voltage of 2.8-4.3V and a multiplying power of 0.2C, the capacity retention rate of the NCM ternary cathode material is improved compared with that of an unmodified material, which shows that the high-density dislocation on the surface of the NCM ternary cathode material can inhibit the occurrence of intragranular cracks caused by stress accumulation in the cycle process, so that the corrosion process of the electrolyte to the cathode material is inhibited, the interface side reaction is reduced, and the cycle stability retention rate of the material in the long cycle process is improved.
Example 2
Mixing a citric acid-sodium hydroxide-hydrochloric acid buffer solution with pH of 5.3 and ethanol according to a volume ratio of 5:1, and uniformly stirring and mixing at 30 ℃ for 20min to obtain a mixed solution;
step (2) adding 20g of NCM ternary cathode material into the mixed solution obtained in the step (1), and continuously maintaining the stirring temperature of 30 ℃ for 5min to obtain a suspension;
step (3) decompressing and filtering the suspension obtained in the step (2) to obtain a solid filtering material;
and (4) placing the solid material in a tube furnace, and annealing for 3h at 400 ℃ in a nitrogen atmosphere at a controlled temperature to obtain the NCM ternary cathode material with high-density dislocation on the surface.
Example 3
Mixing a citric acid-sodium citrate buffer solution with the pH value of 4.0 and ethanol according to the volume ratio of 1:1, and uniformly stirring and mixing at 60 ℃ for 30min to obtain a mixed solution;
step (2) adding 20g of NCM ternary positive electrode material into the mixed solution obtained in the step (1), and continuously maintaining the stirring temperature at 60 ℃ for 10min to obtain suspension;
step (3) filtering the suspension obtained in the step (2) under reduced pressure to obtain a solid filtering material;
and (4) placing the solid material in a tube furnace, and annealing for 8 hours at 500 ℃ in a nitrogen atmosphere to obtain the NCM ternary cathode material with high-density dislocation on the surface.
Example 4
Mixing acetic acid-sodium acetate buffer solution with pH of 4.6 and ethanol according to a volume ratio of 1:3, and stirring and mixing uniformly at 50 ℃ for 40min to obtain a mixed solution;
step (2) adding 20g of NCM ternary positive electrode material into the mixed solution obtained in the step (1), and continuously maintaining the stirring temperature of 50 ℃ for 15min to obtain suspension;
step (3) filtering the suspension obtained in the step (2) under reduced pressure to obtain a solid filtering material;
and (4) placing the solid material in a tube furnace, and annealing for 10 hours at 600 ℃ in a nitrogen atmosphere at a controlled temperature to obtain the NCM ternary cathode material with high-density dislocation on the surface.
Example 5
Mixing phthalic acid-hydrochloric acid buffer solution with pH of 3.0 and ethanol according to a volume ratio of 1:7, and stirring and mixing uniformly at 30 ℃ for 40min to obtain mixed solution;
step (2) adding 20g of NCM ternary cathode material into the mixed solution obtained in the step (1), and continuously maintaining the stirring temperature at 30 ℃ for 10min to obtain a suspension;
step (3) filtering the suspension obtained in the step (2) under reduced pressure to obtain a solid filtering material;
and (4) placing the solid material in a tube furnace, and annealing for 8 hours at 300 ℃ in a nitrogen atmosphere at a controlled temperature to obtain the NCM ternary cathode material with high-density dislocation on the surface.
Example 6
Mixing a barbital sodium-hydrochloric acid buffer solution with the pH value of 6.8 and ethanol according to the volume ratio of 1:10, and uniformly stirring and mixing at 50 ℃ for 10min to obtain a mixed solution;
step (2) adding 20g of NCM ternary positive electrode material into the mixed solution obtained in the step (1), and continuously maintaining the stirring temperature at 50 ℃ for 30min to obtain a suspension;
step (3) filtering the suspension obtained in the step (2) under reduced pressure to obtain a solid filtering material;
and (4) placing the solid material in a tube furnace, and annealing for 4 hours at 400 ℃ under the control of the temperature in the nitrogen atmosphere to obtain the NCM ternary cathode material with high-density dislocation on the surface.
The present invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the principle of the spirit of the present invention are considered to be within the scope of the present invention.

Claims (10)

1. A preparation method of a surface high-density dislocation NCM ternary cathode material is characterized by comprising the following steps:
(1) mixing an acidic buffer solution with the pH value of 3-7 and volatile alcohols according to the volume ratio of 10: 1-1: 10, and stirring and mixing uniformly at the temperature of 30-60 ℃ for 10-60 min to obtain a mixed solution;
(2) adding 20g of NCM ternary cathode material into the mixed solution obtained in the step (1), and continuously maintaining the stirring temperature of 30-60 ℃ for 1-30 min to obtain suspension;
(3) filtering the suspension obtained in the step (2) under reduced pressure to obtain a solid filtering material;
(4) and (3) placing the solid material in a tube furnace, and annealing for 1-10 h at 200-600 ℃ in an inert gas atmosphere to obtain the NCM ternary cathode material with high-density dislocation on the surface.
2. The method for producing a surface high density dislocation NCM ternary positive electrode material as claimed in claim 1, characterized in that in step (1), the acidic buffer solution is one or a mixture of more of disodium hydrogen phosphate-citric acid buffer solution, citric acid-sodium hydroxide-hydrochloric acid buffer solution, citric acid-sodium citrate buffer solution, acetic acid-sodium acetate buffer solution, phthalic acid-hydrochloric acid buffer solution, barbituric acid sodium-hydrochloric acid buffer solution;
in the step (1), the volatile alcohol is ethanol.
3. The method for preparing the surface high-density dislocation NCM ternary cathode material as claimed in claim 1, wherein in the step (2), the NCM ternary cathode material is Li (Ni)0.8Co0.1Mn0.1)O2。
4. The method for preparing the surface high density dislocation NCM ternary cathode material as claimed in claim 1, wherein in step (4), the inert atmosphere is nitrogen atmosphere.
5. The method for preparing the surface high-density dislocation NCM ternary cathode material according to claim 1, characterized in that the NCM ternary cathode material is obtained by a hydroxide coprecipitation method and a high-temperature solid phase method.
6. The method for preparing the surface high-density dislocation NCM ternary cathode material according to claim 1, wherein the surface of the primary particles of the NCM ternary cathode material has a high-density dislocation structure, and the dislocation structure comprises screw dislocation, edge dislocation and the mixture of the screw dislocation and the edge dislocation.
7. The method for producing a surface high density dislocation NCM ternary positive electrode material as claimed in claim 6, wherein said high density dislocation structure is composed of a large number of oxygen vacancies.
8. The method for preparing the surface high-density dislocation NCM ternary cathode material according to claim 1, characterized in that the molar ratio of Ni, Co and Mn in the NCM ternary cathode material is 8:1: 1.
9. A lithium ion positive electrode material comprising the surface high density dislocation NCM ternary positive electrode material obtained by the method of any one of claims 1 to 8.
10. A lithium ion battery comprising the surface high density dislocation NCM ternary positive electrode material obtained by the method of any one of claims 1 to 8 and the lithium ion positive electrode material of claim 9.
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