CN115224264B - Protective lithium battery positive electrode material and preparation method thereof - Google Patents

Protective lithium battery positive electrode material and preparation method thereof Download PDF

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CN115224264B
CN115224264B CN202211039078.5A CN202211039078A CN115224264B CN 115224264 B CN115224264 B CN 115224264B CN 202211039078 A CN202211039078 A CN 202211039078A CN 115224264 B CN115224264 B CN 115224264B
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solution
powder
positive electrode
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lithium battery
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CN115224264A (en
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严学庆
袁朝勇
袁朝明
钱军
李国辉
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JIANGSU OLITER ENERGY TECHNOLOGY 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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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/362—Composites
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    • H—ELECTRICITY
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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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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • 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
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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 relates to a protective lithium battery anode material and a preparation method thereof, and belongs to the technical field of lithium batteries. The positive electrode material is Ni 0.6 Co 0.18 Mn 0.22 (OH) 2 The ternary precursor has higher capacity, the first discharge capacity reaches 201.5-207.9mAh/g through testing, double bonds are grafted on the surface through vinyl trimethoxy silane, then the double bonds are oxidized through concentrated sulfuric acid and sodium nitrate, tantalum and silver elements are coated on the surface of matrix powder by utilizing the chelating property of carboxyl, and after reduction, protective layers of tantalum, silver and oxides thereof are formed on the surface, so that the reaction of a positive electrode material and electrolyte is effectively relieved, irreversible phase change and transition metal dissolution are inhibited, the capacity retention rate reaches 95.9-96.7% after the cycle through testing, and the protective layers have good conductivity and have the impedance of only 103.7-110.2 omega through testing.

Description

Protective lithium battery positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a protective lithium battery anode material and a preparation method thereof.
Background
The lithium battery has the advantages of high energy density, good cycle performance and the like, and is widely applied to various fields of electronic products, automobiles, aerospace and the like. As the core of the lithium ion battery, the quality of the positive electrode material directly determines the quality of the battery performance, wherein the energy density of the lithium ion battery mainly depends on the energy density of the positive electrode material, and therefore, the positive electrode material becomes the focus of research of the lithium ion battery.
At present, a layered positive electrode material NCM811 with high specific capacity and low cost is regarded as the positive electrode material with the current most application prospect, but the capacity retention rate is low, the thermal stability is poor, a coating method is adopted to protect the positive electrode material in the prior art, for example, the ternary positive electrode material is protected by lithium silicate in China patent with the application number of 201410730319.X, lithium silicate is deposited on the surface of the ternary positive electrode material, and the lithium silicate is unevenly coated by the method, so that the stable protection effect is difficult to achieve, the impedance of the lithium silicate is larger, the internal resistance of a battery is influenced, and the discharge capacity of the battery is reduced; therefore, the invention develops the protective lithium battery anode material from the perspective of cooperatively improving the capacity and the stability of the battery.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a protective lithium battery anode material and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the protective lithium battery anode material specifically comprises the following steps:
step A1: preparing a nickel source, a cobalt source and a manganese source by deionized water into a nickel, cobalt and manganese element molar mass ratio of 0.6:0.18:0.22, uniformly mixing distilled water and hydrazine hydrate to obtain a base solution, taking a reaction kettle, introducing high-purity nitrogen into the reaction kettle, discharging air in the reaction kettle to enable the reaction kettle to be in a nitrogen protection atmosphere, injecting the base solution into the reaction kettle, heating a water bath of the reaction kettle to 58-65 ℃ for heat preservation, controlling the stirring speed to 240-300rpm, simultaneously and slowly injecting the metal salt solution, the sodium hydroxide solution and ammonia water into the reaction kettle, continuously carrying out heat preservation and stirring for 60-80min after all injection, fully carrying out precipitation reaction, and then leaching a filter cake, adopting nitrogen protection for drying to prepare a ternary precursor;
further, the nickel source, cobalt source and manganese source are selected from sulfate, and the mass fraction of the metal salt solution is 10-15%.
Further, the volume ratio of distilled water to hydrazine hydrate is 100:5-8.
Further, the dosage ratio of the base solution, the metal salt solution, the sodium hydroxide solution and the ammonia water is 1L:600-700mL:60-80mL:120-150mL, 25% of sodium hydroxide solution by mass and 18% of ammonia water.
Step A2: taking lithium hydroxide and a ternary precursor, carrying out dry-method cyclic grinding, and controlling the molar ratio of the lithium element to the metal element in the ternary precursor to be 1.1:1, placing the grinding powder into a muffle furnace preheated to 260 ℃ for roasting for 30min until the median particle diameter of the grinding powder reaches 11 mu m, rapidly removing crystal water, rapidly heating to 820-840 ℃ for roasting for 6-8h, cooling, and placing into a blade type scattering machine for scattering to prepare matrix powder;
step A3: taking matrix powder and ethanol solution for ultrasonic dispersion, adding vinyl trimethoxy silane for mixing, regulating the pH value to 4 by hydrochloric acid, stirring and heating to 55-60 ℃, controlling the heating time to be not more than 10min, avoiding the self-condensation of the vinyl trimethoxy silane, slowly dripping sodium hydroxide solution for stirring and mixing until the pH value is regulated to 9, standing for 12h, taking the lower layer of sediment for washing, filtering and drying to prepare vinyl powder;
further, the usage ratio of the matrix powder, the vinyl trimethoxy silane and the ethanol solution is 100g:5mL:200-250mL, and the volume fraction of the ethanol solution is 30%.
Step A4: mixing vinyl powder and concentrated sulfuric acid under stirring for 20-30min, heating to 40-50deg.C, adding sodium nitrate solution, mixing for 12-18min, oxidizing double bonds grafted on the surface of vinyl powder into carboxyl and partial residual aldehyde groups, press filtering, washing precipitate, and drying to obtain modified powder;
further, the dosage ratio of the vinylation powder, the concentrated sulfuric acid and the sodium nitrate solution is 100g:60-70mL:150-200mL, the mass fraction of concentrated sulfuric acid is 75%, and the mass fraction of sodium nitrate solution is 8%.
Step A5: mixing tantalum ethoxide, silver nitrate solution and absolute ethyl alcohol, regulating the pH value to 5 by sulfuric acid, adding modified powder for mixing in an ultrasonic dispersion state, centrifuging, taking out the lower layer precipitate, washing, drying, placing in a hydrogenation furnace, heating to 300-360 ℃, preserving heat, reducing for 2h, and cooling to obtain the anode material.
Further, the dosage ratio of the modified powder, the tantalum ethoxide and the silver nitrate solution is 100g:5.5-8g:10-15mL, and the mass fraction of the silver nitrate solution is 38%.
The invention has the beneficial effects that:
1. according to the invention, the high-nickel ternary precursor is used as a doped matrix, so that higher capacity is obtained, the manganese content is properly increased, the thermal stability of the positive electrode material is improved, and the initial discharge capacity reaches 201.5-207.9mAh/g through test.
2. The invention provides a protection method for a positive electrode material, which is characterized in that after vinyl trimethoxy silane is hydrolyzed, the vinyl trimethoxy silane is condensed with hydroxyl on the surface of a matrix powder, double bond groups are introduced to the surface of the matrix powder, then concentrated sulfuric acid and sodium nitrate oxidize the double bond groups, through reasonable process research, the double bond grafted on the surface is oxidized into carboxyl and partial residual aldehyde groups, the chelating property of the carboxyl is utilized to coat tantalum and silver on the surface of the matrix powder, after reduction, a protective layer of tantalum, silver and oxides thereof is formed on the surface, the reaction between the positive electrode material and electrolyte is effectively relieved, irreversible phase transition and transition metal dissolution are inhibited, the stability of the positive electrode material is provided, and after the test, after the test is conducted under more severe conditions, the capacity retention rate reaches 95.9-96.7%, the protective layer has good conductivity, after the test, the impedance is only 103.7-110.2 omega, and the protective matrix powder does not have large difference, and the protective layer of tantalum and silver is coated on the surface by adopting a liquid phase matching method, so that the protective layer of tantalum and silver are coated on the surface of the matrix powder, compared with the surface of the protective layer is more severe than the existing, the protective layer can be applied to the preparation of the positive electrode material, and the protective layer has a high boiling point, and has a better passivation cost, and is suitable for the preparation of the positive electrode material.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the protective lithium battery anode material comprises the following specific implementation processes:
1) Preparation of ternary precursors
Taking nickel sulfate, cobalt sulfate and manganese sulfate as a nickel source, a cobalt source and a manganese source respectively, and controlling the molar mass ratio of nickel, cobalt and manganese elements to be 0.6:0.18:0.22, adding deionized water to dissolve and prepare a metal salt solution;
distilled water and hydrazine hydrate are taken according to the volume ratio of 100:5, adding the mixture into a stirrer to be uniformly mixed to obtain a base solution;
taking a reaction kettle, introducing high-purity nitrogen into the reaction kettle, discharging air in the reaction kettle, placing the reaction kettle in a nitrogen protection atmosphere, injecting a base solution into the reaction kettle, heating the reaction kettle to 58 ℃, setting the stirring speed to 240rpm, simultaneously slowly injecting a metal salt solution, a sodium hydroxide solution and ammonia water into the reaction kettle at a constant speed, controlling the injection time to be 20min, continuously preserving heat and stirring for 80min after all injection, then suction-filtering to obtain a filter cake, placing the filter cake into a nitrogen protection type drying box, and drying at 60 ℃ for 2h to obtain a ternary precursor, wherein in the following reaction, the mass fraction of the sodium hydroxide solution is 25%, the concentration of the ammonia water is 18%, and the dosage ratio of the base solution, the metal salt solution, the sodium hydroxide solution and the ammonia water is 1L:600mL:60mL:120mL.
2) Preparation of matrix powder
Taking lithium hydroxide and a ternary precursor, and controlling the molar ratio of the lithium element to the metal element in the ternary precursor to be 1.1:1, adding the powder into a dry grinding machine for cyclic grinding until the median particle diameter of the powder reaches 11 mu m, taking a muffle furnace for preheating to 260 ℃, placing the powder into the middle for roasting for 30min, then heating to 820 ℃ with maximum power for roasting for 8h, opening the furnace for cooling, and adding the roasted sintered material into a high-speed blade type scattering machine for scattering to obtain matrix powder.
3) Preparation of vinylated powder
Taking matrix powder and ethanol solution, performing ultrasonic dispersion at 40kHz for 5min, adding vinyl trimethoxy silane, stirring and mixing, dropwise adding hydrochloric acid to adjust the pH value to 4, stirring and heating to 55 ℃, controlling the overall heating rate to be not more than 10min, slowly dropwise adding sodium hydroxide solution, stirring and mixing until the pH value is adjusted to 9, standing for 12h, taking the lower layer of precipitate, washing with water, filtering out the precipitate again, placing in a drying oven, and drying at 50 ℃ for 3h to obtain vinylation powder, wherein in the reaction, the volume fraction of the ethanol solution is 30%, and the dosage ratio of the matrix powder, the vinyl trimethoxy silane and the ethanol solution is 100g:5mL:200mL.
4) Preparation of modified powder
Mixing vinyl powder and concentrated sulfuric acid for 30min under stirring, heating to 40 ℃, adding sodium nitrate solution, mixing for 18min, press filtering, washing precipitate, drying at 80 ℃ for 1h in a drying oven to obtain modified powder, wherein in the reaction, the mass fraction of the concentrated sulfuric acid is 75%, the mass fraction of the sodium nitrate solution is 8%, and the dosage ratio of the vinyl powder, the concentrated sulfuric acid and the sodium nitrate solution is 100g:60mL:150mL.
5) Preparation of cathode Material
Mixing tantalum ethoxide, silver nitrate solution and absolute ethyl alcohol with 15 times of the mass of the tantalum ethoxide and the silver nitrate solution, regulating the pH value to 5 by sulfuric acid, adding modified powder for mixing in a 28kHz ultrasonic dispersion state, centrifuging, taking the lower layer of precipitate, washing with water, rapidly drying at 120 ℃ to constant weight, placing in a hydrogenation furnace, heating to 300 ℃, preserving heat and reducing for 2 hours, and cooling to obtain a positive electrode material, wherein in the reaction, the dosage ratio of the modified powder to the tantalum ethoxide to the silver nitrate solution is 100g:5.5g:15mL.
Example 2
The preparation method of the protective lithium battery anode material comprises the following specific implementation processes:
1) Preparation of ternary precursors
Taking nickel sulfate, cobalt sulfate and manganese sulfate as a nickel source, a cobalt source and a manganese source respectively, and controlling the molar mass ratio of nickel, cobalt and manganese elements to be 0.6:0.18:0.22, adding deionized water to dissolve and prepare a metal salt solution;
distilled water and hydrazine hydrate are taken according to the volume ratio of 100:8, adding the mixture into a stirrer to be uniformly mixed to obtain a base solution;
taking a reaction kettle, introducing high-purity nitrogen into the reaction kettle, discharging air in the reaction kettle, placing the reaction kettle in a nitrogen protection atmosphere, injecting a base solution into the reaction kettle, heating the reaction kettle to 65 ℃, setting the stirring speed to 300rpm, simultaneously slowly injecting a metal salt solution, a sodium hydroxide solution and ammonia water into the reaction kettle at a constant speed, controlling the injection time to be 20min, continuously preserving heat and stirring for 60min after all injection, then suction-filtering to obtain a filter cake, placing the filter cake into a nitrogen protection type drying box, and drying at 60 ℃ for 2h to obtain a ternary precursor, wherein in the following reaction, the mass fraction of a sodium hydroxide solution is 25%, the concentration of the ammonia water is 18%, and the dosage ratio of the base solution, the metal salt solution, the sodium hydroxide solution and the ammonia water is 1L:700mL:80mL:150mL.
2) Preparation of matrix powder
Taking lithium hydroxide and a ternary precursor, and controlling the molar ratio of the lithium element to the metal element in the ternary precursor to be 1.1:1, adding the powder into a dry grinding machine for cyclic grinding until the median particle diameter of the powder reaches 11 mu m, taking a muffle furnace for preheating to 260 ℃, placing the powder into a middle roasting machine for roasting for 30min, then heating to 840 ℃ with maximum power for roasting for 6h, opening the furnace for cooling, and adding the roasted sintered material into a high-speed blade type scattering machine for scattering to obtain matrix powder.
3) Preparation of vinylated powder
Taking matrix powder and ethanol solution, performing ultrasonic dispersion at 40kHz for 5min, adding vinyl trimethoxy silane, stirring and mixing, dropwise adding hydrochloric acid to adjust the pH value to 4, stirring and heating to 60 ℃, controlling the overall heating rate to be not more than 10min, slowly dropwise adding sodium hydroxide solution, stirring and mixing until the pH value is adjusted to 9, standing for 12h, taking the lower layer of precipitate, washing with water, filtering out the precipitate again, placing in a drying oven, and drying at 50 ℃ for 3h to obtain vinylation powder, wherein in the reaction, the volume fraction of the ethanol solution is 30%, and the dosage ratio of the matrix powder, the vinyl trimethoxy silane and the ethanol solution is 100g:5mL:250mL.
4) Preparation of modified powder
Mixing vinyl powder and concentrated sulfuric acid for 20min, heating to 50 ℃, adding sodium nitrate solution, mixing for 12min, press filtering, washing precipitate, drying at 80 ℃ for 1h in a drying oven to obtain modified powder, wherein in the reaction, the mass fraction of the concentrated sulfuric acid is 75%, the mass fraction of the sodium nitrate solution is 8%, and the dosage ratio of the vinyl powder, the concentrated sulfuric acid and the sodium nitrate solution is 100g:70mL:200mL.
5) Preparation of cathode Material
Mixing tantalum ethoxide, silver nitrate solution and absolute ethyl alcohol with 15 times of the mass of the tantalum ethoxide and the silver nitrate solution, regulating the pH value to 5 by sulfuric acid, adding modified powder for mixing in a 28kHz ultrasonic dispersion state, centrifuging, taking the lower layer precipitate, washing with water, rapidly drying at 120 ℃ to constant weight, placing in a hydrogenation furnace, heating to 300-360 ℃, preserving heat and reducing for 2 hours, and cooling to prepare a positive electrode material, wherein in the reaction, the dosage ratio of the modified powder to the tantalum ethoxide to the silver nitrate solution is 100g:8g:10mL.
Example 3
The preparation method of the protective lithium battery anode material comprises the following specific implementation processes:
1) Preparation of ternary precursors
Taking nickel sulfate, cobalt sulfate and manganese sulfate as a nickel source, a cobalt source and a manganese source respectively, and controlling the molar mass ratio of nickel, cobalt and manganese elements to be 0.6:0.18:0.22, adding deionized water to dissolve and prepare a metal salt solution;
distilled water and hydrazine hydrate are taken according to the volume ratio of 100:7, adding the mixture into a stirrer to be uniformly mixed to obtain a base solution;
taking a reaction kettle, introducing high-purity nitrogen into the reaction kettle, discharging air in the reaction kettle, placing the reaction kettle in a nitrogen protection atmosphere, injecting a base solution into the reaction kettle, heating the reaction kettle to 62 ℃, setting the stirring speed to 300rpm, simultaneously slowly injecting a metal salt solution, a sodium hydroxide solution and ammonia water into the reaction kettle at a constant speed, controlling the injection time to be 20min, continuously preserving heat and stirring for 70min after all injection, then suction-filtering to obtain a filter cake, placing the filter cake into a nitrogen protection type drying box, and drying at 60 ℃ for 2h to obtain a ternary precursor, wherein in the following reaction, the mass fraction of the sodium hydroxide solution is 25%, the concentration of the ammonia water is 18%, and the dosage ratio of the base solution, the metal salt solution, the sodium hydroxide solution and the ammonia water is 1L:660mL:70mL:130mL.
2) Preparation of matrix powder
Taking lithium hydroxide and a ternary precursor, and controlling the molar ratio of the lithium element to the metal element in the ternary precursor to be 1.1:1, adding the powder into a dry grinding machine for cyclic grinding until the median particle diameter of the powder reaches 11 mu m, taking a muffle furnace for preheating to 260 ℃, placing the powder into a middle roasting machine for roasting for 30min, then heating to 830 ℃ with maximum power for roasting for 7.5h, opening the furnace for cooling, and adding the roasted sintered material into a high-speed blade type scattering machine for scattering to obtain matrix powder.
3) Preparation of vinylated powder
Taking matrix powder and ethanol solution, performing ultrasonic dispersion at 40kHz for 5min, adding vinyl trimethoxy silane, stirring and mixing, dropwise adding hydrochloric acid to adjust the pH value to 4, stirring and heating to 58 ℃, controlling the overall heating rate to be not more than 10min, slowly dropwise adding sodium hydroxide solution, stirring and mixing until the pH value is adjusted to 9, standing for 12h, taking the lower layer of precipitate, washing with water, filtering out the precipitate again, placing in a drying oven, and drying at 50 ℃ for 3h to obtain vinylation powder, wherein in the reaction, the volume fraction of the ethanol solution is 30%, and the dosage ratio of the matrix powder, the vinyl trimethoxy silane and the ethanol solution is 100g:5mL:220mL.
4) Preparation of modified powder
Mixing vinyl powder and concentrated sulfuric acid for 30min under stirring, heating to 45 ℃, adding sodium nitrate solution, mixing for 15min, press filtering, washing precipitate, drying at 80 ℃ for 1h in a drying oven to obtain modified powder, wherein in the reaction, the mass fraction of the concentrated sulfuric acid is 75%, the mass fraction of the sodium nitrate solution is 8%, and the dosage ratio of the vinyl powder, the concentrated sulfuric acid and the sodium nitrate solution is 100g:64mL:180mL.
5) Preparation of cathode Material
Mixing tantalum ethoxide, silver nitrate solution and absolute ethyl alcohol with 15 times of the mass of the tantalum ethoxide and the silver nitrate solution, regulating the pH value to 5 by sulfuric acid, adding modified powder for mixing in a 28kHz ultrasonic dispersion state, centrifuging, taking the lower layer of precipitate, washing with water, rapidly drying at 120 ℃ to constant weight, placing in a hydrogenation furnace, heating to 360 ℃, preserving heat and reducing for 2 hours, and cooling to obtain a positive electrode material, wherein in the reaction, the dosage ratio of the modified powder to the tantalum ethoxide to the silver nitrate solution is 100g:7.5g:12mL.
Comparative example 1
This comparative example is the matrix powder prepared in example 3.
Comparative example 2
The comparative example is a positive electrode material prepared by a method provided by chinese patent application No. 201410730319. X.
Taking the positive electrode materials prepared in the examples 1-3 and the comparative examples 1-2, wherein the mass ratio of the positive electrode materials to PVDF to conductive carbon powder is 8: grinding and mixing in a ratio of 1:1, adding N-methyl pyrrolidone for homogenating, then scraping and coating on the surface of an aluminum foil, and controlling the dry load of the positive electrode material on the positive electrode plate to be 2.5mg/cm 2 Drying at 110deg.C for 10 hr, and cutting to obtain circular positive plate with diameter of 10 mm; the negative electrode in the test battery adopts a lithium sheet with the diameter of 14mm, the diaphragm is a diaphragm special for a Celgard 2500 lithium battery, the electrolyte is lithium hexafluorophosphate, and the lithium battery is assembled in an argon glove box;
the lithium battery prepared in the above was tested on a LAND-CT2001A battery test system, the voltage interval was set to 2.0-4.8V, the battery was subjected to a charge-discharge cycle test with a discharge efficiency of 0.1C, after two weeks of cycles, the battery was subjected to a charge-discharge test at 1C for 200 cycles, and then the test was stopped after 0.1C charge-discharge was resumed for 50 cycles. The first specific discharge volume, first discharge efficiency, capacity retention after cycling and impedance of the battery were tested, and specific test data are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the first discharge capacity of the positive electrode material prepared by the invention is 201.5-207.9mAh/g, the first discharge efficiency is 91.4-92.2%, the positive electrode material has higher efficiency and capacity, the retention rate after cyclic test is up to 95.9-96.7%, the retention rate is obviously higher than that of the existing non-coated and coated lithium silicate positive electrode material, the impedance is only 103.7-110.2 omega, and the positive electrode material has lower impedance.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.

Claims (6)

1. The preparation method of the protective lithium battery anode material is characterized by comprising the following steps of:
step A1: ni is synthesized by adopting a coprecipitation method from a nickel source, a cobalt source and a manganese source 0.6 Co 0.18 Mn 0.22 （OH） 2 Powder to prepare ternary precursor;
step A2: the molar ratio of the lithium element to the metal element in the ternary precursor is 1.1:1, taking lithium hydroxide, grinding by a dry method, roasting and scattering to obtain matrix powder;
step A3: dispersing matrix powder in ethanol solution by ultrasonic, adding vinyltrimethoxysilane, mixing, regulating pH value to 4, stirring and heating to 55-60 ℃ and controlling heating time to be not more than 10min, then dripping sodium hydroxide solution until pH value is regulated to 9, standing for 12h, taking precipitate, washing, filtering and drying to obtain vinylation powder, wherein the dosage ratio of the matrix powder, vinyltrimethoxysilane and ethanol solution is 100g:5mL:200-250mL, wherein the volume fraction of the ethanol solution is 30%;
step A4: stirring and mixing the vinylation powder and the concentrated sulfuric acid for 20-30min, heating to 40-50 ℃, adding a sodium nitrate solution for mixing for 12-18min, press-filtering, taking out precipitate, washing and drying to obtain modified powder, wherein the dosage ratio of the vinylation powder to the concentrated sulfuric acid to the sodium nitrate solution is 100g:60-70mL:150-200mL, wherein the mass fraction of concentrated sulfuric acid is 75%, and the mass fraction of sodium nitrate solution is 8%;
step A5: mixing tantalum ethoxide, silver nitrate solution and absolute ethyl alcohol, regulating the pH value to 5 by sulfuric acid, adding modified powder for mixing in an ultrasonic dispersion state, centrifuging, taking a lower layer precipitate, washing, drying, placing in a hydrogenation furnace, preserving heat for 2 hours at 300-360 ℃, and cooling to obtain a positive electrode material, wherein the dosage ratio of the modified powder to the tantalum ethoxide to the silver nitrate solution is 100g:5.5-8g:10-15mL, and the mass fraction of the silver nitrate solution is 38%.
2. The preparation method of the protective lithium battery positive electrode material according to claim 1, wherein the specific preparation method of the ternary precursor is as follows: preparing a nickel source, a cobalt source and a manganese source by deionized water into a nickel, cobalt and manganese element molar mass ratio of 0.6: and (3) uniformly mixing distilled water and hydrazine hydrate to obtain a base solution, heating the base solution to 58-65 ℃ under the protection of nitrogen, simultaneously injecting the metal salt solution, sodium hydroxide solution and ammonia water in a stirring state, continuously preserving heat and stirring for 60-80min after all injection, and suction filtering to obtain a filter cake and drying to obtain the ternary precursor.
3. The method for preparing the protective lithium battery positive electrode material according to claim 2, wherein the nickel source, the cobalt source and the manganese source are selected from sulfates, and the mass fraction of the metal salt solution is 10-15%.
4. The method for preparing the protective lithium battery anode material according to claim 3, wherein the dosage volume ratio of distilled water to hydrazine hydrate is 100:5-8.
5. The method for preparing a protective lithium battery positive electrode material according to claim 4, wherein the dosage ratio of the base solution, the metal salt solution, the sodium hydroxide solution and the ammonia water is 1L:600-700mL:60-80mL:120-150mL, 25% of sodium hydroxide solution by mass and 18% of ammonia water.
6. A protective lithium battery positive electrode material, characterized in that it is prepared by the method of any one of claims 1-5.
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