CN113845155B - Coated ternary positive electrode material and preparation method thereof - Google Patents

Coated ternary positive electrode material and preparation method thereof Download PDF

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CN113845155B
CN113845155B CN202111093538.8A CN202111093538A CN113845155B CN 113845155 B CN113845155 B CN 113845155B CN 202111093538 A CN202111093538 A CN 202111093538A CN 113845155 B CN113845155 B CN 113845155B
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positive electrode
metal fluoride
electrode material
coated
nano tube
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CN113845155A (en
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林浩
汪宇
郑刚
段锐
鲁劲华
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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Abstract

The invention discloses a coated ternary positive electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: carrying out surface hydroxylation treatment on the ternary positive electrode material to obtain a hydroxylated ternary positive electrode material; mixing and ball milling the metal fluoride and the carbon nano tube in a solvent uniformly, and drying, sieving and sintering at high temperature to obtain the carbon nano tube coated metal fluoride; carrying out surface carboxylation treatment on the carbon nano tube coated metal fluoride to obtain carboxylated carbon nano tube coated metal fluoride; adding the hydroxylated ternary anode material and the carboxylated carbon nanotube coated metal fluoride into a solvent, stirring for reaction, then carrying out solid-liquid separation, and drying and sieving the obtained solid substance to obtain the cathode material. The invention can effectively improve the structural stability, electron conductivity and ion conductivity of the ternary positive electrode material, and the prepared ternary positive electrode material has high thermal stability, good conductivity, excellent multiplying power performance and long cycle life.

Description

Coated ternary positive electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a coated ternary positive electrode material and a preparation method thereof.
Background
The energy crisis and the environmental protection problem become two problems which are very concerned by people today, so that the development of new energy is promoted to solve the problems. The lithium ion battery is used as a new energy source and is also a main power of the electric automobile, so that the rapid development is achieved, and the power density and the energy density of the lithium ion battery are required to be higher at present. The performance of the positive electrode material has important influence on the performance of a lithium ion battery, and the existing ternary positive electrode material has the advantages of large specific capacity (more than 250 mAh/g), wide charge-discharge voltage range, low price and the like, and is considered to be the most potential next-generation positive electrode material. However, the ternary positive electrode material has the defects of poor rate performance and poor cycle performance because of poor ionic conductivity and poor electronic conductivity.
Aiming at the defects, the problems are mainly solved by two methods of material modification: one is elemental doping and the other is surface cladding. The doping of the elements is mainly metal cations and fluoride anions, so that the structural stability of the material can be enhanced to a certain extent, but the problem of uneven doping exists, the doping elements are distributed on the surfaces and bulk phases of the material particles, and the impurity phases are easy to form; the surface coating technology is to coat a protective layer on the surface of the lithium-rich ternary positive electrode material, wherein the protective layer is electrochemically inert, can inhibit structural collapse caused by high-voltage charge and discharge of the material to a certain extent, relieves the corrosion of electrolyte to the electrode material, improves the conductivity of the material, but has the problems of uneven coating and complex process, and can form a large amount of toxic industrial wastewater. Because the common element doping and surface coating have the problems of uneven doping and coating, the structural stability of the ternary material is not obviously improved, and the material is seriously oxygen-evolved due to charge and discharge in a wider voltage range, especially under high voltage, and the capacity and the structural stability of the material are reduced.
In view of the foregoing, it is desirable to provide a method for modifying ternary positive electrode materials to overcome the above drawbacks.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a coated ternary positive electrode material and a preparation method thereof, which can improve the structural stability of the material, and improve the electronic conductivity and the ionic conductivity of the material, so that the material has high capacity, high rate performance and excellent cycle stability.
The invention provides a preparation method of a coated ternary positive electrode material, which comprises the following steps:
s1, carrying out surface hydroxylation treatment on a ternary positive electrode material to obtain a hydroxylated ternary positive electrode material;
s2, uniformly mixing and ball-milling the metal fluoride and the carbon nano tube in a solvent, drying, sieving, and then sintering at high temperature in an inert atmosphere or a weak reducing atmosphere to obtain the carbon nano tube coated metal fluoride;
s3, carrying out surface carboxylation treatment on the carbon nano tube coated metal fluoride to obtain carboxylated carbon nano tube coated metal fluoride;
s4, adding the hydroxylated ternary positive electrode material and the carboxylated carbon nanotube coated metal fluoride into a solvent, stirring for reaction, then carrying out solid-liquid separation, and drying and sieving the obtained solid substance to obtain the coated ternary positive electrode material.
The ternary positive electrode material can be a ternary positive electrode material commonly used in lithium ion batteries, and the ternary positive electrode material is not particularly limited in the invention. Preferably, the chemical formula of the ternary positive electrode material is LiNi a Co b Mn c O 2 Wherein 0.5.ltoreq.a.ltoreq.0.9, 0.1 < b < 0.5,0.1 < c < 0.5, and a+b+c=1.
Preferably, the ternary positive electrode material is prepared by taking soluble nickel salt, soluble cobalt salt and soluble manganese salt as raw materials, preparing a precursor through coprecipitation, and then sintering.
Preferably, the soluble nickel salt is at least one of nickel sulfate, nickel nitrate and nickel chloride; preferably, the soluble cobalt salt is at least one of cobalt sulfate, cobalt nitrate and cobalt chloride; preferably, the soluble manganese salt is at least one of manganese sulfate, manganese nitrate and manganese chloride.
Preferably, the mole ratio of the soluble nickel salt, the soluble cobalt salt and the soluble manganese salt is a: b: c= (0.4-0.9): (0.1-0.5): (0.1-0.5), and a+b+c=1.
Preferably, the preparation method of the ternary cathode material comprises the following steps:
weighing soluble nickel salt, soluble cobalt salt and soluble manganese salt according to a mole ratio, dissolving the soluble nickel salt, the soluble cobalt salt and the soluble manganese salt in deionized water to obtain a mixed salt solution, adding the mixed salt solution, an alkali solution and an ammonia solution into a reaction container according to a certain volume ratio, and heating in an inert atmosphereThe ternary cathode material precursor Ni is obtained by reacting for 20 to 60 minutes under the conditions that the temperature is 55+/-5 ℃, the pH value is 10.9 to 11.5 and the stirring frequency is 15 to 20Hz a Co b Mn c (OH) 2 ；
And (3) mixing the ternary cathode material precursor obtained by the method with a lithium source according to a molar ratio (Ni+Co+Mn): and (3) grinding and mixing the materials uniformly with Li of 1 (1.02-1.08), calcining the materials for 6-8 hours at 700-900 ℃ under inert atmosphere or weak reducing atmosphere, cooling the materials, and crushing, sieving and grading the cooled materials to obtain the ternary anode material.
Preferably, the concentration of the mixed salt solution is 1-2mol/L, the concentration of the alkali solution is 4-6mol/L, and the concentration of the ammonia water solution is 3-7mol/L.
Preferably, the alkali solution is an aqueous solution of at least one of sodium hydroxide, potassium hydroxide, and lithium hydroxide.
Preferably, the volume ratio of the mixed salt solution to the alkali solution to the ammonia water solution is (2-4): 3-5): 0.1-2.
Preferably, the lithium source is lithium carbonate, lithium hydroxide, or a combination thereof.
Preferably, in the step S1, the surface hydroxylation treatment of the ternary cathode material includes: adding the ternary positive electrode material into an alkaline solution, firstly stirring for 1-1.5h under the heating and boiling condition, then stopping stirring, continuously boiling for 5-15h, then performing solid-liquid separation, washing the obtained solid matter to be neutral, performing solid-liquid separation, and drying the obtained solid matter to obtain the ternary positive electrode material subjected to hydroxylation treatment; preferably, the mass ratio of the ternary positive electrode material to the alkaline solution is (3-5): (8-13); preferably, the concentration of the alkaline solution is 0.25-2.5mol/L; preferably, the alkaline solution is an aqueous solution of at least one of sodium hydroxide, potassium hydroxide, and lithium hydroxide; preferably, the drying is vacuum drying, and the drying temperature is 80-120 ℃.
Preferably, in the step S2, the high-temperature sintering is performed at a temperature of 300-500 ℃ for 4-8 hours.
Preferably, in the step S2, the ball milling time is 5-7 hours.
Preferably, in the step S2, the drying temperature is 100-120 ℃.
Preferably, in the step S2, the number of the screen meshes used for sieving is 500 mesh.
Preferably, in the step S2, the mass ratio of the metal fluoride to the carbon nano tube is 100 (2-8).
Preferably, in the step S2, the ratio of the sum of the mass of the metal fluoride and the carbon nanotube to the mass of the solvent is 1 (1.2-1.7).
Preferably, in the step S2, the metal fluoride is at least one of aluminum fluoride, ferrous fluoride, titanium fluoride, and calcium fluoride.
Preferably, in the step S2, the solvent is at least one of NMP, ethanol, methanol, propanol, diethyl ether, and acetone.
Preferably, in the step S3, the surface carboxylation treatment of the carbon nanotube-coated metal fluoride includes: adding the carbon nano tube coated metal fluoride into a nitric acid solution, wherein the ratio of the carbon nano tube coated metal fluoride to the nitric acid solution is 1g: (3-5) mL, stirring and reacting for 1.5-3h at 50-55 ℃, then carrying out solid-liquid separation, washing and drying the obtained solid substance to obtain carboxylated carbon nano tube coated metal fluoride; preferably, the concentration of the nitric acid solution is 10-15mol/L; preferably, after the carbon nanotube-coated metal fluoride is added to the nitric acid solution, the method further comprises: uniformly dispersing by ultrasonic at room temperature, wherein the ultrasonic dispersing time is preferably 5-10min; preferably, the washing is specifically: washing with deionized water, absolute ethyl alcohol or a combination thereof as a detergent to neutrality; preferably, the drying is vacuum drying, the temperature of the vacuum drying is 50-70 ℃ and the time is 12-36h.
Preferably, in the step S4, the mass ratio of the ternary cathode material subjected to hydroxylation to the carbon nanotube subjected to carboxylation is 100: (1.5-5).
Preferably, in the step S4, the ratio of the sum of the mass of the hydroxylated ternary cathode material and the carboxylated carbon nanotubes to the volume of the solvent is (5-50) g:100mL.
Preferably, in the step S4, the solvent is at least one of an ethanol solution, a methanol solution, and a propanol solution.
Preferably, in the step S4, the solid-liquid separation method is centrifugation, the centrifugal speed is 2000-5000r/min, and the centrifugal time is 3-15min.
Preferably, in the step S4, the drying temperature is 60-80 ℃.
Preferably, in the step S4, the temperature of the stirring reaction is 25-60 ℃ and the time is 15-30min.
Preferably, in the step S4, the number of the screen meshes used for sieving is 500 mesh.
Preferably, the inert atmosphere is an atmosphere formed by at least one of nitrogen, argon or carbon monoxide, and the weak reducing atmosphere is a mixed atmosphere formed by nitrogen or argon and hydrogen according to the volume ratio of 10 (1-100).
A coated ternary positive electrode material is prepared by the preparation method.
The beneficial effects of the invention are as follows:
according to the invention, the carbon nano tube is coated on the surface of the metal fluoride to be modified, so that the surface of the metal fluoride contains the carboxyl of the functional group which can be bonded with the hydroxyl, and the metal fluoride is coated on the surface of the ternary positive electrode material with the surface hydroxylated, and the metal fluoride coated with the carbon nano tube can be uniformly coated on the surface of the ternary positive electrode material through the bonding effect between the carboxyl and the hydroxyl, so that the monolayer and uniform coating of the coating on the surface of the ternary positive electrode material is realized, the uniformity and stability of the material are ensured, the oxygen evolution problem of the material is effectively improved, the material can keep high capacity and high structural stability, and the uniform surface coating is also beneficial to better improving the electronic conductivity and the ionic conductivity of the material, and reducing the resistance of lithium ion deintercalation, thereby more effectively improving the multiplying power performance and the cycle performance of the battery. Therefore, the invention can effectively improve the structural stability, electron conductivity and ion conductivity of the ternary positive electrode material, and the prepared ternary positive electrode material has high thermal stability, good conductivity, excellent multiplying power performance and long cycle life.
Drawings
Fig. 1 is a schematic structural diagram of a coated ternary cathode material according to the present invention.
Fig. 2 is a graph showing comparison of battery cycle curve test results of lithium ion batteries assembled by the materials prepared in example 1 and comparative example 3 according to the present invention.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
The preparation method of the coated ternary positive electrode material comprises the following steps:
s1, adding 20g of ternary positive electrode material into 50g of sodium hydroxide aqueous solution with the concentration of 0.5mol/L, stirring for 1.2 hours under the heating and boiling condition, stopping stirring, continuously boiling for 10 hours, filtering, washing the obtained solid substance with deionized water to be neutral, filtering, and vacuum drying the obtained solid substance at 90 ℃ to obtain the ternary positive electrode material subjected to hydroxylation treatment;
s2, mixing 10g of aluminum fluoride and 0.2g of carbon nano tube in 15.3-g N-methyl pyrrolidone, ball milling for 5 hours, drying at 110 ℃, sieving by using a screen with the mesh number of 500, and sintering in a muffle furnace at a high temperature of 350 ℃ for 6 hours in an argon atmosphere to obtain the carbon nano tube coated metal fluoride;
s3, adding the carbon nano tube coated metal fluoride prepared in the step S2 into a nitric acid solution with the concentration of 10mol/L, uniformly dispersing the carbon nano tube coated metal fluoride at room temperature for 5min, stirring the mixture at 50 ℃ for reaction for 1.5h, centrifuging the mixture, washing the obtained solid substance to be neutral by using absolute ethyl alcohol, and vacuum drying the solid substance at 60 ℃ for 24h to obtain carboxylated carbon nano tube coated metal fluoride, wherein the ratio of the carbon nano tube coated metal fluoride to the nitric acid solution is 1g:4mL;
s4, adding 10g of the hydroxylation ternary cathode material and 0.15g of the carboxylated carbon nanotube coated metal fluoride into 100mL of ethanol solution, stirring at 30 ℃ for reaction for 30min, centrifuging at 4000r/min for 10min, drying the obtained solid substance at 70 ℃, and sieving with a 500-mesh screen to obtain the coated ternary cathode material.
Wherein the chemical formula of the ternary positive electrode material is LiNi 0.7 Co 0.1 Mn 0.2 O 2 The preparation method comprises the following steps:
the nickel nitrate, the cobalt nitrate and the manganese nitrate are weighed according to the mole ratio and dissolved in deionized water to obtain a mixed salt solution with the concentration of 1.5mol/L, the prepared mixed salt solution, a sodium hydroxide solution with the concentration of 5mol/L and an ammonia water solution with the concentration of 5mol/L are added into a reaction vessel according to the volume ratio of 3:4:1, and react for 30min under the condition of the temperature of 55 ℃ and the pH value of 11 and the stirring frequency of 18Hz in an inert atmosphere to obtain a ternary anode material precursor Ni 0.7 Co 0.1 Mn 0.2 (OH) 2 ；
And mixing the ternary positive electrode material precursor obtained by the method with lithium carbonate according to a molar ratio (Ni+Co+Mn): and (3) grinding and uniformly mixing Li at a ratio of 1:1.05, calcining for 7 hours at 800 ℃ in an argon atmosphere, cooling, crushing, sieving and grading to obtain the ternary anode material.
Example 2
The preparation method of the coated ternary positive electrode material comprises the following steps:
s1, adding 20g of ternary positive electrode material into 50g of sodium hydroxide aqueous solution with the concentration of 0.5mol/L, stirring for 1.2 hours under the heating and boiling condition, stopping stirring, continuously boiling for 10 hours, filtering, washing the obtained solid substance with deionized water to be neutral, filtering, and vacuum drying the obtained solid substance at 90 ℃ to obtain the ternary positive electrode material subjected to hydroxylation treatment;
s2, mixing 10g of aluminum fluoride and 0.4g of carbon nano tube in 15.6-g N-methyl pyrrolidone, ball milling for 5 hours, drying at 110 ℃, sieving by using a screen with the mesh number of 500, and sintering in a muffle furnace at a high temperature of 350 ℃ for 6 hours in an argon atmosphere to obtain the carbon nano tube coated metal fluoride;
s3, adding the carbon nano tube coated metal fluoride prepared in the step S2 into a nitric acid solution with the concentration of 10mol/L, uniformly dispersing the carbon nano tube coated metal fluoride at room temperature for 5min, stirring the mixture at 50 ℃ for reaction for 1.5h, centrifuging the mixture, washing the obtained solid substance to be neutral by using absolute ethyl alcohol, and vacuum drying the solid substance at 60 ℃ for 24h to obtain carboxylated carbon nano tube coated metal fluoride, wherein the ratio of the carbon nano tube coated metal fluoride to the nitric acid solution is 1g:4mL;
s4, adding 10g of the hydroxylation ternary cathode material and 0.25g of the carboxylated carbon nanotube coated metal fluoride into 102.5mL of ethanol solution, stirring at 30 ℃ for reaction for 30min, centrifuging at 4000r/min for 10min, drying the obtained solid substance at 70 ℃, and sieving with a 500-mesh screen to obtain the coated ternary cathode material.
Wherein, the chemical formula and the preparation method of the ternary positive electrode material are the same as those of the example 1.
Example 3
The preparation method of the coated ternary positive electrode material comprises the following steps:
s1, adding 20g of ternary positive electrode material into 50g of sodium hydroxide aqueous solution with the concentration of 0.5mol/L, stirring for 1.2 hours under the heating and boiling condition, stopping stirring, continuously boiling for 10 hours, filtering, washing the obtained solid substance with deionized water to be neutral, filtering, and vacuum drying the obtained solid substance at 90 ℃ to obtain the ternary positive electrode material subjected to hydroxylation treatment;
s2, mixing 10g of aluminum fluoride and 0.6g of carbon nano tube in 15.9-g N-methyl pyrrolidone, ball milling for 5 hours, drying at 110 ℃, sieving by using a screen with the mesh number of 500, and sintering in a muffle furnace at a high temperature of 350 ℃ for 6 hours in an argon atmosphere to obtain the carbon nano tube coated metal fluoride;
s3, adding the carbon nano tube coated metal fluoride prepared in the step S2 into a nitric acid solution with the concentration of 10mol/L, uniformly dispersing the carbon nano tube coated metal fluoride at room temperature for 5min, stirring the mixture at 50 ℃ for reaction for 1.5h, centrifuging the mixture, washing the obtained solid substance to be neutral by using absolute ethyl alcohol, and vacuum drying the solid substance at 60 ℃ for 24h to obtain carboxylated carbon nano tube coated metal fluoride, wherein the ratio of the carbon nano tube coated metal fluoride to the nitric acid solution is 1g:4mL;
s4, adding 10g of the hydroxylation ternary cathode material and 0.4g of the carboxylated carbon nanotube coated metal fluoride into 100mL of ethanol solution, stirring at 30 ℃ for reaction for 30min, centrifuging at 4000r/min for 10min, drying the obtained solid substance at 70 ℃, and sieving with a 500-mesh screen to obtain the coated ternary cathode material.
Wherein, the chemical formula and the preparation method of the ternary positive electrode material are the same as those of the example 1.
Example 4
The preparation method of the coated ternary positive electrode material comprises the following steps:
s1, adding 20g of ternary positive electrode material into 50g of sodium hydroxide aqueous solution with the concentration of 0.5mol/L, stirring for 1.2 hours under the heating and boiling condition, stopping stirring, continuously boiling for 10 hours, filtering, washing the obtained solid substance with deionized water to be neutral, filtering, and vacuum drying the obtained solid substance at 90 ℃ to obtain the ternary positive electrode material subjected to hydroxylation treatment;
s2, mixing 10g of aluminum fluoride and 0.8g of carbon nano tube in 16.2-g N-methyl pyrrolidone, ball milling for 5 hours, drying at 110 ℃, sieving by using a screen with the mesh number of 500, and sintering in a muffle furnace at a high temperature of 350 ℃ for 6 hours in an argon atmosphere to obtain the carbon nano tube coated metal fluoride;
s3, adding the carbon nano tube coated metal fluoride prepared in the step S2 into a nitric acid solution with the concentration of 10mol/L, uniformly dispersing the carbon nano tube coated metal fluoride at room temperature for 5min, stirring the mixture at 50 ℃ for reaction for 1.5h, centrifuging the mixture, washing the obtained solid substance to be neutral by using absolute ethyl alcohol, and vacuum drying the solid substance at 60 ℃ for 24h to obtain carboxylated carbon nano tube coated metal fluoride, wherein the ratio of the carbon nano tube coated metal fluoride to the nitric acid solution is 1g:4mL;
s4, adding 10g of the hydroxylation ternary cathode material and 0.5g of the carboxylated carbon nanotube coated metal fluoride into 100mL of ethanol solution, stirring at 30 ℃ for reaction for 30min, centrifuging at 4000r/min for 10min, drying the obtained solid substance at 70 ℃, and sieving with a 500-mesh screen to obtain the coated ternary cathode material.
Wherein, the chemical formula and the preparation method of the ternary positive electrode material are the same as those of the example 1.
Example 5
The preparation method of the coated ternary positive electrode material comprises the following steps:
s1, adding 30g of ternary positive electrode material into 80g of sodium hydroxide aqueous solution with the concentration of 0.25mol/L, stirring for 1.5 hours under the heating and boiling condition, stopping stirring, continuously boiling for 15 hours, filtering, washing the obtained solid substance to be neutral by deionized water, filtering, and vacuum drying the obtained solid substance at 80 ℃ to obtain the ternary positive electrode material subjected to hydroxylation treatment;
s2, mixing 10g of aluminum fluoride and 0.5g of carbon nano tube in 15.3-g N-methyl pyrrolidone, ball milling for 6 hours, drying at 100 ℃, sieving by using a screen with the mesh number of 500, and sintering at 300 ℃ for 8 hours in a muffle furnace in an argon atmosphere to obtain the carbon nano tube coated metal fluoride;
s3, adding the carbon nano tube coated metal fluoride prepared in the step S2 into a nitric acid solution with the concentration of 12mol/L, uniformly dispersing the carbon nano tube coated metal fluoride at room temperature for 8min, stirring the mixture at the temperature of 52 ℃ for reaction for 2h, centrifuging the mixture, washing the obtained solid substance to be neutral by using absolute ethyl alcohol, and vacuum drying the solid substance at the temperature of 50 ℃ for 36h to obtain carboxylated carbon nano tube coated metal fluoride, wherein the ratio of the carbon nano tube coated metal fluoride to the nitric acid solution is 1g:5mL;
s4, adding 10g of the hydroxylation ternary cathode material and 0.2g of the carboxylated carbon nanotube coated metal fluoride into 100mL of ethanol solution, stirring at 25 ℃ for reaction for 20min, centrifuging at 2000r/min for 15min, drying the obtained solid substance at 60 ℃, and sieving with a 500-mesh screen to obtain the coated ternary cathode material.
Wherein, the chemical formula and the preparation method of the ternary positive electrode material are the same as those of the example 1.
Example 6
The preparation method of the coated ternary positive electrode material comprises the following steps:
s1, adding 50g of ternary positive electrode material into 130g of sodium hydroxide aqueous solution with the concentration of 2.5mol/L, stirring for 1h under the heating and boiling condition, stopping stirring, continuously boiling for 5h, filtering, washing the obtained solid substance with deionized water to be neutral, filtering, and vacuum drying the obtained solid substance at 120 ℃ to obtain the ternary positive electrode material subjected to hydroxylation treatment;
s2, mixing 10g of aluminum fluoride and 0.8g of carbon nano tube in 15.3-g N-methyl pyrrolidone, performing ball milling for 7 hours, drying at 120 ℃, sieving by using a screen with the mesh number of 500, and sintering in a muffle furnace at a high temperature of 500 ℃ for 4 hours in an argon atmosphere to obtain the carbon nano tube coated metal fluoride;
s3, adding the carbon nano tube coated metal fluoride prepared in the step S2 into a nitric acid solution with the concentration of 15mol/L, uniformly dispersing the carbon nano tube coated metal fluoride at room temperature for 10min, stirring the mixture at the temperature of 55 ℃ for reaction for 3h, centrifuging the mixture, washing the obtained solid substance to be neutral by using absolute ethyl alcohol, and vacuum drying the solid substance at the temperature of 70 ℃ for 12h to obtain carboxylated carbon nano tube coated metal fluoride, wherein the ratio of the carbon nano tube coated metal fluoride to the nitric acid solution is 1g:3mL;
s4, adding 10g of the hydroxylation ternary cathode material and 0.5g of the carboxylated carbon nanotube coated metal fluoride into 100mL of ethanol solution, stirring at 60 ℃ for reaction for 15min, centrifuging at the rotating speed of 5000r/min for 3min, drying the obtained solid substance at 80 ℃, and sieving with a 500-mesh screen to obtain the coated ternary cathode material.
Wherein, the chemical formula and the preparation method of the ternary positive electrode material are the same as those of the example 1.
Comparative example 1
A preparation method of a coated ternary positive electrode material comprises the steps of mixing the ternary positive electrode material with aluminum fluoride according to a mass ratio of 100: and (1.5) uniformly mixing, and calcining for 12 hours in an argon atmosphere at 600 ℃ to obtain the catalyst.
Wherein, the chemical formula and the preparation method of the ternary positive electrode material are the same as those of the example 1.
Comparative example 2
A preparation method of a coated ternary positive electrode material comprises the steps of mixing the ternary positive electrode material with aluminum fluoride according to a mass ratio of 100:1.5, calcining for 12 hours in an argon atmosphere at 600 ℃ to obtain a primary coating; and then the mass ratio of the primary coating to the carbon nano tube is 100: and (3) after uniformly mixing, calcining for 6 hours in an argon atmosphere at 800 ℃ to obtain the composite material.
Wherein, the chemical formula and the preparation method of the ternary positive electrode material are the same as those of the example 1.
Comparative example 3
The chemical formula and the preparation method of the ternary positive electrode material are the same as those of the example 1.
Test examples
The positive electrode materials prepared in examples 1-4 and comparative examples 1-3 were matched with the same negative electrode, electrolyte and separator to prepare 3Ah wound soft package lithium ion batteries of the same specification, and electrical performance tests (voltage range 3.0-4.4V) were performed, wherein the test contents include: (1) 0.2C charge and discharge test; (2) high temperature of 45 ℃ is 0.5C/1C multiplying power circulation test; (3) and (3) testing the discharge rate at 25 ℃ at 3 ℃.
The test results are shown in table 1 and fig. 2:
table 1 lithium ion battery performance test results
As can be seen from the comparison of the data in Table 1 and FIG. 2, the ternary positive electrode material prepared by the method has higher cycling stability and higher energy utilization rate (first coulomb efficiency > 90%); and the capacity retention rate after 500 cycles is still more than 95%, and the highest capacity retention rate can be more than 96%.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (13)

1. The preparation method of the coated ternary cathode material is characterized by comprising the following steps of:
s1, adding a ternary positive electrode material into an alkaline solution, heating and boilingStirring for 1-1.5h under boiling conditions, stopping stirring, continuing boiling for 5-15h, performing solid-liquid separation, washing the obtained solid matter to be neutral, performing solid-liquid separation, and drying the obtained solid matter to obtain the ternary anode material subjected to hydroxylation treatment; the chemical formula of the ternary positive electrode material is LiNi a Co b Mn c O 2 Wherein 0.5.ltoreq.a.ltoreq.0.9, 0.1 < b < 0.5,0.1 < c < 0.5, and a+b+c=1;
s2, uniformly mixing and ball-milling the metal fluoride and the carbon nano tube in a solvent, drying, sieving, and then sintering at high temperature in an inert atmosphere or a weak reducing atmosphere to obtain the carbon nano tube coated metal fluoride;
s3, adding the carbon nano tube coated metal fluoride into a nitric acid solution, stirring and reacting for 1.5-3 hours at 50-55 ℃, then carrying out solid-liquid separation, washing and drying the obtained solid substance to obtain the carboxylated carbon nano tube coated metal fluoride;
s4, adding the hydroxylated ternary positive electrode material and the carboxylated carbon nanotube coated metal fluoride into a solvent, stirring for reaction, then carrying out solid-liquid separation, and drying and sieving the obtained solid substance to obtain the coated ternary positive electrode material.
2. The method for preparing a coated ternary positive electrode material according to claim 1, wherein preferably, the mass ratio of the ternary positive electrode material to the alkaline solution is (3-5): (8-13).
3. The method for preparing a coated ternary cathode material according to claim 1, wherein the concentration of the alkaline solution is 0.25-2.5mol/L.
4. The method for producing a coated ternary cathode material according to claim 1, wherein the alkaline solution is an aqueous solution of at least one of sodium hydroxide, potassium hydroxide, and lithium hydroxide.
5. The method for preparing a coated ternary cathode material according to claim 1, wherein in the step S2, the high-temperature sintering temperature is 300-500 ℃ and the time is 4-8h.
6. The preparation method of the coated ternary cathode material according to claim 1, wherein the mass ratio of the metal fluoride to the carbon nano tube is 100 (2-8).
7. The method for preparing a coated ternary cathode material according to claim 1, wherein the ratio of the sum of the mass of the metal fluoride and the mass of the carbon nanotubes to the mass of the solvent is 1 (1.2-1.7).
8. The method for preparing a coated ternary cathode material according to claim 1, wherein the metal fluoride is at least one of aluminum fluoride, ferrous fluoride, titanium fluoride, and calcium fluoride.
9. The method for preparing a coated ternary cathode material according to claim 1, wherein the concentration of the nitric acid solution is 10-15mol/L.
10. The method for preparing a coated ternary cathode material according to claim 1, wherein the ratio of the carbon nanotube coated metal fluoride to the nitric acid solution is 1g: (3-5) mL.
11. The method for preparing a coated ternary cathode material according to claim 1, wherein in the step S4, the mass ratio of the ternary cathode material subjected to hydroxylation to the carbon nanotubes subjected to carboxylation is 100: (1.5-5).
12. The method for preparing a coated ternary cathode material according to claim 1, wherein in the step S4, the temperature of the stirring reaction is 25-60 ℃ and the time is 15-30min.
13. A coated ternary cathode material prepared by the preparation method of any one of claims 1-12.
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