CN112820868A - Coated nickel-cobalt-manganese ternary single crystal material and preparation method thereof - Google Patents

Coated nickel-cobalt-manganese ternary single crystal material and preparation method thereof Download PDF

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CN112820868A
CN112820868A CN202110224094.0A CN202110224094A CN112820868A CN 112820868 A CN112820868 A CN 112820868A CN 202110224094 A CN202110224094 A CN 202110224094A CN 112820868 A CN112820868 A CN 112820868A
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solution
cobalt
titanium
nickel
single crystal
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CN112820868B (en
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林浩
郑刚
汪宇
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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    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • 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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 discloses a coated nickel-cobalt-manganese ternary single crystal material and a preparation method thereof. The preparation method is simple to operate, the reaction conditions are mild, and the obtained coated nickel-cobalt-manganese ternary single crystal material has excellent high-temperature cycle performance.

Description

Coated nickel-cobalt-manganese ternary single crystal material and preparation method thereof
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a coated nickel-cobalt-manganese ternary single crystal material and a preparation method thereof.
Background
With the development of new energy, lithium ion batteries develop rapidly, and in the lithium ion battery materials, the positive electrode material is taken as one of important key materials, so that the positive electrode material has important significance for determining the performance of the batteries.
Most of the prior ternary cathode materials are secondary large particles formed by agglomeration of primary particles, have more crystal defects, nonuniform particles and poor battery consistency, so that on one hand, the contact area of the ternary cathode materials and electrolyte is small, and lithium ions are not easy to migrate; on the other hand, the particle size of the material of the secondary particle agglomeration is larger, wherein most of D50 is more than 10 μm, the compaction is generally smaller, and the improvement of the energy density of the battery is not facilitated. How to effectively increase the contact area between the anode material and the electrolyte and improve the structural stability of the anode material is the key to improve the service life of the battery.
At present, aiming at the problems, the method mainly adopted is to prepare a coating or doping type single crystal anode which is a good solution, and the methods still have great limitations, such as complicated steps, uneven doping or too high annealing temperature, and easy separation of structural lithium to cause excessive residual lithium on the surface of the structure, thereby affecting the material performance.
Disclosure of Invention
In view of the above, the invention needs to provide a coated nickel-cobalt-manganese ternary single crystal material and a preparation method thereof, the titanium-aluminum composite oxide is coated on the surface of the nickel-cobalt-manganese ternary single crystal material by the preparation method, the structural stability and the safety of the nickel-cobalt-manganese ternary single crystal material are improved, and the preparation method is simple to operate, strong in feasibility, good in coating effect and capable of effectively improving the high-temperature cycle performance of the lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a preparation method of a coated nickel-cobalt-manganese ternary single crystal material, which comprises the following steps:
providing a titanium-aluminum composite oxide;
obtaining a precursor solid solution: mixing a mixed salt solution, a lithium salt solution and a chelating agent solution, and carrying out hydrothermal treatment at 140-160 ℃ to obtain a precursor solid solution, wherein the mixed salt solution is a mixed solution of nickel salt, cobalt salt and manganese salt;
obtaining a coated nickel-cobalt-manganese ternary single crystal material: and adding the titanium-aluminum composite oxide and the precursor solid solution into an organic solvent, fully and uniformly mixing, separating, drying and sieving to obtain mixed powder, and carrying out heat treatment on the mixed powder and sintering to obtain the nickel-cobalt-manganese ternary single crystal material coated by the titanium-aluminum composite oxide.
Further, the specific steps for providing the titanium-aluminum composite oxide are as follows: inputting a first solution and a second solution into a reaction container added with a complexing agent in a parallel flow mode, meanwhile, introducing carbon dioxide gas into the reaction container, controlling the pH value of the system to be constant at 8.0-11.0, controlling the reaction temperature to be 20-50 ℃, after reacting for 0.5-1.5 h, continuously introducing the carbon dioxide gas for at least 2h, washing, drying and grinding to obtain the titanium-aluminum composite oxide, wherein the first solution is a lithium metaaluminate solution or a sodium metaaluminate solution, and the second solution is a titanium nitrate solution or a titanium sulfate solution.
Further, the concentration of the first solution is 0.15-5 mol/L, and the concentration of the second solution is 0.5-1.5 mol/L;
the complexing agent is selected from at least one of ammonia water, sodium citrate and iminodiacetic acid, the molar ratio of the complexing agent to first ions is 1: 10-15, and the first ions are the sum of the quantity of aluminate ions and titanium ions.
Further, the concentration ratio of the mixed salt solution to the lithium salt solution is 1-1.25, and the concentration of the chelating agent solution is 0.5-1.2 mol/L.
Further, the nickel salt is selected from one or a mixture of two of nickel nitrate and nickel acetate;
the cobalt salt is selected from one or a mixture of two of cobalt nitrate and cobalt acetate;
the manganese salt is selected from one or a mixture of two of manganese nitrate and manganese acetate.
Further, the lithium salt is selected from one or a mixture of more than two of lithium nitrate, lithium acetate and dilithium oxalate.
Further, the chelating agent is one or more than two of citric acid, ethylene diamine tetraacetic acid and glycine, the molar ratio of the chelating agent to second ions is 1: 0.5-8, and the second ions are the sum of the amounts of nickel ions, cobalt ions, manganese ions and lithium ions.
Further, in the step of obtaining the nickel-coated cobalt-manganese ternary single crystal material, the organic solvent is one or a mixture of more than two of methanol, ethanol, propanol, isopropanol, polypropylene alcohol, n-butanol, polyethylene glycol, polyvinylpyrrolidone and acetone;
adding 5-50 g of the titanium-aluminum composite oxide and the precursor solid solution into each 100mL of the organic solvent, wherein the mass ratio of the titanium-aluminum composite oxide to the precursor solid solution is (1-10): 100.
Further, in the step of obtaining the coated nickel-cobalt-manganese ternary single crystal material, the heat treatment comprises the following specific steps: placing the mixed powder at 400-550 ℃ to react for 1-3 h;
the sintering comprises the following specific steps: sintering at 800-980 ℃ for 10-15 h in an oxygen atmosphere.
The invention also provides a coated nickel-cobalt-manganese ternary single crystal material which is prepared by adopting the preparation method of any one of the above materials.
Compared with the prior art, the invention has the following beneficial effects:
the raw materials adopted in the preparation method provided by the invention are common laboratory materials, so that the preparation method is non-toxic, pollution-free and high in safety; the equipment adopted in the preparation process is simple, special equipment is not needed, the reaction condition is mild, the operation is simple, the feasibility is strong, and the prepared coated nickel-cobalt-manganese ternary single crystal material has a good coating effect;
according to the preparation method, the titanium-aluminum composite oxide is used as the coating agent to prepare the high-performance nickel-cobalt-manganese ternary single crystal material for the first time, the titanium-aluminum composite oxide has the characteristics of high melting point, good chemical stability and the like, and the titanium-aluminum composite oxide is used as the coating of the nickel-cobalt-manganese ternary material, so that the structural stability of the nickel-cobalt-manganese ternary positive electrode material can be improved, the contact between a nickel-cobalt-manganese ternary positive electrode material substrate and an electrolyte can be reduced, the corrosion effect of trace hydrofluoric acid in the electrolyte is effectively inhibited, and the safety of a battery is improved.
The battery prepared from the coated nickel-cobalt-manganese ternary single crystal material has excellent high-temperature cycle performance.
Drawings
FIG. 1 is an SEM image of an uncoated Ni-Co-Mn ternary single crystal material prepared in comparative example 1;
FIG. 2 is an SEM image of the coated Ni-Co-Mn ternary single-crystal material prepared in example 1;
fig. 3 is a comparison graph of high-temperature cycle performance of the nickel-cobalt-manganese ternary single crystal materials in comparative examples 1 and 2 and example 1 after being respectively prepared into batteries.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a preparation method of a coated nickel-cobalt-manganese ternary single crystal material, which comprises the following steps:
providing a titanium-aluminum composite oxide;
obtaining a precursor solid solution: mixing a mixed salt solution, a lithium salt solution and a chelating agent solution in a reaction kettle, and drying at 140-160 ℃ to obtain a precursor solid solution, wherein the mixed salt solution is a mixed solution of nickel salt, cobalt salt and manganese salt;
obtaining a coated nickel-cobalt-manganese ternary single crystal material: and adding the titanium-aluminum composite oxide and the precursor solid solution into an ethanol solution, fully and uniformly mixing, separating, drying and sieving to obtain mixed powder, and carrying out heat treatment on the mixed powder and sintering to obtain the nickel-cobalt-manganese ternary single crystal material coated by the titanium-aluminum composite oxide.
The titanium-aluminum composite oxide in the invention is mainly Al2O3-TiO2The composite oxide has excellent high-temperature stability and larger pore volume and specific surface area, and the titanium-aluminum composite oxide and the nickel-cobalt-manganese precursor solid solution are mixed and sintered to prepare the nickel-cobalt-manganese ternary single crystal material coated by the titanium-aluminum composite oxide.
In order to make the preparation method clearer, in the step of obtaining the coated nickel-cobalt-manganese ternary single crystal material, the obtained mixed solution is centrifuged at 2000-5000-.
Further, the obtaining of the titanium aluminum composite oxide in the present invention is not particularly limited, and preferably, the specific steps of providing the titanium aluminum composite oxide in the present invention are: inputting a first solution and a second solution into a reaction container added with a complexing agent in a parallel flow mode, introducing carbon dioxide gas into the reaction container, controlling the pH value of the system to be constant at 8.0-11.0, controlling the reaction temperature to be 20-50 ℃, reacting for 0.5-1.5 h, continuously introducing the carbon dioxide gas for at least 2h, washing, drying and grinding to obtain a titanium-aluminum composite oxide, wherein the first solution is a lithium metaaluminate solution or a sodium metaaluminate solution, and the second solution is a titanium nitrate solution or a titanium sulfate solution; and mixing the first solution and the second solution, and then performing parallel-flow precipitation to obtain the titanium-aluminum composite oxide, and simultaneously introducing carbon dioxide gas to ensure the full action of titanium atoms and aluminum atoms. In the step, the addition of the complexing agent can reduce the supersaturation degree and the nucleation rate to a certain extent, so that the nucleation rate and the crystal growth rate are dynamically balanced, the purpose of improving the crystal morphology is further achieved, and the performance of the obtained titanium-aluminum composite oxide is better. Further, it is understood that the reaction vessel is not particularly limited as long as the above reaction process can be achieved, and a gel forming tank is used in some specific embodiments of the present invention; in addition, in the step of obtaining the titanium-aluminum composite oxide, washing, drying and grinding are all conventional means in the field, and are not particularly limited, and in some specific embodiments of the invention, the product after reaction is washed 3 times by using deionized water, and then is fully dried at 90 ℃ and ground to obtain the titanium-aluminum composite oxide.
The configuration of the first solution and the second solution is not particularly limited, and the corresponding solutes are weighed and dissolved in water according to the need, and the concentrations thereof can be adjusted according to the need, in some specific embodiments of the present invention, the concentration of the first solution is 0.15 to 5mol/L, preferably 3 mol/L; the concentration of the first solution is 0.5-1.5 mol/L, and preferably 1 mol/L.
Furthermore, the selection of a complexing agent in the invention can be adjusted according to requirements, preferably, the complexing agent is at least one selected from ammonia water, sodium citrate and iminodiacetic acid, the molar ratio of the complexing agent to first ions is 1: 10-15, and the first ions are the sum of the amount of the metaaluminate ions and the titanium ions.
Further, the configurations of the mixed salt solution, the lithium salt solution and the chelating agent solution are also not particularly limited, and the solute with corresponding mass is weighed according to the need and dissolved in water to configure, wherein the nickel salt, the cobalt salt and the manganese salt in the mixed salt solution are weighed according to the stoichiometric ratio, and the stoichiometric ratio is determined according to the nickel-cobalt-manganese ternary single crystal material finally required to be prepared, so that the configurations are not particularly limited, and preferably, the ratio of the concentration of the mixed salt solution to the concentration of the lithium salt solution is 1-1.25, in some specific embodiments of the present invention, the concentration of the mixed salt solution is 1mol/L, the concentration of the lithium salt solution is 1mol/L, and the concentration of the chelating agent solution is 0.5-1.2 mol/L, and preferably 0.8 mol/L.
Further, the nickel salt, cobalt salt, manganese salt, lithium salt, etc. described in the present invention are not particularly limited, and any one conventionally used in the art may be used in the present invention, for example, in some specific embodiments, the nickel salt is selected from one or a mixture of two of nickel nitrate and nickel acetate;
the cobalt salt is selected from one or a mixture of two of cobalt nitrate and cobalt acetate;
the manganese salt is selected from one or a mixture of two of manganese nitrate and manganese acetate.
The lithium salt is selected from one or a mixture of more than two of lithium nitrate, lithium acetate and dilithium oxalate.
Preferably, the chelating agent is selected from one or more of citric acid, ethylene diamine tetraacetic acid and glycine, the molar ratio of the chelating agent to second ions is 1: 0.5-8, and the second ions are the sum of the amounts of nickel ions, cobalt ions, manganese ions and lithium ions.
Further, in some specific embodiments of the present invention, in the step of obtaining the nickel-coated cobalt-manganese ternary single crystal material, the organic solvent is selected from one or a mixture of two or more of methanol, ethanol, propanol, isopropanol, polyallyl alcohol, n-butanol, polyethylene glycol, polyvinylpyrrolidone and acetone, and the organic solvent is selected for improving the dispersion purpose, so that the titanium-aluminum composite and the precursor solid solution can be better dispersed therein, thereby achieving uniform coating of the titanium-aluminum composite on the precursor solid solution;
preferably, 5 to 50g of the titanium-aluminum composite oxide and the precursor solid solution are added to 100mL of the organic solvent, wherein the mass ratio of the titanium-aluminum composite oxide to the precursor solid solution is (1 to 10):100, and it is understood that the ratio of the titanium-aluminum composite to the precursor solid solution can be adjusted to improve the coating quality as long as the coating is achieved.
Further, in the step of obtaining the coated nickel-cobalt-manganese ternary single crystal material, the mixed powder is subjected to heat treatment to decompose nitrogen oxide, and the temperature of the heat treatment can be adjusted as required as long as the mixed powder can decompose nitrogen oxide, and in some specific embodiments of the present invention, the heat treatment specifically comprises the following steps: placing the mixed powder at 400-550 ℃ to react for 1-3 h;
sintering the heat-treated product, decomposing the precursor into ternary material by sintering, and controlling the temperature to obtain the expected single crystal material, wherein in some specific embodiments of the invention, the sintering comprises the following specific steps: sintering at 800-980 ℃ for 10-15 h in an oxygen atmosphere.
The invention discloses a coated nickel-cobalt-manganese ternary single crystal material, which is prepared by the preparation method of the first aspect of the invention.
The technical solution of the present invention will be more clearly and completely described below with reference to specific embodiments.
Example 1
Providing a titanium-aluminum composite oxide: inputting 3mol/L lithium metaaluminate solution and 1mol/L titanium nitrate solution into a colloid forming tank in a cocurrent flow manner, simultaneously adding complexing agent ammonia water into the colloid forming tank (wherein the molar ratio of the addition amount of the ammonia water to the sum of metal cations in the lithium metaaluminate solution and the titanium nitrate solution is 1: 10), introducing carbon dioxide gas, controlling the pH value to be constant at 8.0-11.0, reacting at 35 ℃, continuing introducing the carbon dioxide gas for 2 hours after reacting for 1 hour, washing and filtering for 3 times by using deionized water, placing the obtained precipitate in a forced air drying box at 90 ℃ for full drying, and grinding to obtain a titanium-aluminum composite oxide;
obtaining a precursor solid solution: respectively weighing nickel nitrate, cobalt nitrate and manganese nitrate according to the molar ratio of Ni to Co to Mn of 7:1:2 to prepare a mixed salt solution with the concentration of 1mol/L, preparing a lithium nitrate solution with the concentration of 1mol/L, preparing a citric acid solution (wherein the molar ratio of citric acid to metal cations in the mixed salt solution and the lithium salt solution is 1: 0.5), mixing the mixed salt solution, the lithium nitrate solution and the citric acid solution in a reaction kettle, and drying the mixed solution in the reaction kettle at the temperature of 160 ℃ to obtain a nickel-cobalt-manganese ternary single crystal material precursor solid solution;
obtaining a coated nickel-cobalt-manganese ternary single crystal material: according to the mass ratio of 4: mixing 100 parts of titanium-aluminum composite oxide, nickel-cobalt-manganese ternary single crystal material precursor solid solution and ethanol according to the proportion of 35g/100mL, and stirring for 20min at the temperature of 40 ℃ to obtain a mixed solution. And centrifuging, drying and sieving the prepared mixed solution to obtain mixed powder, carrying out reaction treatment on the mixed powder for 3 hours at the temperature of 500 ℃, cooling decomposed nitrogen oxides, and carrying out high-temperature sintering treatment on the obtained metal oxide powder for 12 hours in a roller kiln with the temperature of 890 ℃ and an oxygen atmosphere to obtain the titanium-aluminum composite oxide coated nickel-cobalt-manganese ternary single crystal material.
Comparative example 1
Compared with the example 1, the titanium-aluminum composite oxide coating is not carried out in the comparative example, and other steps and raw material compositions are the same as those in the example 1.
Comparative example 2
Providing a mixture of alumina and titania: according to the weight ratio of Al: respectively weighing alumina and titanium oxide with the Ti molar ratio of 3:1, and mechanically blending to obtain a uniform mixture of the alumina and the titanium oxide;
obtaining a precursor solid solution: the procedure is as in example 1;
the preparation method of the coated nickel-cobalt-manganese ternary single crystal material comprises the following steps: according to the mass ratio of 4: the mixture of 100 parts of alumina and titanium oxide and the solid solution of the precursor of the nickel-cobalt-manganese ternary single crystal material are added into ethanol according to the proportion of 35g/100mL, and the other steps are the same as those in the embodiment 1.
Example 2
Providing a titanium-aluminum composite oxide: inputting 0.15mol/L lithium metaaluminate solution and 0.5mol/L titanium nitrate solution into a colloid forming tank in a cocurrent flow manner, simultaneously adding sodium citrate serving as a complexing agent into the colloid forming tank (wherein the molar ratio of the addition amount of the sodium citrate to the sum of metal cations in the lithium metaaluminate solution and the titanium nitrate solution is 1: 12), introducing carbon dioxide gas, controlling the pH value to be constant at 8.0-11.0, reacting at 25 ℃, continuing introducing the carbon dioxide gas for 3 hours after reacting for 0.5 hour, washing and filtering for 3 times by using deionized water, then placing the obtained precipitate into a 90 ℃ forced air drying box for full drying, and grinding to obtain a titanium-aluminum composite oxide;
obtaining a precursor solid solution: respectively weighing nickel nitrate, cobalt nitrate and manganese nitrate according to the molar ratio of Ni to Co to Mn of 7:1:2 to prepare a mixed salt solution with the concentration of 1mol/L, preparing a lithium nitrate solution with the concentration of 1.15mol/L, preparing a glycine solution (wherein the molar ratio of glycine to metal cations in the mixed salt solution and the lithium salt solution is 1: 4), mixing the mixed salt solution, the lithium nitrate solution and the glycine solution in a reaction kettle, and drying the mixed solution in the reaction kettle at the temperature of 140 ℃ to obtain a nickel-cobalt-manganese ternary single crystal material precursor solid solution;
obtaining a coated nickel-cobalt-manganese ternary single crystal material: according to the mass ratio of 1: mixing 100 parts of titanium-aluminum composite oxide, nickel-cobalt-manganese ternary single crystal material precursor solid solution and ethanol according to the proportion of 5g/100mL, and stirring for 30min at the temperature of 25 ℃ to obtain a mixed solution. And centrifuging, drying and sieving the prepared mixed solution to obtain mixed powder, carrying out reaction treatment on the mixed powder for 2 hours at the temperature of 400 ℃, cooling decomposed nitrogen oxides, and carrying out high-temperature sintering treatment on the obtained metal oxide powder for 15 hours in a roller kiln with the temperature of 800 ℃ and an oxygen atmosphere to obtain the titanium-aluminum composite oxide coated nickel-cobalt-manganese ternary single crystal material.
Example 3
Providing a titanium-aluminum composite oxide: inputting 5mol/L sodium metaaluminate solution and 1.5mol/L titanium sulfate solution into a colloid forming tank in a cocurrent flow manner, simultaneously adding complexing agent iminodiacetic acid into the colloid forming tank (wherein the molar ratio of the addition amount of the iminodiacetic acid to the sum of metal cations in the lithium metaaluminate solution and the titanium nitrate solution is 1: 15), introducing carbon dioxide gas, controlling the pH value to be constant at 8.0-11.0, reacting at 50 ℃, continuing introducing the carbon dioxide gas for 2 hours after reacting for 1.5 hours, washing and filtering for 3 times by using deionized water, placing the obtained precipitate in a 90 ℃ blast drying oven for full drying, and grinding to obtain titanium-aluminum composite oxide;
obtaining a precursor solid solution: respectively weighing nickel acetate, cobalt acetate and manganese acetate according to the molar ratio of Ni to Co to Mn of 7:1:2 to prepare a mixed salt solution with the concentration of 1mol/L, preparing a lithium acetate solution with the concentration of 1.25mol/L, preparing an ethylene diamine tetraacetic acid solution (wherein the molar ratio of ethylene diamine tetraacetic acid to the mixed salt solution and metal cations in the lithium salt solution is 1: 8), mixing the mixed salt solution, the lithium acetate solution and the ethylene diamine tetraacetic acid solution in a reaction kettle, and drying the mixed solution in the reaction kettle at the temperature of 150 ℃ to obtain a nickel-cobalt-manganese ternary single crystal material precursor solid solution;
obtaining a coated nickel-cobalt-manganese ternary single crystal material: according to the mass ratio of 10: mixing 100 parts of titanium-aluminum composite oxide, a nickel-cobalt-manganese ternary single crystal material precursor solid solution and isopropanol according to a ratio of 50g/100mL, and stirring at 60 ℃ for 15min to obtain a mixed solution. And centrifuging, drying and sieving the prepared mixed solution to obtain mixed powder, carrying out reaction treatment on the mixed powder for 1h at the temperature of 550 ℃, cooling decomposed nitrogen oxides, and carrying out high-temperature sintering treatment on the obtained metal oxide powder for 10h in a roller kiln with the temperature of 980 ℃ and an oxygen atmosphere to obtain the titanium-aluminum composite oxide coated nickel-cobalt-manganese ternary single crystal material.
Test example
SEM characteristics of the nickel-cobalt-manganese ternary single crystal materials obtained in the example 1 and the comparative example 1 are respectively carried out, and the comparison between the figure 1 and the figure 2 shows that the surface of the nickel-cobalt-manganese ternary single crystal material in the example 1 is uniformly coated with the titanium-aluminum composite oxide.
The nickel-cobalt-manganese ternary single crystal materials of example 1 and comparative examples 1 to 2 were respectively prepared into wound pouch batteries, and were subjected to 45 ° high temperature cycle tests at test voltages of 3.0 to 4.4V, respectively, and the test results thereof are shown in table 1 and fig. 3.
As can be seen from the test results in FIG. 3, the high-temperature cycle performance of the coated nickel-cobalt-manganese ternary single crystal material under high voltage is obviously improved.
Table 1 pouch cell 45 ° high temperature cycle test results
Figure BDA0002956239390000101
As can be seen from the test results in table 1, the high-temperature cycle performance of the cladding nickel-cobalt-manganese ternary single crystal material in example 1 is obviously better than that of the cladding nickel-cobalt-manganese ternary single crystal material, because the cladding nickel-cobalt-manganese ternary single crystal material is unstable, and the structure is slowly destroyed in the cycle process, so that the cycle performance is deteriorated. Compared with the method of coating by adopting a mixed mode of aluminum oxide and titanium oxide in the comparative example 2, the coating effect of the medium titanium-aluminum composite oxide is better, the coating effect is obviously improved mainly because the titanium-aluminum composite oxide is coated in a solid solution mode, particularly, the nickel-cobalt-manganese ternary material is coated by adopting the aluminum oxide and the titanium oxide, and the excessively thick coating layer can prevent lithium ions from coming out and the electrolyte from contacting the material, so that the conductivity is reduced, and the capacity and the cycle of the battery are influenced to a certain extent.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The preparation method of the coated nickel-cobalt-manganese ternary single crystal material is characterized by comprising the following steps of:
providing a titanium-aluminum composite oxide;
obtaining a precursor solid solution: mixing a mixed salt solution, a lithium salt solution and a chelating agent solution, and carrying out hydrothermal treatment at 140-160 ℃ to obtain a precursor solid solution, wherein the mixed salt solution is a mixed solution of nickel salt, cobalt salt and manganese salt;
obtaining a coated nickel-cobalt-manganese ternary single crystal material: and adding the titanium-aluminum composite oxide and the precursor solid solution into an organic solvent, fully and uniformly mixing, separating, drying and sieving to obtain mixed powder, and carrying out heat treatment on the mixed powder and sintering to obtain the nickel-cobalt-manganese ternary single crystal material coated by the titanium-aluminum composite oxide.
2. The preparation method according to claim 1, wherein the titanium aluminum composite oxide is provided by the following specific steps: inputting a first solution and a second solution into a reaction container added with a complexing agent in a parallel flow mode, meanwhile, introducing carbon dioxide gas into the reaction container, controlling the pH value of the system to be constant at 8.0-11.0, controlling the reaction temperature to be 20-50 ℃, after reacting for 0.5-1.5 h, continuously introducing the carbon dioxide gas for at least 2h, washing, drying and grinding to obtain the titanium-aluminum composite oxide, wherein the first solution is a lithium metaaluminate solution or a sodium metaaluminate solution, and the second solution is a titanium nitrate solution or a titanium sulfate solution.
3. The method according to claim 2, wherein the concentration of the first solution is 0.15 to 5mol/L, and the concentration of the second solution is 0.5 to 1.5 mol/L;
the complexing agent is selected from at least one of ammonia water, sodium citrate and iminodiacetic acid, the molar ratio of the complexing agent to first ions is 1: 10-15, and the first ions are the sum of the quantity of aluminate ions and titanium ions.
4. The method according to claim 1, wherein the ratio of the concentration of the mixed salt solution to the concentration of the lithium salt solution is 1 to 1.25, and the concentration of the chelating agent solution is 0.5 to 1.2 mol/L.
5. The preparation method according to claim 1, wherein the nickel salt is selected from one or a mixture of nickel nitrate and nickel acetate;
the cobalt salt is selected from one or a mixture of two of cobalt nitrate and cobalt acetate;
the manganese salt is selected from one or a mixture of two of manganese nitrate and manganese acetate.
6. The method according to claim 1, wherein the lithium salt is selected from one or a mixture of two or more of lithium nitrate, lithium acetate, and dilithium oxalate.
7. The method according to claim 1, wherein the chelating agent is one or more selected from citric acid, ethylenediaminetetraacetic acid and glycine, the molar ratio of the chelating agent to the second ion is 1:0.5 to 8, and the second ion is the sum of the amounts of nickel ion, cobalt ion, manganese ion and lithium ion.
8. The method according to claim 1, wherein in the step of obtaining the nickel-coated cobalt manganese ternary single crystal material, the organic solvent is selected from one or a mixture of two or more of methanol, ethanol, propanol, isopropanol, polyallyl alcohol, n-butanol, polyethylene glycol, polyvinylpyrrolidone, and acetone;
adding 5-50 g of the titanium-aluminum composite oxide and the precursor solid solution into each 100mL of the organic solvent, wherein the mass ratio of the titanium-aluminum composite oxide to the precursor solid solution is (1-10): 100.
9. The preparation method according to claim 1, wherein in the step of obtaining the coated nickel-cobalt-manganese ternary single crystal material, the heat treatment comprises the following specific steps: placing the mixed powder at 400-550 ℃ to react for 1-3 h;
the sintering comprises the following specific steps: sintering at 800-980 ℃ for 10-15 h in an oxygen atmosphere.
10. A coated nickel-cobalt-manganese ternary single crystal material, characterized in that it is produced by the production method according to any one of claims 1 to 9.
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