CN113809321A - Preparation method and application of precursor of aluminum and zirconium doped lithium nickelate cathode material - Google Patents
Preparation method and application of precursor of aluminum and zirconium doped lithium nickelate cathode material Download PDFInfo
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- CN113809321A CN113809321A CN202111080995.3A CN202111080995A CN113809321A CN 113809321 A CN113809321 A CN 113809321A CN 202111080995 A CN202111080995 A CN 202111080995A CN 113809321 A CN113809321 A CN 113809321A
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- C—CHEMISTRY; METALLURGY
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- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a preparation method and application of a precursor of an aluminum and zirconium doped lithium nickelate positive electrode material, and particularly relates to the field of electrode materials. The method comprises the steps of preparing a sodium metaaluminate solution, preparing product slurry and preparing a precursor to obtain the special precursor spherical nickel hydroxide for preparing the aluminum and zirconium doped spherical lithium nickelate anode material. The precursor prepared by the preparation method of the precursor of the aluminum and zirconium doped lithium nickelate positive material can be applied to preparation of the aluminum and zirconium doped spheroidal lithium nickelate positive material. The aluminum and zirconium doped lithium nickelate precursor synthesized by the method is in the shape of sphere-like secondary particles, the particle shape is uniform, the internal elements are uniformly distributed, and the tap density is high. The lithium nickelate positive electrode material prepared by mixing and sintering the precursor and the lithium hydroxide has high capacity and excellent electrochemical performance such as long cycle.
Description
Technical Field
The invention relates to the field of electrode materials, in particular to a preparation method and application of a precursor of an aluminum and zirconium doped lithium nickelate positive electrode material.
Background
Lithium nickel oxide, also called lithium nickelate for short, has the chemical general formula LiNiO2Is a lithium ion batteryThe positive electrode material is considered as one of the most promising positive electrode materials in the future due to the ultrahigh specific capacity of more than 220mAh/g and the high discharge plateau voltage of 3.8V, but Ni is used as the positive electrode material2+Ions with Li+The ion radius of the nickel oxide is similar, so that the pure lithium nickelate is easy to generate serious nickel-lithium mixed-discharging phenomenon in crystal lattices, thereby reducing the cycle performance of the material.
At present, researchers in the industry aiming at the problems often adopt material modification means such as doping coating and the like to reduce the cation mixed-arranged degree of lithium nickelate so as to improve the electrochemical stability of the material. The patent CN 109286001 a proposes to introduce other metal ion doping in the precipitation link to improve the material performance. However, the introduction mode of the doping element cannot be specifically described in the patent, because the solubility product constants of ions of different metal elements have great difference, if proper introduction modes and element types are not selected, synchronous precipitation and uniform doping of the introduced elements and nickel elements cannot be achieved, and the final appearance of the precursor material after aging is greatly influenced by improper element introduction modes, so that the precursor cannot form spheroidal particles with uniform dispersion, uniform appearance and consistent particle size.
In summary, a synthesis method capable of uniformly and effectively doping modification and greatly improving the performance of the lithium nickelate cathode material is needed in the industry at present.
Disclosure of Invention
Therefore, the invention provides a preparation method and application of a precursor of an aluminum and zirconium doped lithium nickelate positive electrode material, and aims to solve the problem that in the prior art, due to inappropriate element types, the precursor cannot form spheroidal particles which are uniform in dispersion, uniform in appearance and consistent in particle size.
In order to achieve the above purpose, the invention provides the following technical scheme:
according to a first aspect of the present invention, there is provided a method for preparing a precursor of an aluminum-zirconium-doped lithium nickelate positive electrode material, the method comprising the steps of:
step one, preparing sodium metaaluminate solution
Dissolving soluble aluminum salt in a high-concentration sodium hydroxide solution to form a sodium metaaluminate solution;
step two, preparation of product slurry
Enabling the sodium metaaluminate solution, the mixed salt solution containing nickel and zirconium ions and the ammonia water solution to flow in parallel according to a certain flow ratio into a constant-temperature stirring synthesis kettle with 3-10% of ammonia water base solution and capable of automatically regulating and controlling pH value at 40-60 ℃ for coprecipitation, and reacting to obtain product slurry;
step three, preparation of precursor
And aging, filtering, washing and drying the product slurry to obtain the special precursor spherical nickel hydroxide for preparing the aluminum and zirconium doped spherical lithium nickelate anode material.
Further, the soluble aluminum salt is one or more of sulfate, nitrate or chloride.
Further, the concentration of the high-concentration sodium hydroxide solution is 2-10 mol/L.
Further, in the second step, the flow ratio of the sodium metaaluminate solution to the mixed salt solution containing nickel and zirconium ions and the ammonia water solution is 1: 0.5-2.0: 0.1 to 1.
Furthermore, in the mixed salt solution containing nickel and zirconium ions, the concentration of nickel ions is 0.5-2.5 mol/L, and the concentration of zirconium ions is 0.0005-0.1 mol/L.
Further, the aging process is as follows: and fully and uniformly dispersing the product slurry in an aging and stirring tank, wherein the pH value in an aging system is 9-12, the temperature is 40-60 ℃, the solid content is 10-40%, and the aging time is 0.5-24 h.
Further, the washing process is as follows: and (3) alternately washing the mixed slurry by using deionized water at the temperature of 40-60 ℃ and 60-320 g/L sodium hydroxide solution at the temperature of 40-60 ℃ for 3-5 times respectively to obtain the aluminum-zirconium-doped spheroidal nickel hydroxide filter material.
Further, the drying process is as follows: and drying the aluminum-zirconium-doped spheroidal nickel hydroxide filter material at 100-120 ℃ for more than 10h to obtain the special precursor spheroidal nickel hydroxide for preparing the aluminum-zirconium-doped spheroidal lithium nickelate anode material.
The precursor prepared by the preparation method of the precursor of the aluminum and zirconium doped lithium nickelate cathode material provided by the second aspect of the invention can be applied to preparation of an aluminum and zirconium doped spheroidal lithium nickelate cathode material.
According to the method for preparing the aluminum-zirconium-doped spheroidal lithium nickelate positive electrode material provided by the third aspect of the invention, the method comprises the steps of uniformly mixing a special precursor spheroidal nickel hydroxide of the prepared aluminum-zirconium-doped spheroidal lithium nickelate positive electrode material to obtain a precursor compound, sintering the precursor compound at a constant temperature of 600-800 ℃ for 8-20h under a pure oxygen atmosphere, and naturally cooling to obtain the aluminum-zirconium-doped spheroidal lithium nickelate positive electrode material.
Further, in the precursor compound, the molar ratio of the lithium element to the transition metal nickel element is 1.0-1.10: 1.
The invention has the following advantages:
the method adopts the sodium metaaluminate process to introduce the aluminum element in the coprecipitation link, solves the technical problem that the aluminum element and the nickel element cannot be precipitated synchronously, and ensures that the aluminum element and the nickel element can be precipitated uniformly so as to ensure the uniform appearance and uniform particle size of precipitated particles. Due to Zr4+And Ni2+The solubility product constants of the zirconium-zirconium mixed salt solution are similar, so that the zirconium element is introduced by adopting the coprecipitation reaction of the mixed salt solution prepared from the zirconium salt and the nickel salt, and the chemical proportion of the nickel-zirconium element is effectively controlled, so that the controllable morphology of precipitated particles is ensured.
The aluminum and zirconium doped lithium nickelate precursor synthesized by the method is in the shape of sphere-like secondary particles, the particle shape is uniform, the internal elements are uniformly distributed, and the tap density is high. The lithium nickelate positive electrode material prepared by mixing and sintering the precursor and the lithium hydroxide has high capacity and excellent electrochemical performance such as long cycle.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions that the present invention can be implemented, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the effects and the achievable by the present invention, should still fall within the range that the technical contents disclosed in the present invention can cover.
FIG. 1 is an SEM image of a special precursor for aluminum zirconium-doped spheroidal lithium nickelate prepared by the method in example 3 of the invention;
FIG. 2 is an SEM image of an Al-Zr doped spheroidal lithium nickelate cathode material prepared by the method of example 3 of the invention;
fig. 3 is a cycle chart of the electrical properties of the aluminum zirconium doped spheroidal lithium nickelate positive electrode material prepared by the method in example 3 of the invention.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Embodiment 1 preparation method and application of precursor of aluminum and zirconium doped lithium nickelate cathode material
The embodiment of the invention provides a precursor for preparing an aluminum and zirconium doped lithium nickelate positive material and a method for preparing the aluminum and zirconium doped lithium nickelate positive material by using the precursor, which comprises the following steps:
preparing a mixed salt solution with the nickel ion concentration of 2mol/L and the zirconium ion concentration of 0.003 mol/L;
step two, weighing a proper amount of aluminum sulfate hexadecahydrate, adding the aluminum sulfate hexadecahydrate into a sodium hydroxide solution with the concentration of 4.5mol/L to form a 0.1mol/L sodium metaaluminate mixed solution;
step three, adding the mixed salt solution, the sodium metaaluminate mixed solution and the ammonia water solution into a stirring synthesis kettle with 5% mass concentration ammonia water base solution and constant temperature of 55 ℃ in a concurrent flow manner to carry out coprecipitation reaction, and regulating the pH value of a reaction system to be 11.2 by a system;
transferring the precursor slurry obtained by the reaction into an aging tank, stirring and aging, controlling the pH value in an aging system to be more than 11.0, controlling the temperature of the aging system to be 55 ℃, controlling the solid content of the aging system to be 20%, and aging for 12 hours;
step five, alternately washing the aged precursor mixed slurry for 5 times by using deionized water at 50 ℃ and 160g/L sodium hydroxide solution at 50 ℃ to obtain an aluminum-zirconium doped spheroidal nickel hydroxide filter cake;
step six, drying the filter cake in a blast oven at 100 ℃ for 10h to obtain aluminum-zirconium doped spheroidal nickel hydroxide;
step seven, mixing the prepared aluminum-zirconium-doped spheroidal nickel hydroxide with lithium hydroxide to obtain a precursor compound, and controlling the addition amount of the lithium hydroxide according to the ratio of the lithium element to the nickel element in the mixture of 1.03: 1;
and step eight, sintering the uniformly mixed precursor mixture in a pure oxygen atmosphere to 700 ℃, keeping the temperature for 12 hours, and cooling to obtain the aluminum-zirconium-doped spheroidal lithium nickelate anode material with uniform particle size distribution.
The material is tested to have compact particle size distribution, good particle sphericity, a D50 value of 6-8 mu m and excellent electrochemical performance, the 0.2C discharge capacity can reach 221mAh/g, the first coulombic efficiency is 88.9 percent, and the cycle retention rate of 100 circles can reach more than 93 percent in a discharge interval of 3.0-4.3V. The capacity of the 5C capacitor still has 171.2mAh/g under the charge-discharge multiplying power.
Preferably, the flow ratio of the mixed salt solution, the mixed sodium metaaluminate solution and the ammonia water solution is 1:1: 0.1.
Embodiment 2 preparation method and application of precursor of aluminum and zirconium doped lithium nickelate cathode material
The embodiment of the invention provides a precursor for preparing an aluminum and zirconium doped lithium nickelate positive material and a method for preparing the aluminum and zirconium doped lithium nickelate positive material by using the precursor, which comprises the following steps:
step one, preparing a mixed salt solution with the nickel ion concentration of 2mol/L and the zirconium ion concentration of 0.004 mol/L;
step two, weighing a proper amount of aluminum nitrate nonahydrate and adding the aluminum nitrate nonahydrate into a sodium hydroxide solution with the concentration of 4.5mol/L to form a 0.1mol/L sodium metaaluminate mixed solution;
step three, adding the mixed salt solution, the sodium metaaluminate mixed solution and the ammonia water solution into a stirring synthesis kettle with 3% mass concentration ammonia water base solution and constant temperature of 50 ℃ in a concurrent flow manner to carry out coprecipitation reaction, and regulating the pH value of a reaction system to be 11.1 by a system;
transferring the precursor slurry obtained by the reaction into an aging tank, stirring and aging, controlling the pH value in an aging system to be more than 11.0, controlling the temperature of the aging system to be 50 ℃, controlling the solid content of the aging system to be 20%, and aging for 24 hours;
step five, the aged precursor mixed slurry is alternately washed for 5 times by using deionized water at 55 ℃ and 160g/L sodium hydroxide solution at 55 ℃ to obtain an aluminum-zirconium doped spheroidal nickel hydroxide filter cake;
step six, drying the filter cake in a blast oven at 105 ℃ for 10h to obtain aluminum-zirconium doped spheroidal nickel hydroxide;
step seven, mixing the prepared aluminum-zirconium-doped spheroidal nickel hydroxide with lithium hydroxide to obtain a precursor compound, and controlling the addition amount of the lithium hydroxide according to the ratio of the lithium element to the nickel element in the mixture of 1.02: 1;
and step eight, sintering the uniformly mixed precursor mixture in a pure oxygen atmosphere to 700 ℃, keeping the temperature for 12 hours, and cooling to obtain the aluminum-zirconium-doped spheroidal lithium nickelate anode material with uniform particle size distribution.
The material is tested to have compact particle size distribution, good particle sphericity, a D50 value of 8-10 mu m and excellent electrochemical performance, the 0.2C discharge capacity can reach 223mAh/g in a discharge interval of 3.0V-4.3V, the first coulombic efficiency is 88.5%, and the cycle retention rate of 100 circles can reach more than 95%. The capacity of the 5C capacitor still has 165.2mAh/g under the charge-discharge multiplying power.
Preferably, the flow ratio of the mixed salt solution, the mixed sodium metaaluminate solution and the ammonia water solution is 1:1: 0.1.
Embodiment 3 preparation method and application of precursor of aluminum and zirconium doped lithium nickelate cathode material
The embodiment of the invention provides a precursor for preparing an aluminum and zirconium doped lithium nickelate positive material and a method for preparing the aluminum and zirconium doped lithium nickelate positive material by using the precursor, which comprises the following steps:
the invention provides a method for preparing an aluminum and zirconium doped spherical lithium nickelate positive electrode material and a special precursor thereof, which comprises the following steps:
preparing a mixed salt solution with nickel ion concentration of 1.75mol/L and zirconium ion concentration of 0.0025 mol/L;
step two, weighing a proper amount of aluminum nitrate nonahydrate, and adding the aluminum nitrate nonahydrate into a sodium hydroxide solution with the concentration of 4mol/L to form a 0.085mol/L sodium metaaluminate mixed solution;
step three, adding the mixed salt solution, the sodium metaaluminate mixed solution and the ammonia water solution into a stirring synthesis kettle with 8% mass concentration ammonia water base solution and constant temperature of 55 ℃ in a concurrent flow manner to carry out coprecipitation reaction, and regulating the pH value of a reaction system to be 11.5 by a system;
transferring the precursor slurry obtained by the reaction into an aging tank, stirring and aging, controlling the pH value in an aging system to be more than 11.2, controlling the temperature of the aging system to be 55 ℃, controlling the solid content of the aging system to be 15%, and aging for 24 hours;
step five, the aged precursor mixed slurry is alternately washed for 5 times by using deionized water at 55 ℃ and 160g/L sodium hydroxide solution at 55 ℃ to obtain an aluminum-zirconium doped spheroidal nickel hydroxide filter cake;
step six, drying the filter cake in a blast oven at 105 ℃ for 10h to obtain aluminum-zirconium doped spheroidal nickel hydroxide;
step seven, mixing the prepared aluminum-zirconium-doped spheroidal nickel hydroxide with lithium hydroxide to obtain a precursor compound, and controlling the addition amount of the lithium hydroxide according to the ratio of the lithium element to the nickel element in the mixture of 1.02: 1;
and step eight, sintering the uniformly mixed precursor mixture in a pure oxygen atmosphere to 680 ℃, keeping the temperature for 12 hours, and cooling to obtain the aluminum-zirconium-doped spheroidal lithium nickelate anode material with uniform particle size distribution.
The material is tested to have compact particle size distribution, good particle sphericity, D50 value of 4-6 μm and excellent electrochemical performance, the 0.2C discharge capacity can reach 225mAh/g, the initial coulombic efficiency can reach 89.1% in a discharge interval of 3.0V-4.3V, and the 100-circle cycle retention rate can reach more than 93%. The capacity of the 5C capacitor still has 173.4mAh/g under the charge-discharge multiplying power.
Preferably, the flow ratio of the mixed salt solution, the mixed sodium metaaluminate solution and the ammonia water solution is 1:1: 0.1.
As shown in fig. 1, an SEM image of the special precursor, namely, the spherical nickel hydroxide, for the aluminum zirconium doped lithium nickelate special-purpose precursor, according to the method in embodiment 3 of the present invention, shows uniform particle distribution, high sphericity, and a particle size of 4 to 6 μm. As shown in fig. 2, which is an SEM image of the aluminum zirconium doped spheroidal lithium nickelate positive electrode material prepared by the method of example 3 of the present invention, the prepared lithium nickelate has high tap density and excellent electrochemical properties. Fig. 3 is a cycle chart of the electrical properties of the aluminum zirconium doped spheroidal lithium nickelate positive electrode material of example 3 of the invention.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a precursor of an aluminum and zirconium doped lithium nickelate cathode material is characterized by comprising the following steps:
step one, preparing sodium metaaluminate solution
Dissolving soluble aluminum salt in a high-concentration sodium hydroxide solution to form a sodium metaaluminate solution;
step two, preparation of product slurry
Enabling the sodium metaaluminate solution, the mixed salt solution containing nickel and zirconium ions and the ammonia water solution to flow in parallel according to a certain flow ratio into a constant-temperature stirring synthesis kettle with 3-10% of ammonia water base solution and capable of automatically regulating and controlling pH value at 40-60 ℃ for coprecipitation, and reacting to obtain product slurry;
step three, preparation of precursor
And aging, filtering, washing and drying the product slurry to obtain the special precursor spherical nickel hydroxide for preparing the aluminum and zirconium doped spherical lithium nickelate anode material.
2. The method for preparing the precursor of the aluminum and zirconium doped lithium nickelate cathode material according to claim 1, wherein the soluble aluminum salt is one or more of sulfate, nitrate or chloride.
3. The method for preparing the precursor of the aluminum and zirconium doped lithium nickelate cathode material according to claim 1, wherein the concentration of the high-concentration sodium hydroxide solution is 2-10 mol/L.
4. The method for preparing the precursor of the aluminum-zirconium-doped lithium nickelate cathode material according to claim 1, wherein in the second step, the flow ratio of the sodium metaaluminate solution to the mixed salt solution containing nickel and zirconium ions to the ammonia water solution is 1: 0.5-2.0: 0.1 to 1.
5. The method for preparing the precursor of the aluminum-zirconium-doped lithium nickelate cathode material according to claim 1, wherein the concentration of nickel ions in the mixed salt solution containing nickel ions and zirconium ions is 0.5-2.5 mol/L, and the concentration of zirconium ions in the mixed salt solution containing nickel ions and zirconium ions is 0.0005-0.1 mol/L.
6. The method for preparing the precursor of the aluminum-zirconium-doped lithium nickelate cathode material according to claim 1, wherein the aging process comprises the following steps: and fully and uniformly dispersing the product slurry in an aging and stirring tank, wherein the pH value in an aging system is 9-12, the temperature is 40-60 ℃, the solid content is 10-40%, and the aging time is 0.5-24 h.
7. The method for preparing the precursor of the aluminum and zirconium doped lithium nickelate cathode material according to claim 1, wherein the washing process comprises the following steps: and (3) alternately washing the mixed slurry by using deionized water at the temperature of 40-60 ℃ and 60-320 g/L sodium hydroxide solution at the temperature of 40-60 ℃ for 3-5 times respectively to obtain the aluminum-zirconium-doped spheroidal nickel hydroxide filter material.
8. The method for preparing the precursor of the aluminum-zirconium-doped lithium nickelate cathode material according to claim 1, wherein the drying process comprises the following steps: and drying the aluminum-zirconium-doped spheroidal nickel hydroxide filter material at 100-120 ℃ for more than 10h to obtain the precursor spheroidal nickel hydroxide special for preparing the aluminum-zirconium-doped spheroidal lithium nickelate anode material.
9. The precursor prepared by the method for preparing the precursor of the aluminum and zirconium-doped lithium nickelate positive electrode material according to any one of claims 1 to 8, and the precursor is used for preparing the aluminum and zirconium-doped spheroidal lithium nickelate positive electrode material.
10. The application of claim 9, wherein the preparation method of the aluminum-zirconium-doped spheroidal lithium nickelate positive electrode material comprises the steps of uniformly mixing a special precursor spheroidal nickel hydroxide of the prepared aluminum-zirconium-doped spheroidal lithium nickelate positive electrode material to obtain a precursor compound, sintering the precursor compound at a constant temperature of 600-800 ℃ for 8-20 hours under a pure oxygen atmosphere, and naturally cooling to obtain the aluminum-zirconium-doped spheroidal lithium nickelate positive electrode material.
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| CN114368792A (en) * | 2022-01-10 | 2022-04-19 | 荆门市格林美新材料有限公司 | Preparation method of aluminum-doped cobaltosic oxide particles |
| CN115321610A (en) * | 2022-08-31 | 2022-11-11 | 荆门市格林美新材料有限公司 | Zirconium-aluminum double-doped nickel-cobalt-manganese hydroxide and preparation method and application thereof |
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