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CN111029545A - Nano lithium aluminate coated nickel-based multi-element positive electrode material and preparation method thereof - Google Patents

Nano lithium aluminate coated nickel-based multi-element positive electrode material and preparation method thereof Download PDF

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CN111029545A
CN111029545A CN201911239723.6A CN201911239723A CN111029545A CN 111029545 A CN111029545 A CN 111029545A CN 201911239723 A CN201911239723 A CN 201911239723A CN 111029545 A CN111029545 A CN 111029545A
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aluminate
based multi
lithium
nickel
precursor
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张云
周金伟
吴昊
王倩
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Sichuan University
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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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/48—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract

The application relates to the technical field of preparation of anode materials, in particular to a nano lithium aluminate coated nickel-based multi-element anode material and a preparation method thereof. The nano lithium aluminate coated nickel-based multi-element cathode material can slowly generate Al (OH) by regulating the concentration of aluminate and bicarbonate and the amount of substances3The deposition reaction of (1). By the coating method, a thin and compact layer of Al (OH) can be uniformly deposited on the surface of the precursor of the nickel-based multi-element cathode material3The layered structure forms a composite precursor, which is coated with Al (OH)3Of nickel seriesAnd mixing the multi-element anode material composite precursor with a lithium source, and finally sintering at high temperature to obtain the nano lithium aluminate coated nickel-based multi-element anode material. The coating layer of the nickel-based multi-element cathode material coated by the nano lithium aluminate can effectively protect the cathode and improve the stability of the cathode material, so that the cycle performance of the battery is improved, and the rate capability of the battery can be improved.

Description

Nano lithium aluminate coated nickel-based multi-element positive electrode material and preparation method thereof
Technical Field
The application relates to the technical field of preparation of anode materials, in particular to a nano lithium aluminate coated nickel-based multi-element anode material and a preparation method thereof.
Background
With the excessive consumption of fossil energy and the increasing severity of environmental problems, clean energy is rapidly developed, which in turn drives the development of energy storage devices. The early lithium iron phosphate can not meet the market requirement due to the problems of low specific capacity and the like, so that various large battery manufacturers aim at nickel-based multi-element cathode materials with higher capacity. The nickel-based multi-element cathode material also receives more and more attention, and gradually becomes a hot cathode material for the research of lithium ion batteries.
At present, most of nickel-based multi-element cathode materials are synthesized by a coprecipitation method reinforced phase sintering method, namely, a multi-element material precursor prepared by the coprecipitation method is matched with a lithium source and then is sintered at high temperature. The nickel-based multi-element positive electrode material is prepared from Li+And Ni2+The ionic radii are very similar, lithium-nickel mixed discharge is easy to occur, particularly for nickel-based multi-element cathode materials with high Ni content, lithium-nickel mixed discharge is easy to occur, and further the structural stability of the material is poor. In addition, the nickel-based multi-element anode material is easier to react with H in the air2O and CO2Reaction occurs, leading to the formation of LiCO on the surface3And LiOH, etc., to form an insulating layer on the surface of the electrode, thereby blocking Li+The diffusion and the transport of electrons of (a) severely degrade the performance of the battery.
Disclosure of Invention
The invention provides a preparation method of a nickel-based multi-element anode material coated by nano lithium aluminate, which is characterized by comprising the following steps:
1) taking NixCoyM1-x-y(OH)2Adding the precursor and aluminate into deionized water to form a suspension;
2) adding a bicarbonate solution into the suspension, and aging to obtain a composite precursor;
3) washing the composite precursor by using deionized water and drying;
4) uniformly mixing the dried composite precursor with a lithium source according to the proportion that the sum of the amounts of Ni, Co, M and Al elements and the amount of Li elements is 1 (1-1.08), and sintering at the temperature of 700-950 ℃ for 4-20 hours under the environment that the oxygen content is 21-100% to obtain the nano lithium aluminate coated nickel-based multi-element cathode material;
in the step 1), M is one or more of Mn, Al, Mg or W.
Further, the NixCoyM1-x-y(OH)2The precursor satisfies x is more than or equal to 0.60 and less than 1, y is more than 0 and less than or equal to 0.20, and x + y is less than or equal to 1.
Further, in step 1), the NixCoyM1-x-y(OH)2The mass ratio of the precursor to the aluminate is 1 (0.01-0.05).
Further, in the step 1), the aluminate is one or more of potassium aluminate and sodium aluminate.
Further, in the step 2), the amount of the bicarbonate substance added is 1-5 times of the amount of the aluminate substance.
Further, in the step 2), the bicarbonate is a saturated solution of sodium bicarbonate, and the adding speed of the saturated solution of sodium bicarbonate is 0.1-2 ml/min.
Further, in the step 2), the aging time is 2-5 hours.
Further, in step 4), the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate or lithium citrate.
Further, in the step 4), before sintering at the temperature of 700-950 ℃ for 4-20 hours, the mixture of the composite precursor and the lithium source is pre-sintered at the temperature of 300-600 ℃ for 2-8 hours under the environment with the oxygen content of 21-100%.
The invention also provides a nickel-based multi-element cathode material coated by the nano lithium aluminate, and the nickel-based multi-element cathode material coated by the nano lithium aluminate is prepared by adopting the preparation method.
The application discloses a nickel-based multi-element anode material coated by nano lithium aluminate coats a precursor of the nickel-based multi-element anode material by using a wet chemical coating method, which comprises the following specific implementation modes: by regulating aluminate and carbonThe concentration of hydrogen acid salt and the amount of substance can make the two occur more slowly Al (OH)3In the process, because aluminate and bicarbonate are both alkalescent, the precursor body of the nickel-based multi-element cathode material is not affected. By the coating method, a thin layer of Al (OH) can be uniformly deposited on the surface of the nickel-based multi-element cathode material precursor3The layered structure forms a composite precursor, which is coated with Al (OH)3The composite precursor of the nickel-based multi-element anode material is mixed with a lithium source, and finally, the nano lithium aluminate coated nickel-based multi-element anode material can be obtained through high-temperature sintering. The coating layer of the nickel-based multi-element cathode material coated by the nano lithium aluminate can effectively protect the cathode and improve the stability of the cathode material, so that the cycle performance of the battery is improved, and the rate capability of the battery can be improved.
Drawings
FIG. 1 is an electron microscope image of a precursor before coating;
FIG. 2 shows the coating with Al (OH)3Taking an electron microscope image of the composite precursor;
FIG. 3 is a graph showing the results of rate capability tests of example 1 and comparative example;
FIG. 4 is a graph of the cycle performance test results of example 1 and comparative example at 2C.
Detailed Description
The application provides a nickel-based multi-element anode material coated by nano lithium aluminate and a preparation method thereof, wherein the preparation method comprises the following steps:
1)NixCoyM1-x-y(OH)2adding the precursor and aluminate into deionized water according to the mass ratio of 1: 0.01-0.05 to form a suspension, wherein the Ni isxCoyM1-x-y(OH)2In the precursor, x is more than or equal to 0.60 and less than or equal to 1, y is more than 0 and less than or equal to 0.20, x + y is less than or equal to 1, M is one or more of Mn, Al, Mg or W, and aluminate is soluble salt, preferably one or more of potassium aluminate and sodium aluminate;
2) adding a certain amount of bicarbonate solution into the suspension obtained in the step 1), and aging for 2-5 hours to obtain a composite precursor, wherein the addition amount of the bicarbonate satisfies the following conditions: the amount of bicarbonate is 1-5 times of the amount of aluminate substances added in the step 1), the bicarbonate is preferably a saturated solution of sodium bicarbonate, and the adding speed is controlled to be 0.1-2 ml/min;
3) washing the composite precursor for many times by using deionized water, carrying out suction filtration, and then drying the composite precursor in a vacuum oven at the drying temperature of 80-100 ℃ for 12-16 hours;
4) uniformly mixing the dried composite precursor with a lithium source according to the ratio of the sum of the amounts of Ni, Co, M and Al elements to the amount of Li elements of 1: 1-1.08, and sintering at 700-950 ℃ for 4-20 hours in an environment with the oxygen content of 21-100% to obtain the nano lithium aluminate coated nickel-based multi-element cathode material; the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate or lithium citrate, and preferably, before sintering at the temperature of 700-950 ℃ for 4-20 hours, the mixture of the composite precursor and the lithium source is pre-sintered at the temperature of 300-600 ℃ for 2-8 hours in an environment with the oxygen content of 21-100%, wherein the sintering process can be started from room temperature, and the temperature rising rate is 3-5 ℃/min.
The application also provides a nickel-based multi-element cathode material coated by the nano lithium aluminate, and the nickel-based multi-element cathode material coated by the nano lithium aluminate is prepared by adopting the preparation method.
As shown in fig. 1 and 2, the nano lithium aluminate-coated nickel-based multi-element cathode material disclosed in the present application is prepared by coating a precursor of a nickel-based multi-element cathode material by using a wet chemical coating method, and the specific implementation manner is as follows: by controlling the concentration of aluminate and bicarbonate and the amount of the substances, the aluminate and bicarbonate can generate slower Al (OH)3In the process, because aluminate and bicarbonate are both alkalescent, the precursor body of the nickel-based multi-element cathode material is not influenced. By the coating method, a thin and compact layer of Al (OH) can be uniformly deposited on the surface of the precursor of the nickel-based multi-element cathode material3The layered structure forms a composite precursor, which is coated with Al (OH)3Nickel series multielement positive electrodeThe composite precursor of the cathode material is mixed with a lithium source, and finally, the nano lithium aluminate coated nickel-based multi-element cathode material can be obtained through high-temperature sintering, and the coating layer has uniform components and controllable thickness.
The practical effects of the nano lithium aluminate-coated nickel-based multi-element cathode material according to the present invention will be described below with reference to specific examples.
Example 1
The nano lithium aluminate coated nickel-based multi-element cathode material is prepared by the following steps:
1)NixCoyM1-x-y(OH)2adding the precursor and aluminate into deionized water according to the mass ratio of 1:0.03 to form a suspension, wherein the Ni isxCoyM1-x-y(OH)2In the precursor, x is 0.80, y is 0.1, M is Mn, and the aluminate is sodium aluminate;
2) adding a saturated sodium bicarbonate solution into the suspension obtained in the step 1) at a speed of 1ml/min, and aging for 4 hours to obtain a composite precursor, wherein the amount of the bicarbonate substance is 3 times of the amount of the aluminate substance added in the step 1);
3) washing the composite precursor with deionized water for many times, carrying out suction filtration, and drying the composite precursor in a vacuum oven at 100 ℃ for 14 hours;
4) uniformly mixing the composite precursor with a lithium source according to the ratio of the sum of the amounts of Ni, Co, Mn and Al elements to the amount of Li elements being 1:1.04, presintering for 2 hours at the temperature of 400 ℃ in the environment with the oxygen content of 50%, and sintering for 15 hours at the temperature of 850 ℃ to obtain the nano lithium aluminate coated nickel-based multi-element cathode material; wherein the lithium source is lithium hydroxide.
The nano lithium aluminate-coated nickel-based multi-element cathode material described in example 1 was prepared by the above preparation method.
Example 2
The nano lithium aluminate coated nickel-based multi-element cathode material is prepared by the following steps:
1)NixCoyM1-x-y(OH)2adding the precursor and aluminate into deionized water according to the mass ratio of 1:0.01 to form a suspension, wherein the Ni isxCoyM1-x-y(OH)2In the precursor, x is 0.80, y is 0.1, M is Mn, and the aluminate is sodium aluminate;
2) adding a saturated sodium bicarbonate solution into the suspension obtained in the step 1) at a speed of 1ml/min, and aging for 4 hours to obtain a composite precursor, wherein the amount of the bicarbonate substance is 3 times of the amount of the aluminate substance added in the step 1);
3) washing the composite precursor with deionized water for many times, carrying out suction filtration, and drying the composite precursor in a vacuum oven at 100 ℃ for 14 hours;
4) uniformly mixing the dried composite precursor with a lithium source according to the ratio of the sum of the amounts of Ni, Co, Mn and Al elements to the amount of Li elements being 1:1.04, presintering the mixture at 400 ℃ for 2 hours under the environment with the oxygen content of 50 percent, and sintering the mixture at 850 ℃ for 15 hours to obtain the nano lithium aluminate coated nickel-based multi-element cathode material; wherein the lithium source is lithium hydroxide.
The nano lithium aluminate-coated nickel-based multi-element cathode material of example 2 is prepared by the preparation method. The nano lithium aluminate coated nickel-based multi-element cathode material of the embodiment 2 is prepared by the preparation method, and compared with the preparation method of the embodiment 1, the preparation method of the nano lithium aluminate coated nickel-based multi-element cathode material of the embodiment 2 only has Ni in the step 1)xCoyM1-x-y(OH)2The mass ratio of the precursor to the aluminate is different, and the rest is the same.
Example 3
The nano lithium aluminate coated nickel-based multi-element cathode material is prepared by the following steps:
1)NixCoyM1-x-y(OH)2adding the precursor and aluminate into deionized water according to the mass ratio of 1:0.05 to form a suspension, wherein the Ni isxCoyM1-x-y(OH)2In the precursor, x is 0.80, y is 0.1, and M isMn, wherein the aluminate is sodium aluminate;
2) adding a saturated sodium bicarbonate solution into the suspension obtained in the step 1) at a speed of 1ml/min, and aging for 4 hours to obtain a composite precursor, wherein the amount of the bicarbonate substance is 3 times of the amount of the aluminate substance added in the step 1);
3) washing the composite precursor with deionized water for many times, carrying out suction filtration, and drying the composite precursor in a vacuum oven at 100 ℃ for 14 hours;
4) uniformly mixing the dried composite precursor with a lithium source according to the ratio of the sum of the amounts of Ni, Co, Mn and Al elements to the amount of Li elements being 1:1.04, presintering the mixture at 400 ℃ for 2 hours under the environment with the oxygen content of 50 percent, and sintering the mixture at 850 ℃ for 15 hours to obtain the nano lithium aluminate coated nickel-based multi-element cathode material; wherein the lithium source is lithium hydroxide.
The nano lithium aluminate coated nickel-based multi-element cathode material of the embodiment 3 is prepared by the preparation method, and compared with the preparation method of the embodiment 1, the preparation method of the nano lithium aluminate coated nickel-based multi-element cathode material of the embodiment 3 only has Ni in the step 1)xCoyM1-x-y(OH)2The mass ratio of the precursor to the aluminate is different, and the rest is the same.
Example 4
The nano lithium aluminate coated nickel-based multi-element cathode material is prepared by the following steps:
1)NixCoyM1-x-y(OH)2adding the precursor and aluminate into deionized water according to the mass ratio of 1:0.03 to form a suspension, wherein the Ni isxCoyM1-x-y(OH)2In the precursor, x is 0.80, y is 0.1, M is Mn, and the aluminate is sodium aluminate;
2) adding a saturated sodium bicarbonate solution into the suspension obtained in the step 1) at a speed of 1ml/min, and aging for 4 hours to obtain a composite precursor, wherein the amount of the bicarbonate substance is 1 time of the amount of the aluminate substance added in the step 1);
3) washing the composite precursor with deionized water for many times, carrying out suction filtration, and drying the composite precursor in a vacuum oven at 100 ℃ for 14 hours;
4) uniformly mixing the dried composite precursor with a lithium source according to the ratio of the sum of the amounts of Ni, Co, Mn and Al elements to the amount of Li elements being 1:1.04, presintering the mixture at 400 ℃ for 2 hours under the environment with the oxygen content of 50 percent, and sintering the mixture at 850 ℃ for 15 hours to obtain the nano lithium aluminate coated nickel-based multi-element cathode material; wherein the lithium source is lithium hydroxide.
The nano lithium aluminate coated nickel-based multi-component cathode material of example 4 was prepared by the above preparation method, and the preparation method of the nano lithium aluminate coated nickel-based multi-component cathode material of example 4 was different from the preparation method of example 1 only in the amount of the bicarbonate substance added in step 2), and the rest was the same.
Example 5
The nano lithium aluminate coated nickel-based multi-element cathode material is prepared by the following steps:
1)NixCoyM1-x-y(OH)2adding the precursor and aluminate into deionized water according to the mass ratio of 1:0.03 to form a suspension, wherein the Ni isxCoyM1-x-y(OH)2In the precursor, x is 0.80, y is 0.1, M is Mn, and the aluminate is sodium aluminate;
2) adding a saturated sodium bicarbonate solution into the suspension obtained in the step 1) at a speed of 1ml/min, and aging for 4 hours to obtain a composite precursor, wherein the amount of the bicarbonate substance is 5 times of the amount of the aluminate substance added in the step 1);
3) washing the composite precursor with deionized water for many times, carrying out suction filtration, and drying the composite precursor in a vacuum oven at 100 ℃ for 14 hours;
4) uniformly mixing the dried composite precursor with a lithium source according to the ratio of the sum of the amounts of Ni, Co, Mn and Al elements to the amount of Li elements being 1:1.04, presintering the mixture at 400 ℃ for 2 hours under the environment with the oxygen content of 50 percent, and sintering the mixture at 850 ℃ for 15 hours to obtain the nano lithium aluminate coated nickel-based multi-element cathode material; wherein the lithium source is lithium hydroxide.
The nano lithium aluminate coated nickel-based multi-component cathode material according to example 5 was prepared by the above preparation method, and the preparation method of the nano lithium aluminate coated nickel-based multi-component cathode material according to example 5 was different from the preparation method according to example 1 only in the amount of the bicarbonate added in step 2), and the rest was the same.
Example 6
The nano lithium aluminate coated nickel-based multi-element cathode material is prepared by the following steps:
1)NixCoyM1-x-y(OH)2adding the precursor and aluminate into deionized water according to the mass ratio of 1:0.03 to form a suspension, wherein the Ni isxCoyM1-x-y(OH)2In the precursor, x is 0.80, y is 0.1, M is Mn, and the aluminate is sodium aluminate;
2) adding a saturated sodium bicarbonate solution into the suspension obtained in the step 1) at a speed of 1ml/min, and aging for 4 hours to obtain a composite precursor, wherein the amount of the bicarbonate substance is 3 times of the amount of the aluminate substance added in the step 1);
3) washing the composite precursor with deionized water for many times, carrying out suction filtration, and drying the composite precursor in a vacuum oven at 100 ℃ for 14 hours;
4) uniformly mixing the dried composite precursor with a lithium source according to the ratio of the sum of the amounts of Ni, Co, Mn and Al elements to the amount of Li elements being 1:1, presintering the mixture for 2 hours at the temperature of 400 ℃ in the environment with the oxygen content of 50%, and sintering the mixture for 15 hours at the temperature of 850 ℃ to obtain the nano lithium aluminate coated nickel-based multi-element cathode material; wherein the lithium source is lithium hydroxide.
The lithium nano-aluminate coated nickel-based multi-component cathode material of example 6 was prepared by the above preparation method, and the preparation method of the lithium nano-aluminate coated nickel-based multi-component cathode material of example 6 was different from the preparation method of example 1 only in the difference between the sum of the amounts of Ni, Co, Mn, and Al element substances of the composite precursor and the amount of the lithium source Li element substance in step 4), and the rest was the same.
Example 7
The nano lithium aluminate coated nickel-based multi-element cathode material is prepared by the following steps:
1)NixCoyM1-x-y(OH)2adding the precursor and aluminate into deionized water according to the mass ratio of 1:0.03 to form a suspension, wherein the Ni isxCoyM1-x-y(OH)2In the precursor, x is 0.80, y is 0.1, M is Mn, and the aluminate is sodium aluminate;
2) adding a saturated sodium bicarbonate solution into the suspension obtained in the step 1) at a speed of 1ml/min, and aging for 4 hours to obtain a composite precursor, wherein the amount of the bicarbonate substance is 3 times of the amount of the aluminate substance added in the step 1);
3) washing the composite precursor with deionized water for many times, carrying out suction filtration, and drying the composite precursor in a vacuum oven at 100 ℃ for 14 hours;
4) uniformly mixing the dried composite precursor with a lithium source according to the ratio of the sum of the amounts of Ni, Co, Mn and Al elements to the amount of Li elements being 1:1.08, presintering the mixture at 400 ℃ for 2 hours under the environment with the oxygen content of 50 percent, and sintering the mixture at 850 ℃ for 15 hours to obtain the nano lithium aluminate coated nickel-based multi-element cathode material; wherein the lithium source is lithium hydroxide.
The lithium nano-aluminate coated nickel-based multi-component cathode material of example 7 was prepared by the above preparation method, and the preparation method of the lithium nano-aluminate coated nickel-based multi-component cathode material of example 7 was different from the preparation method of example 1 only in the difference between the sum of the amounts of Ni, Co, Mn, and Al element substances of the composite precursor and the amount of the lithium source Li element substance in step 4), and the rest was the same.
Example 8
The nano lithium aluminate coated nickel-based multi-element cathode material is prepared by the following steps:
1)NixCoyM1-x-y(OH)2adding the precursor and aluminate into deionized water according to the mass ratio of 1:0.03 to form a suspension, wherein the Ni isxCoyM1-x-y(OH)2In the precursor, x is 0.6, y is 0.2, M is Mn, and the aluminate is sodium aluminate;
2) adding a saturated sodium bicarbonate solution into the suspension obtained in the step 1) at a speed of 1ml/min, and aging for 4 hours to obtain a composite precursor, wherein the amount of the bicarbonate substance is 3 times of the amount of the aluminate substance added in the step 1);
3) washing the composite precursor with deionized water for many times, carrying out suction filtration, and drying the composite precursor in a vacuum oven at 100 ℃ for 14 hours;
4) uniformly mixing the dried composite precursor with a lithium source according to the ratio of the sum of the amounts of Ni, Co, Mn and Al elements to the amount of Li elements being 1:1.04, presintering the mixture at 400 ℃ for 2 hours under the environment with the oxygen content of 50 percent, and sintering the mixture at 850 ℃ for 15 hours to obtain the nano lithium aluminate coated nickel-based multi-element cathode material; wherein the lithium source is lithium hydroxide.
The nano lithium aluminate coated nickel-based multi-element cathode material of the embodiment 8 is prepared by the preparation method, and compared with the preparation method of the embodiment 1, the preparation method of the nano lithium aluminate coated nickel-based multi-element cathode material of the embodiment 8 only has Ni in the step 1)xCoyM1-x-y(OH)2The metal cation metering ratios of the precursors are different, and the rest are the same.
Comparative example
The nickel-based multi-element cathode material of the comparative example is directly prepared by sintering the same precursor and lithium source as the above-mentioned embodiment, i.e. without coating lithium aluminate or any other coating material, and specifically, the nickel-based multi-element cathode material of the comparative example is prepared by the following steps:
taking dry NixCoyM1-x-y(OH)2Precursor for use, the NixCoyM1-x-y(OH)2In the precursor, x is 0.80, y is 0.1, and M is Mn; then press NixCoyM1-x-y(OH)2The ratio of the sum of the amounts of Ni, Co and Mn element substances to the amount of Li element substance in the precursor is 1:1.04, and adding NixCoyM1-x-y(OH)2Uniformly mixing the precursor with a lithium source, presintering for 2 hours at the temperature of 400 ℃ in the environment with the oxygen content of 50%, and sintering for 15 hours at the temperature of 850 ℃ to obtain the nano lithium aluminate coated nickel-based multi-element cathode material; wherein the lithium source is lithium hydroxide.
The nickel-based multi-element positive electrode material not coated with lithium aluminate or other materials as described in the comparative example was prepared by the above preparation method.
In order to compare the durability of the nano lithium aluminate coated nickel-based multi-element cathode material and the cathode material obtained by the comparative example, the design experiment is as follows: the button cell is assembled by adopting the positive electrode materials of the embodiment and the comparative example respectively, the first discharge specific capacity is tested at 2.8-4.3V and 1C under the test environment at 25 +/-5 ℃, then the battery is charged and discharged once at 1C every day under the test conditions of 25 +/-5 ℃ and 30-60% of humidity, the cycle charge and discharge performance of the battery for long-time use is simulated, and the final test result is shown in the following table:
Figure BDA0002305870750000131
in order to compare the rate capability of the nano lithium aluminate coated nickel-based multi-element cathode material and the cathode material obtained by the comparative example, the design experiment is as follows: the positive electrode materials of the embodiment 1 and the comparative example are respectively assembled into button cells, the first discharge specific capacities of different currents are tested under the voltage of 2.8-4.3V in the test environment at 25 +/-5 ℃, and the final test result is shown in fig. 3.
In order to compare the cycle performance of the nano lithium aluminate coated nickel-based multi-element cathode material and the cathode material obtained by the comparative example, the design experiment is as follows: the positive electrode materials of the embodiment 1 and the comparative example are respectively assembled into button cells, the discharge specific capacity of multiple-cycle charge and discharge is tested under the test environment of 25 +/-5 ℃ and the voltage of 2.8-4.3V and the discharge specific capacity of 2C, and the final test result is shown in fig. 4
The above data show that the rate capability and the cycle performance of the nickel-based multi-element positive electrode material coated with the nano lithium aluminate can be effectively improved under the condition that the first discharge specific capacity of the battery is not affected basically, and the nickel-based multi-element positive electrode material coated with the nano lithium aluminate still has good charge-discharge cycle performance under the condition of long-time placement, so that the battery positive electrode can be effectively protected, the stability of the battery positive electrode is improved, and the overall performance of the battery is improved.
It should be noted that, the present application includes but is not limited to the above embodiments, and technical features that are not described in the present application may be implemented by or using the prior art, which is not described herein again; the above embodiments are only used for illustrating the technical solutions of the present application and are not meant to limit the present application. The present application has been described in detail with reference to the preferred embodiments only, and it will be understood by those skilled in the art that changes, additions and substitutions may be made therein without departing from the spirit of the application and the scope of the claims of the application.

Claims (10)

1. A preparation method of a nickel-based multi-element anode material coated by nano lithium aluminate is characterized by comprising the following steps:
1) taking NixCoyM1-x-y(OH)2Adding the precursor and aluminate into deionized water to form a suspension;
2) adding a bicarbonate solution into the suspension, and aging to obtain a composite precursor;
3) washing the composite precursor by using deionized water and drying;
4) uniformly mixing the dried composite precursor with a lithium source according to the proportion that the sum of the amounts of Ni, Co, M and Al elements and the amount of Li elements is 1 (1-1.08), and sintering at the temperature of 700-950 ℃ for 4-20 hours under the environment that the oxygen content is 21-100% to obtain the nano lithium aluminate coated nickel-based multi-element cathode material;
in the step 1), M is one or more of Mn, Al, Mg or W.
2. The method according to claim 1, wherein in step 1), the Ni is presentxCoyM1-x-y(OH)2The precursor satisfies x is more than or equal to 0.60 and less than 1, y is more than 0 and less than or equal to 0.20, and x + y is less than or equal to 1.
3. The method according to claim 1, wherein in step 1), the Ni is presentxCoyM1-x-y(OH)2The mass ratio of the precursor to the aluminate is 1 (0.01-0.05).
4. The preparation method according to claim 1, wherein in step 1), the aluminate is one or more of potassium aluminate and sodium aluminate.
5. The method according to claim 1, wherein the bicarbonate is added in an amount of 1 to 5 times the amount of the aluminate in the step 2).
6. The method according to claim 1, wherein the bicarbonate in step 2) is a saturated solution of sodium bicarbonate, and the addition rate of the saturated solution of sodium bicarbonate is 0.1 to 2 ml/min.
7. The method according to claim 1, wherein the aging time in step 2) is 2 to 5 hours.
8. The method according to claim 1, wherein in step 4), the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate, or lithium citrate.
9. The preparation method according to claim 1, wherein in the step 4), the mixture of the composite precursor and the lithium source is pre-sintered at a temperature of 300 ℃ to 600 ℃ for 2 to 8 hours in an environment with an oxygen content of 21% to 100% before sintering at a temperature of 700 ℃ to 950 ℃ for 4 to 20 hours.
10. A nano lithium aluminate coated nickel-based multi-element cathode material is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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