CN111509205A - Ternary cathode material for zirconium-coated lithium ion battery and preparation method thereof - Google Patents

Ternary cathode material for zirconium-coated lithium ion battery and preparation method thereof Download PDF

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CN111509205A
CN111509205A CN202010317424.6A CN202010317424A CN111509205A CN 111509205 A CN111509205 A CN 111509205A CN 202010317424 A CN202010317424 A CN 202010317424A CN 111509205 A CN111509205 A CN 111509205A
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zirconium
cathode material
ternary cathode
nickel
cobalt
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史镇洪
范江
马真
简健明
蓝秋明
张键鹏
吴建华
司兰杰
万国江
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Jiangmen Kanhoo Industry Co ltd
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Abstract

The invention relates to a preparation method of a ternary cathode material for a zirconium-coated lithium ion battery, which comprises the following steps: (1) mixing a nickel-cobalt-manganese precursor, a lithium source and an additive to obtain a mixed material, and then firing and crushing to obtain a ternary cathode material to be coated; (2) mixing an ammonium zirconium carbonate solution and pure water to prepare a solution A, adding a ternary cathode material to be coated into the solution A, and stirring to obtain a slurry B; and heating the slurry B, continuously stirring to obtain a dry material, and firing to obtain the ternary cathode material. The invention adopts the submicron-order precursor with higher reaction activity and adds the fluxing agent, thereby being capable of firing at lower temperature to generate the single crystal nickel cobalt manganese ternary material which meets the performance requirement.

Description

Ternary cathode material for zirconium-coated lithium ion battery and preparation method thereof
Technical Field
The invention relates to a ternary cathode material for a zirconium-coated lithium ion battery and a preparation method thereof, belonging to the technical field of lithium ion batteries.
Background
The monocrystalline nickel-cobalt-manganese ternary positive electrode for the lithium ion battery applied to the market at present is generally prepared by a micron-sized precursor and a lithium source through high-temperature firing in a synthesis process, and after initial monocrystalline particles are prepared, a coating process usually adopts a dry mixing mode by adding a nanoscale oxide as a coating agent to coat.
When the micron-sized precursor is used for preparing the micron-sized single crystal nickel-cobalt-manganese ternary material, the activity of the micron-sized precursor is low, so that the high ignition temperature needs to be kept during ignition of the single crystal ternary material. Under higher burning temperature, the negative effects of the single crystal ternary material such as increased lithium-nickel mixed-discharging degree, low gram capacity of the material and the like are easily caused.
The nano-scale oxide is added as a coating agent, and dry mixing coating is carried out, so that the coating agent is easily formed and attached to the surface of the material in a dotted manner. The surface of the material cannot be uniformly and comprehensively covered, so that the effect of isolating the electrolyte in the true sense is achieved, the internal resistance of the material is higher after the partial coating is finished, and the rate capability of the material is reduced.
Therefore, a preparation method of the single crystal nickel-cobalt-manganese ternary cathode material for the lithium ion battery must be developed, so that the firing temperature required for preparing the single crystal nickel-cobalt-manganese ternary material can be reduced, the lithium-nickel mixed discharge of the single crystal nickel-cobalt-manganese ternary material is reduced, and the gram capacity is improved; meanwhile, the coating uniformity is improved, so that the coating agent can completely cover the surface of the material, the effect of really isolating the electrolyte to protect the surface of the material is achieved, the surface structure stability of the material is improved, and the multiplying power performance of the material is improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the ternary cathode material for the zirconium-coated lithium ion battery and the preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a ternary cathode material for a zirconium-coated lithium ion battery comprises the following steps:
(1) preparing a ternary cathode material: mixing a nickel-cobalt-manganese precursor, a lithium source and an additive to obtain a mixed material; firing and crushing the mixed material to obtain a ternary cathode material to be coated;
(2) coating of the ternary cathode material: mixing an ammonium zirconium carbonate solution and pure water to prepare a solution A, adding the ternary cathode material to be coated, which is prepared in the step (1), into the solution A, and stirring to obtain a slurry B; and heating the slurry B, continuously stirring to obtain a dry material, and firing the dry material to obtain the ternary cathode material for the zirconium-coated lithium ion battery.
The invention uses the submicron nickel cobalt manganese precursor as the raw material, so that the activity of the reaction system is higher and the reaction is more violent.
As a preferred embodiment of the preparation method of the present invention, in the step (1), the mixing operation is: mix at 300r/min for 5min and then at 800r/min for 20 min.
In a preferred embodiment of the preparation method of the invention, in the step (1), the molar mass ratio of the nickel-cobalt-manganese precursor to the lithium source is Me (total nickel-cobalt-manganese content): L i ═ 0.91-0.98): 1, and the amount of the additive is 0.01-0.5% of the total mass of the mixture.
In a preferred embodiment of the preparation method of the present invention, in the step (1), the additive is at least one of lithium borate and lithium hexafluoroaluminate. The invention uses lithium borate and lithium hexafluoroaluminate as reaction fluxing agent to improve the speed of fusing and growing up of raw materials in high-temperature reaction.
In a preferred embodiment of the preparation method of the present invention, in the step (1), the particle size distribution of the nickel-cobalt-manganese precursor is in a submicron state, the particle size of D50 is 0.1 to 1.0 μm, and the molar ratio of elements in the nickel-cobalt-manganese precursor is: nickel: cobalt: manganese ═ a: b: (1-a-b), wherein a is 0.5-0.95, and b is 0.03-0.2.
As a preferred embodiment of the preparation method of the invention, in the step (1), the burning temperature is 650-800 ℃, and the burning time is 8-12 h. The temperature selected by burning is lower, so that the internal structure of the burned ternary material cannot generate the phenomenon of lithium-nickel mixed discharge.
As a preferred embodiment of the preparation method of the present invention, in the step (2), the preparation method of the ammonium zirconium carbonate solution comprises:
(i) dissolving zirconium oxychloride in pure water to obtain a zirconium oxychloride aqueous solution, adding saturated ammonia water into the zirconium oxychloride aqueous solution, and introducing carbon dioxide to react to generate a white precipitate; filtering and washing with pure water to obtain zirconium carbonate;
(ii) dispersing zirconium carbonate in pure water, adding saturated ammonia water, and introducing carbon dioxide until the zirconium carbonate is dissolved to obtain an ammonium zirconium carbonate solution.
The invention uses self-made soluble ammonium zirconium carbonate as a coating agent and realizes the effect of uniformly coating zirconium in a wet method.
In a preferred embodiment of the preparation method of the invention, in the step (i), the zirconium ion concentration in the zirconium oxychloride aqueous solution is 2.5-3.0 mol/L, the molar ratio of ammonia water to zirconium oxychloride is (1.2-1.6): 1, the introduction speed of carbon dioxide is 10L/min, the introduction of carbon dioxide is stopped until white precipitates are not increased any more, the temperature of pure water used for washing is not higher than 30 ℃, the amount of pure water used for washing is 10-15 times of the volume of the white precipitates, in the step (ii), the concentration of zirconium carbonate dispersed in the pure water is 1.5-2.5 mol/L, the molar ratio of ammonia water to zirconium carbonate is (2.5-3.5): 1, and the introduction speed of carbon dioxide is 10L/min.
In the step (2), the concentration of the zirconium element in the solution A is 10-100 g/L, the weight ratio of the zirconium element in the slurry B to the ternary cathode material to be coated is (0.001-0.01): 1, the temperature of the slurry B is increased to 80-90 ℃, the firing temperature is 450-650 ℃, and the firing time is 5-8 h.
The invention also provides the ternary cathode material for the zirconium-coated lithium ion battery prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts the submicron-order precursor with higher reaction activity and adds proper fluxing agent, thereby being capable of firing at lower temperature to generate the single crystal nickel cobalt manganese ternary material which meets the performance requirement.
(2) The invention uses the self-made soluble coating agent to coat the single crystal nickel-cobalt-manganese ternary material by a wet method, thereby achieving the effect of uniform coating; the uniformly coated ammonium zirconium carbonate is decomposed under the firing condition to release carbon dioxide, and the final coating zirconium dioxide is remained, wherein the zirconium dioxide is in a microporous state and is beneficial to the conduction of lithium ions of the ternary cathode material, so that the internal resistance of the material is reduced, and the multiplying power performance of the material is improved.
Drawings
Fig. 1 is a morphology diagram of the ternary cathode material for the zirconium-coated lithium ion battery prepared in example 1.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
A preparation method of a ternary cathode material for a zirconium-coated lithium ion battery comprises the following steps:
(1) preparing a nickel-cobalt-manganese precursor and a lithium source according to a molar ratio Me (total nickel-cobalt-manganese content) of L i-0.91, adding 0.01% of an additive based on the total mass of a mixed material, mixing the mixed material in a high-speed mixing tank at a low speed of 300r/min for 5min, and then mixing at a high speed of 800r/min for 20min to obtain a mixed material;
the additive is lithium borate; the particle size distribution of the nickel-cobalt-manganese precursor is in a submicron state, the particle size D50 is 0.1-1.0 μm, and the molar ratio of elements in the nickel-cobalt-manganese precursor is as follows: nickel: cobalt: manganese 0.55: 0.15: 0.3;
placing the mixed material in a roller furnace containing air atmosphere, burning for 8 hours at the constant temperature of 650 ℃ to obtain a blocky sintering material, and crushing the blocky sintering material to obtain a particle-dispersed ternary cathode material;
(2) coating the ternary cathode material, namely preparing a solution A with the zirconium content of 10 g/L by using ammonium zirconium carbonate solution and pure water, adding the ternary cathode material to be coated into the solution A, stirring the solution A properly to obtain slurry B, and keeping the weight ratio of the zirconium element in the slurry B to the ternary cathode material to be coated to be 0.001;
and heating the slurry B to 80-90 ℃ by using a water bath, keeping stirring at a low speed at the same time until most of water in the slurry B is evaporated, transferring the material into a mullite sagger, firing the material in a roller furnace for 5-8 hours at a constant temperature of 450-650 ℃, and firing to obtain the ternary cathode material with uniformly coated zirconium on the surface and a plurality of micropores on the surface.
The preparation method of the ammonium zirconium carbonate solution comprises the following steps:
(i) zirconium oxychloride (ZrOCl) with oxygen2·8(H2O)) and pure water were prepared into a zirconium oxychloride solution having a zirconium concentration of 2.5 mol/L, and oxygen was added theretoSlowly injecting saturated ammonia water into the zirconium chloride solution, and keeping NH in the total introduction amount of the ammonia water3·H2O and ZrOCl2·8(H2O) is 1.2, simultaneously introducing carbon dioxide into the solution at the speed of 10L/min until white precipitates are not increased any more, filtering the reaction material, and washing the material by pure water with the temperature of less than or equal to 30 ℃ and the weight of about 10-15 times of the weight of the white precipitates to obtain white precipitated zirconium carbonate;
(ii) dispersing white precipitated zirconium carbonate in pure water, keeping the concentration of the zirconium carbonate at 1.5 mol/L, introducing saturated ammonia water in an amount of keeping NH3·H2The molar ratio of O to Zr is 2.5, carbon dioxide is introduced at the speed of 10L/min until the white precipitate is dissolved, and the introduction of carbon dioxide is stopped to obtain colorless and transparent ammonium zirconium carbonate solution.
The topography (4000 times enlargement under an electron microscope) of the ternary cathode material for the zirconium-coated lithium ion battery prepared in the embodiment is shown in fig. 1. As can be seen from FIG. 1, the prepared ternary cathode material particles are basically in a single crystal state, the overall particle size is 3-4 μm, and the proper firing temperature is shown. The surface of the material particles is smooth, and no obvious point-like attachments exist on the surface, which indicates that the material is uniformly coated.
Example 2
A preparation method of a ternary cathode material for a zirconium-coated lithium ion battery comprises the following steps:
(1) preparing a nickel-cobalt-manganese precursor and a lithium source according to a molar ratio Me (total nickel-cobalt-manganese content) of L i-0.95, adding 0.25% of an additive, mixing the mixed materials in a high-speed mixing tank at a low speed of 300r/min for 5min, and then at a high speed of 800r/min for 20min to obtain a mixed material;
the additive is lithium hexafluoroaluminate; the particle size distribution of the nickel-cobalt-manganese precursor is in a submicron state, and the particle size D50 is 0.1-1.0 μm. The molar ratio of elements in the nickel-cobalt-manganese precursor is as follows: nickel: cobalt: manganese 0.55: 0.15: 0.3;
placing the mixed material in a roller furnace containing air atmosphere, firing for 10h at the constant temperature of 700 ℃ to obtain a blocky sintering material, and crushing the blocky sintering material to obtain a particle-dispersed ternary cathode material;
(2) coating the ternary cathode material, namely preparing a solution A with the zirconium content of 50 g/L by using ammonium zirconium carbonate solution and pure water, adding the ternary cathode material to be coated into the solution A, stirring the solution A properly to obtain slurry B, and keeping the weight ratio of the zirconium element in the slurry B to the ternary cathode material to be coated to be 0.005;
and heating the slurry B to 80-90 ℃ by using a water bath, keeping stirring at a low speed at the same time until most of water in the slurry B is evaporated, transferring the material into a mullite sagger, firing the material in a roller furnace for 5-8 hours at a constant temperature of 450-650 ℃, and firing to obtain the ternary cathode material with uniformly coated zirconium on the surface and a plurality of micropores on the surface.
The preparation method of the ammonium zirconium carbonate solution comprises the following steps:
(i) zirconium oxychloride (ZrOCl) with oxygen2·8(H2O)) and pure water to prepare a zirconium oxychloride solution with the zirconium concentration of 2.7 mol/L, slowly injecting saturated ammonia water into the zirconium oxychloride solution, and keeping the total introduction amount of the ammonia water to keep NH3·H2O and ZrOCl2·8(H2O) is 1.4, simultaneously introducing carbon dioxide into the solution at the speed of 10L/min until white precipitates are not increased any more, filtering the reaction material, and washing the material by pure water with the temperature of less than or equal to 30 ℃ and the weight of about 10-15 times of the weight of the white precipitates to obtain white precipitated zirconium carbonate;
(ii) dispersing white precipitated zirconium carbonate in pure water, keeping the concentration of the zirconium carbonate at 2.0 mol/L, introducing saturated ammonia water in an amount of keeping NH3·H2The molar ratio of O to Zr is 3.0, carbon dioxide is introduced at the speed of 10L/min until the white precipitate is dissolved, and the introduction of carbon dioxide is stopped to obtain colorless and transparent ammonium zirconium carbonate solution.
Example 3
A preparation method of a ternary cathode material for a zirconium-coated lithium ion battery comprises the following steps:
(1) preparing a nickel-cobalt-manganese precursor and a lithium source according to a molar ratio Me (total nickel-cobalt-manganese content) of L i-0.98, adding 0.5% of an additive, mixing the mixed material in a high-speed mixing tank at a low speed of 300r/min for 5min, and then at a high speed of 800r/min for 20min to obtain a mixed material;
the additive is lithium borate and lithium hexafluoroaluminate with the mass ratio of 1: 1; the particle size distribution of the nickel-cobalt-manganese precursor is in a submicron state, and the particle size D50 is 0.1-1.0 μm. The mole ratio of elements in the nickel-cobalt-manganese precursor, nickel: cobalt: manganese 0.55: 0.15: 0.3;
placing the mixed material in a roller furnace containing air atmosphere, burning for 12h at the constant temperature of 800 ℃ to obtain a blocky sintering material, and crushing the blocky sintering material to obtain a particle-dispersed ternary cathode material;
(2) coating the ternary cathode material, namely preparing a solution A with the zirconium content of 100 g/L by using ammonium zirconium carbonate solution and pure water, adding the ternary cathode material to be coated into the solution A, stirring the solution A properly to obtain slurry B, and keeping the weight ratio of the zirconium element in the slurry B to the ternary cathode material to be coated to be 0.01;
and heating the slurry B to 80-90 ℃ by using a water bath, keeping stirring at a low speed at the same time until most of water in the slurry B is evaporated, transferring the material into a mullite sagger, firing the material in a roller furnace for 5-8 hours at a constant temperature of 450-650 ℃, and firing to obtain the ternary cathode material with uniformly coated zirconium on the surface and a plurality of micropores on the surface.
The preparation method of the ammonium zirconium carbonate solution comprises the following steps:
(i) zirconium oxychloride (ZrOCl) with oxygen2·8(H2O)) and pure water to prepare a zirconium oxychloride solution with the zirconium concentration of 3.0 mol/L, slowly injecting saturated ammonia water into the zirconium oxychloride solution, and keeping the total introduction amount of the ammonia water to keep NH3·H2O and ZrOCl2·8(H2O) is 1.6, simultaneously introducing carbon dioxide into the solution at the speed of 10L/min until white precipitates are not increased any more, filtering the reaction material, and washing the material by pure water with the temperature of less than or equal to 30 ℃ and the weight of about 10-15 times of the weight of the white precipitates to obtain white precipitated zirconium carbonate;
(ii) white precipitated zirconium carbonate was dispersed in pure water while maintaining the concentration of zirconium carbonate at 2.5mol/L introducing saturated ammonia water in an amount to maintain NH3·H2The molar ratio of O to Zr is 3.5, carbon dioxide is introduced at the speed of 10L/min until the white precipitate is dissolved, and the introduction of carbon dioxide is stopped to obtain colorless and transparent ammonium zirconium carbonate solution.
Comparative example 1
A preparation method of a ternary cathode material for a lithium ion battery comprises the following steps:
(1) preparing a nickel-cobalt-manganese precursor and a lithium source according to a molar ratio Me (total nickel-cobalt-manganese content): L i is 0.91, adding no additive, mixing the mixed materials in a high-speed mixing tank at a low speed of 300r/min for 5min, and then at a high speed of 800r/min for 20min to obtain a mixed material;
the particle size distribution of the nickel-cobalt-manganese precursor is in a submicron state, and the particle size D50 is 0.1-1.0 μm. The mole ratio of elements in the nickel-cobalt-manganese precursor, nickel: cobalt: manganese 0.55: 0.15: 0.3;
placing the mixed material in a roller furnace containing air atmosphere, burning for 8 hours at the constant temperature of 650 ℃ to obtain a blocky sintering material, and crushing the blocky sintering material to obtain a particle-dispersed ternary cathode material;
(2) coating of the ternary cathode material: the same as in example 1.
The preparation method of the ammonium zirconium carbonate solution was the same as that of example 1.
Comparative example 2
A preparation method of a ternary cathode material for a lithium ion battery comprises the following steps:
(1) preparing a ternary cathode material: the same as example 1 except that the particle size distribution of the nickel-cobalt-manganese precursor is in a micron-sized state, and the particle size D50 is 4.0-6.0 μm;
(2) coating of the ternary cathode material: the same as in example 1.
The preparation method of the ammonium zirconium carbonate solution was the same as that of example 1.
Comparative example 3
A preparation method of a ternary cathode material for a lithium ion battery comprises the following steps:
(1) preparing a ternary cathode material: the same as example 1;
(2) coating of the ternary cathode material: adding the ternary cathode material to be coated and common nano-grade zirconium dioxide into a high-speed mixer, mixing for 10min at a low speed of 200r/min, and then mixing for 20min at a high speed of 700r/min to obtain a coating mixed material, wherein the weight ratio of the zirconium element to the ternary cathode material to be coated is 0.01;
and (3) transferring the coated mixed material into a mullite sagger, firing for 5-8 h in a roller furnace at the constant temperature of 450-650 ℃, and firing to obtain the ternary cathode material with the surface coated with zirconium element.
Examples of effects
The physical property and the electrochemical property of the ternary cathode materials prepared in the examples 1-3 and the comparative examples 1-3 are detected. The carrier used for detecting the electrochemical performance is a half-cell CR2032, and the evaluation voltage interval is 4.45V-3.0V. The test results are shown in table 1.
TABLE 1
Figure BDA0002460089430000081
As can be seen from Table 1, the ternary cathode material for the zirconium-coated lithium ion battery prepared by the method has the characteristic of high tap density in physical properties, and not only can the half-gram capacity be exerted by more than 186mAh/g in the aspect of electrical properties, but also the rate capability and the cycle performance are excellent.
The analysis of the embodiment 1 and the comparative example 1 shows that in the preparation stage of the ternary cathode material, the additive with the fluxing function is introduced to participate in the reaction, so that the prepared ternary cathode material can reach the required particle size at no need of overhigh temperature, and the higher tap density, gram capacity, rate capability and cycle performance of the ternary cathode material are better than those of the ternary cathode material prepared by the traditional method.
As can be seen from comparative example 2, if the submicron nickel-cobalt-manganese precursor is not selected as the raw material of the ternary cathode material, the formation reactivity of the material is low, which results in a small particle size at a suitable temperature, the specific surface in this state is high, and the cycle performance of the ternary cathode material is negatively affected, for example, the cycle performance of the material in comparative example 2 is reduced by 5.5% compared with that in example 1.
From the analysis of comparative example 3, if the ternary cathode material is coated with zirconium element, the zirconium-coated ternary cathode material obtained by the method has cross-correlation in gram volume, rate capability and cycle performance by using the conventional zirconium dioxide for dry coating. The method is mainly characterized in that elements cannot be uniformly coated on the surfaces of material particles by dry coating, so that the thick part of a coating agent on the surfaces of the materials is thin, the conduction of lithium ions is influenced, and the surface structure of the materials cannot be well protected. The invention adopts the self-made soluble coating agent to carry out wet coating, thus well solving the problem.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. A preparation method of a ternary cathode material for a zirconium-coated lithium ion battery is characterized by comprising the following steps:
(1) preparing a ternary cathode material: mixing a nickel-cobalt-manganese precursor, a lithium source and an additive to obtain a mixed material; firing and crushing the mixed material to obtain a ternary cathode material to be coated;
(2) coating of the ternary cathode material: mixing an ammonium zirconium carbonate solution and pure water to prepare a solution A, adding the ternary cathode material to be coated, which is prepared in the step (1), into the solution A, and stirring to obtain a slurry B; and heating the slurry B, continuously stirring to obtain a dry material, and firing the dry material to obtain the ternary cathode material for the zirconium-coated lithium ion battery.
2. The method according to claim 1, wherein in the step (1), the mixing operation is: mix at 300r/min for 5min and then at 800r/min for 20 min.
3. The preparation method according to claim 1, wherein in the step (1), the molar mass ratio of the nickel-cobalt-manganese precursor to the lithium source is Me (total nickel-cobalt-manganese content): L i ═ (0.91-0.98): 1, and the additive is used in an amount of 0.01-0.5% of the total mass of the mixture.
4. The method according to claim 1, wherein in the step (1), the additive is at least one of lithium borate and lithium hexafluoroaluminate.
5. The method according to claim 1, wherein in the step (1), the particle size distribution of the nickel-cobalt-manganese precursor is in a submicron state, the particle size of D50 is 0.1-1.0 μm, and the molar ratio of elements in the nickel-cobalt-manganese precursor is as follows: nickel: cobalt: manganese ═ a: b: (1-a-b), wherein a is 0.5-0.95, and b is 0.03-0.2.
6. The method according to claim 1, wherein in the step (1), the burning temperature is 650 to 800 ℃ and the burning time is 8 to 12 hours.
7. The method according to claim 1, wherein in the step (2), the ammonium zirconium carbonate solution is prepared by:
(i) dissolving zirconium oxychloride in pure water to obtain a zirconium oxychloride aqueous solution, adding saturated ammonia water into the zirconium oxychloride aqueous solution, and introducing carbon dioxide to react to generate a white precipitate; filtering and washing with pure water to obtain zirconium carbonate;
(ii) dispersing zirconium carbonate in pure water, adding saturated ammonia water, and introducing carbon dioxide until the zirconium carbonate is dissolved to obtain an ammonium zirconium carbonate solution.
8. The method according to claim 7, wherein in the step (i), the zirconium ion concentration of the aqueous solution of zirconium oxychloride is 2.5 to 3.0 mol/L, the molar ratio of ammonia water to zirconium oxychloride is (1.2 to 1.6): 1, the introduction rate of carbon dioxide is 10L/min, the introduction of carbon dioxide is stopped until the white precipitate is not increased any more, the temperature of pure water used for washing is not higher than 30 ℃, the amount of pure water used for washing is 10 to 15 times the volume of the white precipitate, in the step (ii), the concentration of zirconium carbonate dispersed in pure water is 1.5 to 2.5 mol/L, the molar ratio of ammonia water to zirconium carbonate is (2.5 to 3.5): 1, and the introduction rate of carbon dioxide is 10L/min.
9. The preparation method according to claim 1, wherein in the step (2), the concentration of the zirconium element in the solution A is 10-100 g/L, the weight ratio of the zirconium element in the slurry B to the ternary cathode material to be coated is (0.001-0.01): 1, the temperature of the slurry B is increased to 80-90 ℃, the ignition temperature is 450-650 ℃, and the ignition time is 5-8 h.
10. The ternary cathode material for the zirconium-coated lithium ion battery prepared by the preparation method according to any one of claims 1 to 9.
CN202010317424.6A 2020-04-21 2020-04-21 Ternary cathode material for zirconium-coated lithium ion battery and preparation method thereof Pending CN111509205A (en)

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