CN114538533A - Nickel-cobalt lithium manganate and preparation method and application thereof - Google Patents

Nickel-cobalt lithium manganate and preparation method and application thereof Download PDF

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CN114538533A
CN114538533A CN202210084652.2A CN202210084652A CN114538533A CN 114538533 A CN114538533 A CN 114538533A CN 202210084652 A CN202210084652 A CN 202210084652A CN 114538533 A CN114538533 A CN 114538533A
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nickel cobalt
lithium
mixture
sintering
lithium manganate
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CN114538533B (en
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李刚
朱二涛
徐涛
胡刚刚
赵亚楠
陆胡彪
吴胜坤
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Hefei Rongjie Energy Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses nickel cobalt lithium manganate and a preparation method and application thereof, wherein the preparation method comprises the following steps: ni precursor of nickel, cobalt and manganesexCoyMn1‑x‑y(OH)2Uniformly mixing the mixture with a lithium source to obtain a first mixture, wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y is less than 1; carrying out primary sintering on the first mixture to obtain primary sintered nickel cobalt lithium manganate; uniformly mixing the primary sintered nickel cobalt lithium manganate, zirconium dioxide and sodium carbonate to obtain a mixture II; and carrying out secondary sintering on the mixture II to obtain secondary sintered nickel cobalt lithium manganate. The nickel cobalt lithium manganate prepared by the preparation method has excellent high-temperature cycle performance, the problem of high-temperature gas expansion is solved, and the process is clean and environment-friendly.

Description

Nickel-cobalt lithium manganate and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery ternary positive electrode materials, and particularly relates to a preparation method of nickel cobalt lithium manganate, nickel cobalt lithium manganate prepared by the preparation method, and application of the nickel cobalt lithium manganate in preparation of a lithium ion battery.
Background
At present, the anode material of the lithium ion battery is mainly lithium cobaltate, ternary material and lithium iron phosphate. Compared with other anode materials, the ternary material has the most advantages in comprehensive performance, is lower in price than lithium cobaltate, good in safety and higher in voltage than lithium iron phosphate, can be used for small batteries for mobile phones and notebook computers, can also be used for large power lithium batteries for electric vehicles, and has huge market potential.
The problems of high-temperature gas expansion and poor high-temperature circulation of the battery exist in the common high-nickel ternary material, and how to improve the high-temperature performance of the high-nickel ternary material is the key to mass production of the material.
Disclosure of Invention
In view of the above, the invention needs to provide a preparation method of lithium nickel cobalt manganese oxide, which adopts dry doping and is simple in operation, clean and environment-friendly; through secondary sintering, zirconium dioxide and sodium carbonate are subjected to high-temperature alkali fusion, so that a sodium zirconate coating layer is formed on the surface of the ternary cathode material, the corrosion of electrolyte to the surface of the material is reduced, the transfer efficiency of lithium ions is improved, and the high-temperature cycle performance of the material is greatly improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of lithium nickel cobalt manganese oxide, which comprises the following steps:
ni precursor of nickel, cobalt and manganesexCoyMn1-x-y(OH)2Uniformly mixing the mixture with a lithium source to obtain a first mixture, wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y is less than 1;
carrying out primary sintering on the first mixture to obtain primary sintered nickel cobalt lithium manganate;
uniformly mixing the primary sintered nickel cobalt lithium manganate, zirconium dioxide and sodium carbonate to obtain a mixture II;
and carrying out secondary sintering on the mixture II to obtain secondary sintered nickel cobalt lithium manganate.
Further, the lithium source is selected from lithium hydroxide or lithium carbonate.
In a further scheme, the nickel cobalt lithium manganate NixCoyMn1-x-y(OH)2In the formula, x is more than or equal to 7 and less than 8.
In a further aspect, the nickel cobalt manganese precursor NixCoyMn1-x-y(OH)2The particle size D50 of (B) is 3-4 μm.
In a further aspect, the nickel cobalt manganese precursor NixCoyMn1-x-y(OH)2And taking the lithium source according to the molar ratio of the lithium to the nickel-cobalt-manganese precursor of 1.02-1.08.
In a further scheme, the temperature of the primary sintering is 500-800 ℃, and the time is 10-15 h.
Further, the adding amounts of the zirconium dioxide and the sodium carbonate are respectively 1500ppm and 1000ppm of the primary sintered nickel cobalt lithium manganate.
In a further scheme, the temperature of the secondary sintering is 700-950 ℃, and the time is 8-15 h.
The invention also provides nickel cobalt lithium manganate prepared by adopting the preparation method of any one of the nickel cobalt lithium manganate.
The invention further provides the application of the nickel cobalt lithium manganate in the preparation of the lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the invention adopts dry doping, and has simple operation, cleanness and environmental protection.
According to the invention, through zirconium and sodium double doping and coating of a sodium zirconate coating layer, the nickel cobalt lithium manganate prepared by secondary sintering is completely reacted, has good appearance and excellent high-temperature cycle performance, and solves the problem of high-temperature gas expansion.
Drawings
FIG. 1 is a scanning electron microscope picture of sodium zirconate coated lithium nickel cobalt manganese oxide prepared in example 3 of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative only and should not be construed as limiting the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention discloses a preparation method of nickel cobalt lithium manganate, which mainly comprises the following steps:
s100, primary mixing
Specifically, a nickel-cobalt-manganese precursor and a lithium source are uniformly mixed to obtain a first mixture; wherein the nickel-cobalt-manganese precursor is nickel-cobalt-manganese hydroxide NixCoyMn1-x-y(OH)2In the chemical general formula, x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y is less than 1, it can be understood that the nickel-cobalt-manganese precursor is used as a conventional raw material of nickel-cobalt lithium manganate, and the specific composition thereof is not particularly limited and can be selected according to actual conditions. Because the capacity density of the 7 series single crystal ternary is higher than that of the 5 series ternary and the 6 series ternary, the processing performance and the cycle performance, the high-temperature performance and the safety performance are better than those of the 8 series ternary and the 9 series ternary, and the cost performance is extremely high, the technical scheme of the invention can improve the high-temperature cycle performance of the whole series lithium nickel cobalt manganese oxide, and the 7 series lithium nickel cobalt manganese oxide is optimal, so the invention is preferablexCoyMn1-x-y(OH)2In the formula, x is more than or equal to 7 and less than 8. Further, in the embodiment of the invention, the particle size of the nickel-cobalt-manganese precursor is 3-4 μm. In addition, the proportion of the nickel-cobalt-manganese precursor and the lithium source is selected according to the composition of the nickel-cobalt-manganese acid lithium as a final productAlternatively, in one or more embodiments of the invention, the nickel-cobalt-manganese precursor, NixCoyMn1-x-y(OH)2Taking the lithium source according to the molar ratio of the lithium to the nickel-cobalt-manganese precursor of 1.02-1.08; it is to be understood that the selection of the lithium source in the present invention is a routine choice in the art, and is not particularly limited, and specifically, lithium hydroxide or lithium carbonate may be mentioned as an example.
Further, in the process of obtaining the first mixture, the mixing parameters of the raw materials are not particularly limited as long as the purpose of uniform mixing can be achieved, and in one or more embodiments of the invention, the mixing is performed for 20-30min at a rotation speed of 500 rpm.
S200, primary sintering
Specifically, the obtained first mixed material is sintered to obtain primary sintered nickel cobalt lithium manganate, and in the embodiment of the invention, the specific steps are as follows: and putting the mixture I into a sagger, shaking up and marking lines, sintering at the temperature of 500 plus materials and 800 ℃ for 10-15h, and crushing until the granularity D50 is 4-5 mu m to obtain the primary sintered lithium nickel cobalt manganese oxide. It is to be understood that the potting, the pulverization, and the like are conventional means in the art and are not particularly limited, and the pulverization in this step is carried out by jet pulverization at a classifying frequency of 2 to 20Hz and a feeding frequency of 5 to 30Hz according to the examples of the present invention.
S300, secondary mixing
Specifically, the primary sintered nickel cobalt lithium manganate obtained in the step S200 is uniformly mixed with zirconium dioxide and sodium carbonate to obtain a second mixture. It is understood that the amount of the surface coating layer of the lithium nickel cobalt manganese oxide can be adjusted by adjusting the addition amounts of zirconium dioxide and sodium carbonate in this step, and in one or more embodiments of the present invention, the addition amounts of zirconium dioxide and sodium carbonate are respectively 1500ppm and 200 ppm and 1000ppm of the once-sintered lithium nickel cobalt manganese oxide.
Further, in the step of obtaining the mixture two, the mixing parameters are not particularly limited as long as the purpose of uniform mixing can be achieved, and according to the embodiment of the invention, the mixing is performed for 20-30min at the rotation speed of 200-1000 rpm.
S400, secondary sintering
Specifically, the mixture II obtained in the step S300 is sintered at a high temperature, and during the high-temperature sintering, partial zirconium dioxide and sodium carbonate are subjected to an alkali fusion reaction on the surface of the nickel cobalt lithium manganate crystal to form a zirconium carbonate coating layer, so that the corrosion resistance and the thermal stability of the nickel cobalt lithium manganate can be improved; in addition, a small part of zirconium particles and sodium ions can permeate into the lithium nickel cobalt manganese oxide crystal during high-temperature reaction, wherein the zirconium ions replace cobalt ions to occupy space, and the structure stability is improved; the sodium ions penetrate into the lithium layer, so that a lithium ion migration channel can be widened, the migration efficiency is improved, the mixed lithium-nickel arrangement can be reduced, and the high-temperature performance of the nickel-cobalt lithium manganate is greatly improved by combining a sodium zirconate coating layer.
According to the embodiment of the invention, the temperature of the secondary sintering is based on the alkali fusion reaction of zirconium dioxide and sodium carbonate, and in some specific embodiments, the temperature of the secondary sintering is 700-950 ℃, and the time is 8-15 h.
The method also comprises a crushing step after sintering, wherein the crushing in the embodiment of the invention adopts jet milling, the grading frequency of the jet milling is 2-20Hz, the feeding frequency is 5-30Hz, and the secondary sintering nickel cobalt lithium manganate is crushed to the granularity D50 of 3-4 μm.
In a second aspect, the invention provides lithium nickel cobalt manganese oxide, which is prepared by the preparation method according to any one of the first aspect of the invention.
In a third aspect of the invention, the application of the nickel cobalt lithium manganate in the preparation of lithium ion batteries is provided.
The present invention is illustrated below by way of specific examples, which are intended to be illustrative only and not to limit the scope of the present invention in any way, and reagents and materials used therein are commercially available, unless otherwise specified, and conditions or steps thereof are not specifically described.
Example 1
S1, primary mixing: according to Li, frontThe molar ratio of the precursor is 1.05, and Ni with the granularity of 3-4 mu m is taken0.7Co0.1Mn0.2(OH)2Mixing the mixture and lithium hydroxide in a high-speed mixer at 500rpm/min for 25min to obtain a first mixture;
s2, primary sintering: putting the first mixture into a sagger, shaking up and marking lines, sintering at 800 ℃ for 12 hours, crushing the materials subjected to primary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so that the primary sintered nickel cobalt lithium manganate with the granularity D50 of 4.5 mu m is obtained;
s3, secondary mixing: mixing the primary sintered nickel cobalt lithium manganate, 1400ppm of zirconium dioxide and 900ppm of sodium carbonate in a high-speed mixer at 500rpm/min for 25min to obtain a mixture II;
s4, secondary sintering: putting the mixture II into a sagger, shaking up and marking lines, sintering at 900 ℃ for 10h, crushing the materials after secondary sintering by an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so as to obtain secondary sintered nickel cobalt lithium manganate with the granularity D50 of 4.8 mu m, namely sodium zirconate coated LiNi0.7Co0.1Mn0.2O2。
Example 2
S1, primary mixing: taking Ni with the particle size of 3-4 mu m according to the molar ratio of lithium to precursor of 1.050.7Co0.1Mn0.2(OH)2Mixing the lithium carbonate and the mixture in a high-speed mixer at 500rpm/min for 25min to obtain a first mixture;
s2, primary sintering: putting the first mixture into a sagger, shaking up and marking lines, sintering at 800 ℃ for 12 hours, crushing the materials subjected to primary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so that the primary sintered nickel cobalt lithium manganate with the granularity D50 of 4.2 mu m is obtained;
s3, secondary mixing: mixing the primary sintered nickel cobalt lithium manganate, 600ppm of zirconium dioxide and 300ppm of sodium carbonate in a high-speed mixer at 500rpm/min for 25min to obtain a mixture II;
s4, secondary sintering: putting the mixture II into a sagger and shaking upAnd marking lines, sintering for 10h at 900 ℃, crushing the materials after secondary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so as to obtain the secondary sintering lithium nickel cobalt manganese oxide granularity D50 of 4.3 mu m, namely the LiNi coated with sodium zirconate0.7Co0.1Mn0.2O2。
Example 3
S1, primary mixing: taking Ni with the particle size of 3-4 mu m according to the molar ratio of lithium to precursor of 1.050.7Co0.1Mn0.2(OH)2Mixing the lithium carbonate and the mixture in a high-speed mixer at 500rpm/min for 25min to obtain a first mixture;
s2, primary sintering: putting the first mixture into a sagger, shaking up and marking lines, sintering at 750 ℃ for 12 hours, crushing the materials after primary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so as to obtain the primary sintered nickel cobalt lithium manganate with the granularity D50 of 4.5 mu m;
s3, secondary mixing: mixing the primary sintered nickel cobalt lithium manganate, 1000ppm of zirconium dioxide and 600ppm of sodium carbonate in a high-speed mixer at 500rpm/min for 25min to obtain a mixture II;
s4, secondary sintering: putting the mixture II into a sagger, shaking up and marking lines, sintering at 900 ℃ for 10h, crushing the materials after secondary sintering by an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so as to obtain secondary sintered nickel cobalt lithium manganate with the granularity D50 of 4.5 mu m, namely sodium zirconate coated LiNi0.7Co0.1Mn0.2O2The scanning electron microscope characterization result is shown in fig. 1.
Example 4
S1, primary mixing: taking Ni with the particle size of 3-4 mu m according to the molar ratio of lithium to precursor of 1.080.7Co0.1Mn0.2(OH)2Mixing the lithium carbonate and the mixture in a high-speed mixer at 500rpm/min for 25min to obtain a first mixture;
s2, primary sintering: putting the first mixture into a sagger, shaking up and marking lines, sintering at 750 ℃ for 12 hours, crushing the materials after primary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so as to obtain primary sintered nickel cobalt lithium manganate with the granularity D50 of 4.8 mu m;
s3, secondary mixing: mixing the primary sintered nickel cobalt lithium manganate, 1000ppm of zirconium dioxide and 600ppm of sodium carbonate in a high-speed mixer at 500rpm/min for 25min to obtain a mixture II;
s4, secondary sintering: putting the mixture II into a sagger, shaking up and marking lines, sintering at 900 ℃ for 10h, crushing the materials after secondary sintering by an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so as to obtain secondary sintered nickel cobalt lithium manganate with the granularity D50 of 4.4 mu m, namely sodium zirconate coated LiNi0.7Co0.1Mn0.2O2。
Example 5
S1, primary mixing: taking Ni with the particle size of 3-4 mu m according to the molar ratio of lithium to precursor of 1.050.7Co0.1Mn0.2(OH)2Mixing the lithium carbonate and the mixture in a high-speed mixer at 500rpm/min for 25min to obtain a first mixture;
s2, primary sintering: putting the first mixture into a sagger, shaking up and marking lines, sintering at 700 ℃ for 12h, crushing the materials subjected to primary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so that the primary sintered nickel cobalt lithium manganate with the granularity D50 of 4.6 mu m is obtained;
s3, secondary mixing: mixing the primary sintered nickel cobalt lithium manganate, 1000ppm of zirconium dioxide and 600ppm of sodium carbonate in a high-speed mixer at 500rpm/min for 25min to obtain a mixture II;
s4, secondary sintering: putting the mixture II into a sagger, shaking up and marking lines, sintering at 850 ℃ for 10h, crushing the secondarily sintered material by an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so that the secondarily sintered nickel cobalt lithium manganate with the granularity D50 of 4.4 mu m, namely sodium zirconate coated LiNi, is obtained0.7Co0.1Mn0.2O2。
Example 6
S1, primary mixing: taking Ni with the particle size of 3-4 mu m according to the molar ratio of lithium to precursor of 1.050.7Co0.1Mn0.2(OH)2Mixing the lithium carbonate and the mixture in a high-speed mixer at 500rpm/min for 25min to obtain a first mixture;
s2, primary sintering: putting the first mixture into a sagger, shaking up and marking lines, sintering at 650 ℃ for 12 hours, and crushing the materials subjected to primary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so that the primary sintered nickel cobalt lithium manganate with the granularity D50 of 4.7 mu m is obtained;
s3, secondary mixing: mixing the primary sintered nickel cobalt lithium manganate, 1000ppm of zirconium dioxide and 600ppm of sodium carbonate in a high-speed mixer at 500rpm/min for 25min to obtain a mixture II;
s4, secondary sintering: putting the mixture II into a sagger, shaking up and marking lines, sintering at 920 ℃ for 10h, crushing the materials after secondary sintering by an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so as to obtain secondary sintered nickel cobalt lithium manganate with the granularity D50 of 4.5 mu m, namely sodium zirconate coated LiNi0.7Co0.1Mn0.2O2。
Example 7
S1, primary mixing: taking Ni with the particle size of 3-4 mu m according to the molar ratio of lithium to precursor of 1.050.8Co0.1Mn0.1(OH)2Mixing the lithium carbonate and the mixture in a high-speed mixer at 500rpm/min for 25min to obtain a first mixture;
s2, primary sintering: putting the first mixture into a sagger, shaking up and marking lines, sintering at 750 ℃ for 12 hours, crushing the materials after primary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so as to obtain primary sintered nickel cobalt lithium manganate with the granularity D50 of 4.8 mu m;
s3, secondary mixing: mixing the primary sintered nickel cobalt lithium manganate, 1000ppm of zirconium dioxide and 600ppm of sodium carbonate in a high-speed mixer at 500rpm/min for 25min to obtain a mixture II;
s4, secondary sintering: putting the mixture II into a sagger, shaking up and marking lines, sintering at 900 ℃ for 10h, crushing the materials after secondary sintering by an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so as to obtain secondary sintered nickel cobalt lithium manganate with the granularity D50 of 4.5 mu m, namely sodium zirconate coated LiNi0.8Co0.1Mn0.1O2。
Example 8
S1, primary mixing: taking Ni with the particle size of 3-4 mu m according to the molar ratio of lithium to precursor of 1.050.6Co0.2Mn0.2(OH)2Mixing the lithium carbonate and the mixture in a high-speed mixer at 500rpm/min for 25min to obtain a first mixture;
s2, primary sintering: putting the first mixture into a sagger, shaking up and marking lines, sintering at 750 ℃ for 12 hours, crushing the materials after primary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so that the granularity of the primary sintered nickel cobalt lithium manganate with the D50 of 4.5 mu m is obtained;
s3, secondary mixing: mixing the primary sintered nickel cobalt lithium manganate, 1000ppm of zirconium dioxide and 600ppm of sodium carbonate in a high-speed mixer at 500rpm/min for 25min to obtain a mixture II;
s4, secondary sintering: putting the mixture II into a sagger, shaking up and marking lines, sintering at 900 ℃ for 10h, crushing the materials after secondary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so that the granularity of the secondary sintered nickel cobalt lithium manganate with D50 of 4.3 mu m, namely the LiNi coated with the sodium zirconate is obtained0.6Co0.2Mn0.2O2。
Comparative example 1
S1, primary mixing: taking Ni with the particle size of 3-4 mu m according to the molar ratio of lithium to precursor of 1.050.7Co0.1Mn0.2(OH)2Mixing the lithium carbonate and the mixture in a high-speed mixer at 500rpm/min for 25min to obtain a first mixture;
s2, primary sintering: putting the first mixture into a sagger, shaking up and marking lines, sintering at 750 ℃ for 12 hours, crushing the materials after primary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so as to obtain primary sintered nickel cobalt lithium manganate with the granularity D50 of 4.5 mu m;
s3, secondary mixing: mixing the primary sintered nickel cobalt lithium manganate with 1000ppm of zirconium dioxide in a high-speed mixer at 500rpm/min for 25min to obtain a mixture II;
s4, secondary sintering: putting the mixture II into a sagger, shaking up and marking lines, sintering at 900 ℃ for 10h, crushing the secondarily sintered material by an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so that the secondarily sintered nickel cobalt lithium manganate with the granularity D50 of 4.5 mu m, namely LiNi, is obtained0.7Co0.1Mn0.2O2。
Comparative example 2
S1, primary mixing: taking Ni with the particle size of 3-4 mu m according to the molar ratio of lithium to precursor of 1.050.7Co0.1Mn0.2(OH)2Mixing the lithium carbonate and the mixture in a high-speed mixer at 500rpm/min for 25min to obtain a first mixture;
s2, primary sintering: putting the mixture II into a sagger, shaking up, making grids and lines, sintering at 750 ℃ for 12 hours, crushing the materials subjected to primary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so that the primary sintered nickel cobalt lithium manganate with the granularity D50 of 4.5 mu m is obtained;
s3, secondary mixing: mixing the primary sintered nickel cobalt lithium manganate with 600ppm of sodium carbonate in a high-speed mixer at 500rpm/min for 25min to obtain a mixture II;
s4, secondary sintering: putting the mixture II into a sagger, shaking up and marking lines, sintering at 900 ℃ for 10h, crushing the secondarily sintered material by an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so that the secondarily sintered nickel cobalt lithium manganate with the granularity D50 of 4.5 mu m, namely LiNi, is obtained0.7Co0.1Mn0.2O2。
Comparative example 3
S1, primary mixing: taking Ni with the particle size of 3-4 mu m according to the molar ratio of lithium to precursor of 1.050.7Co0.1Mn0.2(OH)2Mixing the lithium carbonate and the mixture in a high-speed mixer at 500rpm/min for 25min to obtain a first mixture;
s2, primary sintering: putting the mixture I into a sagger, shaking up and marking lines, sintering at 750 ℃ for 12h, crushing the material after primary sintering by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz, and the feeding frequency is 20Hz, so that the primary sintered nickel cobalt lithium manganate with the granularity D50 of 4.5 mu m, namely LiNi, is obtained0.7Co0.1Mn0.2O2。
Test example
The nickel cobalt lithium manganate prepared in the examples and comparative examples was used as a positive active material, graphite was used as a negative electrode to assemble a soft-packed battery, and the battery was subjected to an electrical property test using a battery property tester, wherein the charge-discharge cut-off voltage was 3 to 4.35V, the charge-discharge rate was 1C, and the high-temperature storage and high-temperature cycle properties at 45 ℃ were tested, and the results are shown in tables 1 and 2.
TABLE 1 test results of high-temperature storage performance of lithium nickel cobalt manganese oxide
Figure BDA0003486961390000091
Note: in table 1, capacity retention ratio = test capacity after full-electric battery high-temperature storage/capacity before storage × 100;
the capacity recovery rate is equal to the capacity multiplied by 100 of the full-electricity battery which is recovered to room temperature after high-temperature storage/capacity before storage;
thickness change = (battery thickness after full battery high temperature storage-thickness before storage)/thickness before storage × 100.
TABLE 2 test results of 45 ℃ cycle performance of lithium nickel cobalt manganese oxide
Figure BDA0003486961390000101
The test results in tables 1 and 2 show that the high-temperature storage and high-temperature cycle performance of the 7-series nickel cobalt lithium manganate prepared by introducing zirconium dioxide and sodium carbonate while performing secondary sintering are obviously improved. The reason is that partial zirconium dioxide and sodium carbonate are sintered at high temperature, and alkali fusion reaction is carried out on the surface of the nickel cobalt lithium manganate crystal to produce the sodium zirconate coating layer. The coating layer has high corrosion resistance and thermal stability, and can effectively reduce the corrosion of electrolyte on the surface of the nickel cobalt lithium manganate crystal when a lithium battery is prepared. In addition, a small amount of zirconium ions and sodium ions can permeate into the lithium nickel cobalt manganese oxide crystal during high-temperature reaction, the zirconium ions can improve the stability of the crystal structure, the sodium ions can broaden the migration rate of the lithium ions, and the high-temperature performance of the material is greatly improved by combining the corrosion prevention effect of the sodium zirconate coating on the electrolyte.
The embodiment also shows that the preparation method can improve the high-temperature performance of the full-system nickel cobalt lithium manganate, particularly the high-temperature performance of the 7-system ternary material, and the improvement effect is optimal.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A preparation method of lithium nickel cobalt manganese oxide is characterized by comprising the following steps:
ni precursor of nickel, cobalt and manganesexCoyMn1-x-y(OH)2Uniformly mixing the mixture with a lithium source to obtain a first mixture, wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y is less than 1;
carrying out primary sintering on the first mixture to obtain primary sintered nickel cobalt lithium manganate;
uniformly mixing the primary sintered nickel cobalt lithium manganate, zirconium dioxide and sodium carbonate to obtain a mixture II;
and carrying out secondary sintering on the mixture II to obtain secondary sintered nickel cobalt lithium manganate.
2. The method of claim 1, wherein the lithium source is selected from lithium hydroxide or lithium carbonate.
3. The method of claim 1, wherein the nickel cobalt manganese precursor, NixCoyMn1-x-y(OH)2In the formula, x is more than or equal to 7 and less than 8.
4. The method of claim 1, wherein the nickel cobalt manganese precursor, NixCoyMn1-x-y(OH)2The particle size D50 of (B) is 3-4 μm.
5. The method of claim 1, wherein the nickel cobalt manganese precursor, NixCoyMn1-x-y(OH)2And taking the lithium source according to the molar ratio of the lithium to the nickel-cobalt-manganese precursor of 1.02-1.08.
6. The method as claimed in claim 1, wherein the temperature of the primary sintering is 500-800 ℃ and the time is 10-15 h.
7. The method according to claim 1, wherein the amounts of the zirconium dioxide and the sodium carbonate added are respectively 1500ppm and 200 ppm and 1000ppm of the primary sintered lithium nickel cobalt manganese oxide.
8. The method as claimed in claim 1, wherein the temperature of the second sintering is 700-950 ℃ and the time is 8-15 h.
9. A lithium nickel cobalt manganese oxide produced by the production method according to any one of claims 1 to 8.
10. Use of the nickel cobalt lithium manganate according to claim 9 for the preparation of lithium ion batteries.
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