CN116443954A - Positive electrode material, preparation method thereof, positive electrode and lithium ion battery - Google Patents

Positive electrode material, preparation method thereof, positive electrode and lithium ion battery Download PDF

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CN116443954A
CN116443954A CN202310686251.9A CN202310686251A CN116443954A CN 116443954 A CN116443954 A CN 116443954A CN 202310686251 A CN202310686251 A CN 202310686251A CN 116443954 A CN116443954 A CN 116443954A
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positive electrode
heat treatment
lithium
precursor
potassium chloride
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CN116443954B (en
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张洪允
吴锋
苏岳锋
陈来
石奇
聂园林
王政强
张彬
范未峰
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Yibin Libao New 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

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Abstract

The invention relates to the technical field of lithium battery materials, and discloses a positive electrode material, a preparation method thereof, a positive electrode and a lithium ion battery. The preparation method of the positive electrode material with the single crystal morphology comprises the following steps: mixing: mixing the precursor, a lithium source and potassium chloride to obtain a mixture, wherein the mass of the potassium chloride is 1/3-2 times of the sum of the mass of the precursor and the mass of the lithium source; primary heat treatment: placing the mixture at 850-950 ℃ and performing heat treatment for 10-15 h in an atmosphere with oxygen; desalting: removing potassium chloride in the product obtained after primary heat treatment; and (3) secondary heat treatment: and (3) placing the product after the potassium chloride is removed at the temperature of 500-750 ℃ and performing heat treatment for 4-12 hours in an atmosphere with oxygen. The positive electrode material is prepared by adopting the preparation method. The positive electrode is prepared by adopting the positive electrode material. The lithium ion battery comprises the positive electrode. The method provided by the invention has low production difficulty and can prepare the high-nickel anode material with good performance.

Description

Positive electrode material, preparation method thereof, positive electrode and lithium ion battery
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a positive electrode material, a preparation method thereof, a positive electrode and a lithium ion battery.
Background
After sony developed the first commercial lithium ion battery in the world in 1991, the lithium ion battery production technology developed rapidly, and is currently the main power supply equipment of 3C products such as mobile phones/notebook computers. The new energy automobile industry as a power battery is also receiving more and more attention, and is actively developing. However, the new energy automobile industry using lithium ion batteries as power batteries still faces a plurality of problems, and the first problem is the problem of safety and driving mileage. The main technical bottleneck of the problem is the power battery, and the power-assisted industry is further developed, so that the solution of the energy density and the safety of the lithium ion battery is required to be focused.
The commercial lithium ion power battery mainly comprises a positive electrode, a negative electrode, a diaphragm, electrolyte, a current collector and packaging materials. In terms of the currently mature industrialization technology, the energy density of the negative electrode is far greater than that of the positive electrode, so that the important point and difficulty of increasing the energy density are the positive electrode side. Currently, the main commercialized anode has two main types of lithium iron phosphate and high-nickel ternary layered anode materials, wherein the energy density of the high-nickel ternary layered anode material is far greater than that of the lithium iron phosphate, and the high-nickel ternary layered anode material is a more ideal power battery anode material. However, its higher nickel content also presents safety problems and the thermal stability of the material is poor. How to achieve a balance between higher energy density and better safety? Monocrystallization is a direction of very powerful potential forces. Although the single-crystal high-nickel layered cathode material is slightly lower in capacity than the polycrystalline material of the same composition, the high-voltage stability and the thermal stability of the single-crystal high-nickel layered cathode material are often greatly improved. Therefore, the development of a preparation method of the stable single-crystal high-nickel layered cathode material is significant.
In view of this, it is possible, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a positive electrode material with a single crystal morphology, a preparation method thereof, a positive electrode and a lithium ion battery.
The invention is realized in the following way:
in a first aspect, the present invention provides a method for preparing a positive electrode material having a single crystal morphology, comprising:
mixing: mixing the precursor, a lithium source and potassium chloride to obtain a mixture, wherein the mass of the potassium chloride is 1/3-2 times of the sum of the mass of the precursor and the mass of the lithium source;
primary heat treatment: placing the mixture at 850-950 ℃ and performing heat treatment for 10-15 h in an atmosphere with oxygen;
desalting: removing potassium chloride in the product obtained after primary heat treatment;
and (3) secondary heat treatment: and (3) placing the product after the potassium chloride is removed at the temperature of 500-750 ℃ and performing heat treatment for 4-12 hours in an atmosphere with oxygen.
In an alternative embodiment, the desalting step is performed by:
cleaning the product after primary heat treatment with pure water; and (5) cleaning and drying.
In an alternative embodiment, the drying mode is that the drying is carried out for 24-36 hours at the temperature of 70-90 ℃ in a vacuum drying box.
In an alternative embodiment, the molar ratio of the metal element in the precursor to the lithium element in the lithium source is 1:1.30-1.75 during mixing.
In an alternative embodiment, the precursor is Ni x TM 1-x (OH) 2 Wherein TM is one or a combination of a plurality of Co/Mn/Al, x is more than or equal to 0.8 and less than or equal to 0.9
In an alternative embodiment, the precursor is Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 。
In an alternative embodiment, the lithium source is at least one of lithium hydroxide and lithium hydroxide monohydrate.
In a second aspect, the present invention provides a positive electrode material having a single crystal morphology, prepared by a method according to any one of the preceding embodiments.
In a third aspect, the present invention provides a positive electrode made from a positive electrode material having a single crystal morphology as in the previous embodiments.
In a fourth aspect, the present invention provides a lithium ion battery comprising the positive electrode of the previous embodiment.
The invention has the following beneficial effects:
KCl is introduced as a fused salt auxiliary material in a lithium preparation calcination stage to grow crystals, after potassium chloride is removed after the crystal growth, the surface structure of the material is repaired after secondary calcination at a lower temperature, and the high-nickel layered anode material with single crystal morphology is obtained. Compared with the prior art, the method remarkably reduces the production difficulty of the high nickel layered anode material with single crystal morphology, reduces the heat treatment temperature for material preparation, and reduces the subsequent crushing treatment process. The high nickel layered anode material with good dispersion and uniform size and single crystal morphology can be easily obtained.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the positive electrode material prepared in example 1;
FIG. 2 is a graph showing the results of X-ray diffractometer testing of the positive electrode material prepared in example 1;
FIG. 3 is a scanning electron microscope image of the positive electrode material prepared in example 2;
FIG. 4 is a scanning electron microscope image of the positive electrode material prepared in example 3;
FIG. 5 is a scanning electron microscope image of the positive electrode material prepared in example 4;
FIG. 6 is a graph showing the results of X-ray diffractometer testing of the positive electrode material prepared in example 4;
FIG. 7 is a graph showing the results of X-ray diffractometer testing of the positive electrode material prepared in example 5;
FIG. 8 is a scanning electron microscope image of the positive electrode material prepared in comparative example 1;
FIG. 9 is a scanning electron microscope image of the positive electrode material prepared in comparative example 2;
FIG. 10 is a scanning electron microscope image of the positive electrode material prepared in comparative example 3;
fig. 11 is a scanning electron microscope image of the positive electrode material prepared in comparative example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following specifically describes a positive electrode material, a preparation method thereof, a positive electrode and a lithium ion battery.
The preparation method of the positive electrode material with the single crystal morphology provided by the embodiment of the invention comprises the following steps:
mixing: mixing the precursor, a lithium source and potassium chloride to obtain a mixture, wherein the mass of the potassium chloride is 1/3-2 times of the sum of the mass of the precursor and the mass of the lithium source;
primary heat treatment: placing the mixture at 850-950 ℃ and performing heat treatment for 10-15 h in an atmosphere with oxygen;
desalting: removing potassium chloride in the product obtained after primary heat treatment;
and (3) secondary heat treatment: and (3) placing the product after the potassium chloride is removed at the temperature of 500-750 ℃ and performing heat treatment for 4-12 hours in an atmosphere with oxygen.
According to the preparation method provided by the invention, KCl is introduced as a fused salt auxiliary material for crystal growth in a lithium preparation calcination stage, after potassium chloride is removed after crystal growth, the surface structure of the material is repaired after secondary calcination at a lower temperature, and the high-nickel layered cathode material with single crystal morphology is obtained. In the method, the heat treatment temperature is important, if the temperature is too low or slightly higher than the melting point of KCl molten salt in the first heat treatment process, the auxiliary molten salt cannot be fully converted into a molten state, and further the effect of converting a solid phase reaction into a solid-liquid two-phase reaction so as to promote crystal growth cannot be well exerted, and the lower energy consumption can be realized on the basis of ensuring the shape/size of the material by the temperature setting at the present stage; in the second heat treatment process, if the temperature is too low, the effect of repairing the surface structure of the material cannot be achieved, and the temperature setting at the present stage can realize lower energy consumption on the basis of ensuring the structure and the performance of the material.
Compared with the prior art, the method remarkably reduces the production difficulty of the high nickel layered anode material with single crystal morphology, reduces the heat treatment temperature for material preparation, and reduces the subsequent crushing treatment process. The high nickel layered anode material with good dispersion and uniform size and single crystal morphology can be easily obtained.
Specifically, the preparation method comprises the following steps:
s1, preparing a precursor by a coprecipitation method, wherein the precursor is a high nickel precursor, and the chemical formula of the precursor is Ni x TM 1-x (OH) 2 Wherein TM is one or a combination of a plurality of Co/Mn/Al, and x is more than or equal to 0.8 and less than or equal to 0.9.
Preferably, the precursor is Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 。
It should be noted that, although the precursors involved in the embodiments provided in the present invention are all high nickel precursors, the method is equally applicable to the preparation of low nickel cathode materials.
S2, mixing materials
And fully and uniformly mixing the precursor, the lithium source and the potassium chloride to obtain a mixture.
The molar ratio of the metal element in the precursor to the lithium element in the lithium source is 1:1.30-1.75 (e.g., 1:1.30, 1:1.40, 1:1.50, 1:1.60, 1:1.70, or 1:1.75).
In the scheme, the addition amount of the lithium source is slightly more than that of the existing ternary material preparation process, because the loss amount of lithium is greatly increased in the preparation process due to the existence of KCl auxiliary molten salt and the subsequent desalting step, and the lithium distribution amount needs to be obviously improved to ensure the formation of a material structure. Preferably, the molar ratio of precursor lithium salt is 1:1.60.
the mass of potassium chloride is 1/3 to 2 times (e.g., 1/3 times, 1/2 times, 1 times, or 2 times) the sum of the mass of the precursor and the lithium source. Preferably, the potassium chloride is 1/2 times the total mass of precursor and lithium source.
The quality of the prepared positive electrode material can be ensured by introducing the potassium chloride with the above amount in the preparation process, if the potassium chloride amount is too large and exceeds the above range, the crystal growth can be limited, the size of the obtained finished product material crystal particles is too small, and if the potassium chloride amount is too small and is less than the above range, the effect of auxiliary molten salt can be weakened, and the problems of serious material agglomeration and the like occur.
Further, the lithium source in the present invention is preferably at least one of lithium hydroxide and lithium hydroxide monohydrate.
S2, primary heat treatment
The mixture is subjected to a heat treatment at a temperature of 850-950 ℃ (e.g. 850 ℃, 870 ℃, 900 ℃, 920 ℃ or 950 ℃) for 10-15 hours (e.g. 10 hours, 12 hours or 15 hours) in an atmosphere with oxygen. The process enables the precursor and the lithium source to react in a solid-liquid two-phase environment so as to grow to obtain the positive electrode material with the single crystal morphology.
S3, desalting
And removing potassium chloride in the product obtained after the primary heat treatment.
Specifically, the method for removing the potassium chloride is to clean the product after primary heat treatment by pure water, and remove the potassium chloride along with water after dissolving the potassium chloride in the water; and (3) carrying out reduced pressure suction filtration after cleaning, and placing the solid material obtained by suction filtration into a vacuum drying box to be dried for 24-36 h (for example, 24h, 30h or 36 h) at a temperature of 70-90 ℃ (for example, 70 ℃, 80 ℃ or 90 ℃).
In the step, clear water is adopted for cleaning and removing potassium chloride, and the operation is simple and effective.
S4, secondary heat treatment
And (3) placing the cleaned product at 500-750 ℃ (e.g. 500 ℃, 600 ℃, 700 ℃ or 750 ℃) and carrying out heat treatment for 4-12 hours (e.g. 4 hours, 6 hours, 8 hours, 10 hours or 12 hours) in an oxygen atmosphere, and repairing the surface structure of the material to obtain the positive electrode material with the single crystal morphology and the better morphology.
The positive electrode material with the single crystal morphology, which is provided by the embodiment of the invention, is prepared by adopting the preparation method provided by the embodiment of the invention, and has the characteristics of good dispersion and uniform size.
The anode provided by the embodiment of the invention is prepared from the anode material with the single crystal morphology. The positive electrode is prepared from the positive electrode material provided by the embodiment of the invention, so that the positive electrode has the characteristic of good electrochemical performance.
The lithium ion battery provided by the embodiment of the invention comprises the anode provided by the embodiment of the invention. The lithium ion battery has the characteristic of good electrochemical performance due to the positive electrode provided by the embodiment of the invention.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
(1) Ni to be produced by the coprecipitation method 0.83 Co 0.11 Mn 0.06 (OH) 2 The molar ratio of the precursor to the lithium hydroxide monohydrate is 1:1.60 ratioPreparing lithium, wherein KCl which is 1/2 times of the mass sum of the precursor and the lithium hydroxide monohydrate is simultaneously added as auxiliary molten salt in the process, and fully grinding to obtain a uniformly dispersed mixture;
(2) Placing the mixture obtained in the step (1) in a tube furnace, and performing heat treatment for 12 hours at 900 ℃ in an oxygen atmosphere to obtain a crude product;
(3) Washing the crude product obtained in the step (2) with warm water at about 60 ℃, and performing vacuum filtration to obtain a solid filter material; the solid filter material was dried in a vacuum oven at 80 ℃ for 30h.
(4) And (3) placing the product obtained after the drying in the step (3) in a tube furnace, and performing heat treatment for 5 hours at the temperature of 500 ℃ in an oxygen atmosphere to obtain the high-nickel layered anode material with the single crystal morphology.
The test results of a scanning electron microscope and an inductively coupled plasma mass spectrometer of the obtained high-nickel layered cathode material with single crystal morphology are shown in fig. 1, the test results of an inductively coupled plasma mass spectrometer are shown in table 1, and the test results of an X-ray diffractometer are shown in fig. 2. As can be seen from FIG. 1, the final product has good morphology, basically distributed particle size of 1-3 μm, good dispersion and uniform size. From table 1, it can be seen that KCl molten salt can be easily removed by washing with water, and the proportions of the other elements are not affected. From fig. 2 it can be seen that the structure of the resulting end product is good.
Table 1 inductively coupled plasma mass spectrometer test results for example 1
Example 2
(1) Ni to be produced by the coprecipitation method 0.83 Co 0.11 Mn 0.06 (OH) 2 The molar ratio of the precursor to the lithium hydroxide monohydrate is 1:1.60, adding KCl which is 2 times of the sum of the mass of the precursor and the mass of the lithium hydroxide monohydrate as auxiliary molten salt in the process, and fully grinding to obtain a uniformly dispersed mixture;
(2) Placing the mixture obtained in the step (1) in a tube furnace, and performing heat treatment for 14 hours at 900 ℃ in an oxygen atmosphere to obtain a crude product;
(3) Washing the crude product obtained in the step (2) with warm water at about 60 ℃, and performing vacuum filtration to obtain a solid filter material; the solid filter material was dried in a vacuum oven at 70 ℃ for 36h.
(4) And (3) placing the product obtained after the drying in the step (3) in a tube furnace, and performing heat treatment for 10 hours at 750 ℃ in an oxygen atmosphere to obtain the high-nickel layered anode material with single crystal morphology.
The scanning electron microscope test result of the obtained high nickel layered cathode material with single crystal morphology is shown in fig. 3, and it can be seen from the graph that the morphology of the obtained final product is good.
Example 3
(1) Ni to be produced by the coprecipitation method 0.83 Co 0.11 Mn 0.06 (OH) 2 The molar ratio of the precursor to the lithium hydroxide monohydrate is 1:1.75, adding KCl which is 1 time of the sum of the mass of the precursor and the mass of the lithium hydroxide monohydrate as auxiliary molten salt in the process, and fully grinding to obtain a uniformly-dispersed mixture;
(2) Placing the mixture obtained in the step (1) in a tube furnace, and performing heat treatment for 10 hours at 950 ℃ in an oxygen atmosphere to obtain a crude product;
(3) Washing the crude product obtained in the step (2) with warm water at about 60 ℃, and performing vacuum filtration to obtain a solid filter material; the solid filter material was dried in a vacuum oven at 90 ℃ for 24h.
(4) And (3) placing the product obtained after the drying in the step (3) in a tube furnace, and performing heat treatment for 4 hours at the temperature of 500 ℃ in an oxygen atmosphere to obtain the high-nickel layered anode material with the single crystal morphology.
The scanning electron microscope test result of the obtained high nickel layered cathode material with single crystal morphology is shown in fig. 4, and it can be seen from the graph that the morphology of the obtained final product is good.
Example 4
This embodiment is substantially the same as embodiment 1, except that:
preparing lithium from the precursor and lithium hydroxide monohydrate according to the molar ratio of metal element to lithium element of 1:1.30, and simultaneously adding KCl which is 1/3 times of the mass sum of the precursor and the lithium hydroxide monohydrate as auxiliary molten salt in the process;
in the primary heat treatment process, the heat treatment temperature is controlled to 850 ℃ and the time is 15 hours; in the secondary heat treatment process, the temperature is controlled to be 600 ℃ and the time is 12 hours.
The test result of a scanning electron microscope of the obtained high-nickel layered anode material with single crystal morphology is shown in fig. 5, the test result of an X-ray diffractometer is shown in fig. 6, and the obtained final product has good morphology and complete structure.
Example 5
This embodiment is substantially the same as embodiment 4, except that: the precursor and lithium hydroxide monohydrate are subjected to lithium matching according to the molar ratio of metal elements to lithium elements of 1:1.15.
The test result of the X-ray diffractometer of the obtained high-nickel layered cathode material with single crystal morphology is shown in fig. 7, and it can be seen from the graph that the structure growth of the obtained final product is not ideal.
Comparative example 1
This comparative example is a control experiment of example 1, which was performed under substantially the same conditions as example 1, except that: the KCl fused salt is not added to assist the calcination process, and the post-treatment process of water washing and secondary calcination is not needed correspondingly, and the specific steps are as follows:
(1) Ni to be produced by the coprecipitation method 0.83 Co 0.11 Mn 0.06 (OH) 2 The molar ratio of the precursor to the lithium hydroxide monohydrate is 1:1.60, fully grinding to obtain a uniformly dispersed mixture;
(2) And (3) placing the mixture obtained in the step (1) in a tube furnace, and performing heat treatment for 12 hours in an oxygen atmosphere at 900 ℃ to obtain a final product.
The scanning electron microscope test result of the obtained high-nickel layered cathode material with the single crystal morphology is shown in fig. 8, and it can be seen from the graph that the same precursor has a poor structure and serious agglomeration phenomenon and needs further crushing and sieving when no KCl molten salt is used for auxiliary calcination. Compared with the traditional lithium-doped calcination preparation process, the method can reduce the calcination temperature and time of the subsequent crystal growth and save the cost of industrial production by converting the solid phase reaction into a solid-liquid two-phase reaction. Meanwhile, the material subjected to water washing and secondary calcination can reduce agglomeration, and the high-nickel layered anode material with good dispersion and uniform size and single crystal morphology can be obtained more easily. The links of subsequent crushing and screening and the like are reduced, and the industrial production flow is simplified.
Comparative example 2
This comparative example is substantially the same as example 4, except that: the primary heat treatment temperature was 800 ℃.
The scanning electron microscope test result of the obtained high-nickel layered cathode material with the single crystal morphology is shown in fig. 9, and it can be seen from the graph that the material does not generate good single crystal morphology. In the preparation process, the primary heat treatment temperature should not be too low, and even if the temperature is higher than the melting point of potassium chloride, the primary heat treatment temperature is not too high, so that the advantage of molten salt assistance is difficult to be exerted, and the positive electrode material with good monocrystal morphology is obtained.
Comparative example 3
This comparative example is substantially the same as example 1, except that: the secondary heat treatment temperature was 400 ℃.
The scanning electron microscope test result of the obtained high-nickel layered cathode material with single crystal morphology is shown in fig. 10, and it can be seen from the graph that the surface of the material particle is not smooth. The method shows that the temperature of the secondary heat treatment is not too low in the preparation process, and the surface morphology of the monocrystal with too low temperature in the secondary heat treatment process cannot be well repaired.
Comparative example 4
This comparative example is substantially the same as example 1, except that: the KCl addition was 1/5 times the sum of the mass of the precursor and the lithium source.
The scanning electron microscope test result of the obtained high nickel layered cathode material with single crystal morphology is shown in fig. 11, and the material agglomeration is obvious from the graph. In the preparation process, the adding amount of KCl is not too small, and the anode material with good dispersion cannot be obtained if the adding amount is too small.
In summary, the preparation method of the positive electrode material with the monocrystal morphology provided by the invention introduces KCl as a molten salt auxiliary material for crystal growth in a lithium preparation calcination stage, repairs the surface structure of the material after secondary calcination at a lower temperature after potassium chloride is removed after crystal growth, and obtains the high-nickel lamellar positive electrode material with the monocrystal morphology. Compared with the prior art, the method remarkably reduces the production difficulty of the high nickel layered anode material with single crystal morphology, reduces the heat treatment temperature for material preparation, and reduces the subsequent crushing treatment process. The high nickel layered anode material with good dispersion and uniform size and single crystal morphology can be easily obtained.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the positive electrode material with the single crystal morphology is characterized by comprising the following steps of:
mixing: mixing a precursor, a lithium source and potassium chloride to obtain a mixture, wherein the mass of the potassium chloride is 1/3-2 times of the sum of the mass of the precursor and the mass of the lithium source;
primary heat treatment: placing the mixture at 850-950 ℃ and performing heat treatment for 10-15 h in an atmosphere with oxygen;
desalting: removing potassium chloride in the product obtained after primary heat treatment;
and (3) secondary heat treatment: and (3) placing the product after the potassium chloride is removed at the temperature of 500-750 ℃ and performing heat treatment for 4-12 hours in an atmosphere with oxygen.
2. The method of claim 1, wherein the desalting step is performed by:
cleaning the product after primary heat treatment with pure water; and (5) cleaning and drying.
3. The preparation method according to claim 2, wherein the drying mode is drying in a vacuum drying oven at a temperature of 70 ℃ to 90 ℃ for 24 to 36 hours.
4. The preparation method of claim 1, wherein the molar ratio of the metal element in the precursor to the lithium element in the lithium source is 1:1.30-1.75 during mixing.
5. The method of claim 1, wherein the precursor is Ni x TM 1-x (OH) 2 Wherein TM is one or a combination of a plurality of Co/Mn/Al, and x is more than or equal to 0.8 and less than or equal to 0.9.
6. The method of claim 2, wherein the precursor is Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 。
7. The method of claim 1, wherein the lithium source is at least one of lithium hydroxide and lithium hydroxide monohydrate.
8. A positive electrode material having a single crystal morphology, characterized by being produced by the production method according to any one of claims 1 to 7.
9. A positive electrode prepared from the positive electrode material having a single crystal morphology according to claim 8.
10. A lithium ion battery comprising the positive electrode of claim 9.
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