CN110380041B - Preparation method and application of hierarchical-structure positive electrode material for lithium ion battery - Google Patents
Preparation method and application of hierarchical-structure positive electrode material for lithium ion battery Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a hierarchical structure cathode material for a lithium ion battery and a preparation method thereofxCoyAl1‑x‑yOzCl2‑z(ii) a X is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.9, z is more than or equal to 1.5 and less than or equal to 1.95, the anode material is prepared by water mixing, molten salt mixing, sintering and crushing, and Cl element is added to replace O element in the original NCA material, so that an NCA-like anode different from the traditional NCA material is formed.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a hierarchical structure cathode material for a lithium ion battery, and a preparation method and application thereof.
Background
Lithium ion batteries are the latest generation of rechargeable batteries following nickel hydrogen batteries. Lithium ion batteries have the advantages of high lithium intercalation voltage, high specific energy, no memory effect, small self-discharge, no toxicity and the like, become a battery system widely applied at present, and are generally accepted on high-energy portable electronic equipment. The positive electrode material of the lithium ion battery is one of the cores of the lithium ion battery. The anode material provides a large amount of freely-deintercalated lithium ions in the charging work of the lithium ion battery, and is important for improving the electrochemical properties of the lithium ion battery, such as working voltage, specific energy, cycle life and the like.
The anode material for the existing high-specific energy lithium ion battery is a ternary material. Ni improves the material capacity and affects the cyclicity too much; co reduces cation mixed discharge and stabilizes a laminated structure; the cost of Mn is reduced, and the safety and the stability are improved; al improves the lattice structure and improves the cyclability. By adjusting the proportion of Ni, Co, Mn and Al, ternary materials with different properties are prepared. It is classified into NCM and NCA, and both of them essentially solve the problem of lithium cobaltate (LiCoO)2) Or lithium nickelate (LiNiO)2) Stability of the layered structure. The NCA anode has the advantage of high specific capacity, but the NCA material has poor cycle performance and low rate discharge efficiency, and the traditional method has complex preparation, low preparation efficiency and impure phases.
In order to overcome the problems in the prior art, patent 201410720895.6 proposes a modification method of the lithium ion battery cathode material NCA in the prior art, but the micro morphology is seriously aggregated, the size is large, the capacity release is not facilitated, and the preparation method is complex.
Patent 201510878319.9 proposes a preparation method for improving the compaction density of the lithium ion battery NCA cathode material, but the molten salt medium method proposed in the claims is that after the NCA is prepared, the NCA is physically mixed in situ, the interface contact resistance is large, and in appearance, the micro-appearance irregular contact is large.
Patent 201510175555.4 proposes a lithium ion battery LiNi1-x-yCoxAlyO2The patent data show that the material prepared by the method has large granularity, serious appearance agglomeration, irregular structure and serious discharge performance attenuation under the 2C multiplying power.
Patent CN201610741604.0 discloses a method for preparing NCA ternary positive electrode material by adding LiCl into nickel-cobalt-aluminum coprecipitation precursor and co-calcining, and the obtained NCA ternary positive electrode material has a reversible specific capacity of 148mAh/g and a capacity retention rate of 85%, because LiCl is not added in the precursor stage but is added to the formed NCA as lithium saltThe modification advantage of LiCl cannot be exerted by calcining after body driving, and the finally obtained product is still LiNixCoyAlzO2(x + y + z ═ 1), Cl element was lost after high-temperature sintering, and O element was not replaced, so that discharge performance was not satisfactory.
In a word, no effective method in the prior art can rapidly prepare the NCA anode material with good high-rate performance, and the existing NCA anode material is difficult to have three characteristics of high potential, high specific energy and high-rate output, and does not meet the power supply requirement of modern advanced electronic equipment.
Disclosure of Invention
The invention provides a hierarchical structure anode material for a lithium ion battery, a preparation method and application for solving the technical problems.
The method is realized by the following technical scheme:
the chemical formula of the hierarchical structure cathode material is LiNixCoyAl1-x-yOzCl2-z(ii) a X is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.9, and z is more than or equal to 1.5 and less than or equal to 1.95; the micro-morphology of the anode material with the hierarchical structure comprises a primary structure and a secondary structure; the primary structure is a layered structure, and the secondary structure is a spherical structure; the layered structure is a nanosheet; the spherical structure is a microsphere.
The micro-morphology is a microsphere formed by stacking at least 10 single-layer nanosheets.
The single-layer thickness of the nano sheet is 30 nm-180 nm.
The invention also aims to provide a preparation method of the hierarchical structure cathode material for the lithium ion battery, which comprises the following steps:
(1) mixing water: putting lithium salt, nickel salt, cobalt salt and aluminum salt into a stirrer, adding water, and stirring until the solution is clear to obtain an aqueous solution for later use;
(2) molten salt mixing: heating LiCl to a molten state to obtain a clear liquid A; secondly, placing the aqueous solution obtained in the step (1) in an air-blast drying oven at the temperature of 80-180 ℃ for heating for 2-24 h to obtain molten liquid B, taking out the molten liquid B and placing the molten liquid B in a drying environment for later use; thirdly, injecting the clear liquid A into the molten liquid B, and then placing the clear liquid A in an air-blast drying oven at 160-200 ℃ for heating for 1-4 h to obtain a precursor molten liquid C;
(3) and (3) sintering: putting the precursor molten liquid C obtained in the step (2) into a sintering furnace, heating to 750-950 ℃ in an aerobic environment, carrying out heat preservation treatment for 8-16 h, and cooling to obtain a solid of the anode material with the hierarchical structure;
(4) crushing: and (4) crushing and sieving the solid of the anode material with the hierarchical structure obtained in the step (4) to obtain the anode material with the hierarchical structure.
In the step (1), the lithium salt is lithium nitrate; the nickel salt is any one or a composition of more of nickel nitrate and nickel nitrate hexahydrate; the cobalt salt is any one or a combination of more of cobalt nitrate and cobalt nitrate hexahydrate; the aluminum salt is any one or a combination of more of aluminum nitrate and aluminum nitrate nonahydrate.
In the step (2), the mass ratio of the water to the mixture of lithium salt, nickel salt, cobalt salt and aluminum salt is 3-10: 1.
in the step (2), the water is any one of deionized water, distilled water and ultrapure water.
In the step (2), the stirring speed is 80 r/min-600 r/min.
In the step (3), the heating temperature of LiCl is 620-700 ℃.
In the step (3), the drying environment has a humidity of less than or equal to 3%.
In the step (5), the rotating speed of the pulverizer is 5000-6000 r/min, and the pulverizing time is 1-3 min.
The anode material with the hierarchical structure is powder, and the granularity of the powder is more than or equal to 200 meshes.
The invention also aims to provide application of the cathode material with the hierarchical structure in a lithium ion battery.
Has the advantages that:
firstly, the conductivity is improved. By adding Cl element to replace O element in original NCA material, an NCA-like type positive electrode different from the conventional NCA material is formed, and LiCl tape is usedThe inherent strong ionic conductivity of improves Li+Insertion and extraction kinetics of (i.e. Li of O-Li-O intermediate layer)+Does not suffer from electron exchange because of Cl-Than O2-Losing electrons more easily. Therefore, Li at high rate discharge+The degree of de-intercalation will be faster, thereby reducing the impedance and weakening the polarization phenomenon. Thereby improving the overall conductivity of the NCA material, and substituting the element of O by the element of Cl to lead Ni to be represented by Ni2+And Ni3+Coexists in the graded-structure cathode material, and Ni increased with the doping amount of Cl element2+The ratio of (c) is also increased, resulting in performance degradation, and thus the amount of Cl doping is defined in the present invention to reduce cation shuffling. And secondly, a hierarchical structure is constructed, so that specific energy is improved, and high-rate output is realized. Compared with a direct water mixing mode, the fused salt blending method provided by the invention can ensure that all precursor materials are subjected to atom uniform mixing in a molten state, and a batched hierarchical structure positive electrode material LiNi can be obtained by sinteringxCoyAl1-x-yOzCl2-zThe positive electrode material having a hierarchical structure has the dual advantages of a layered structure and a spherical structure. And thirdly, the coating has regular micro-morphology. According to the scanning electron microscope image, the following steps are shown: the anode material has an obvious hierarchical structure, and the size of the hierarchical structure is uniform and regular; under a scanning electron microscope with low multiplying power, a uniformly distributed spherical structure is presented, and compared with an agglomerated spherical structure, the spherical structure increases the specific surface area, so that more active sites are obtained to be in contact with electrolyte, and the specific energy is improved; meanwhile, under high multiplying power, the nano-layered structure with the longest length of the plane being more than or equal to 1 mu m is easy to strip electrons on the contact interface of the anode material and the electrolyte, and the multiplying power and the cyclicity are improved.
In conclusion, the cathode material with the hierarchical structure prepared by the invention has regular and uniform micro-morphology and also has the high potential and high specific capacity of the NCA, and the capacity output of the NCA material under high rate is greatly optimized by the enhancing principle, so that the cathode of the NCA with the hierarchical structure provided by the invention has three characteristics of high potential, high specific capacity and high rate output.
In addition, the invention strictly controls the water-solid ratio of water to lithium salt, nickel salt, cobalt salt and aluminum salt, improves the mixing efficiency and avoids the problem of overlong dehydration time; the stirring speed of water, lithium salt, nickel salt, cobalt salt and aluminum salt is strictly controlled, and is determined according to the water-solid mass ratio and the quality of the stirred material, so that the materials are fully mixed without centrifugation, the dispersibility of the materials is improved, and the energy consumption of mixing is reduced; strictly controlling the heating temperature of the lithium chloride, wherein the heating temperature is determined according to the mass of the lithium chloride to ensure the melting efficiency of materials and reduce the melting energy consumption, and the heating temperature is also determined according to the mass of the molten liquid B to ensure that when the lithium chloride can be quenched from a liquid state above 620 ℃ to a snowflake solid state below 180 ℃ (the lithium chloride is rapidly solidified and elongated by being driven by thermal stress), enough heat can be released by self-quenching to accelerate the molecular reaction kinetics so as to rapidly diffuse the lithium chloride into the molten liquid B; the heating temperature is strictly controlled, if the heating temperature is too high, energy consumption is increased, and simultaneously agglomeration accumulation of a precursor containing lithium chloride is easy to generate, so that ordered stacking of nanosheets in a hierarchical structure is not facilitated, the heating time temperature is too low, uniform atom doping of lithium chloride and molten liquid B is not facilitated, the proportion of local elements is unbalanced, molecular micro-region products are inconsistent, and lattice distortion is easy to generate, and in addition, the temperature for removing 1/2 crystal water by the lithium chloride is 160 ℃, so that the temperature is selected as the lowest heating temperature; strictly controlling the humidity of a drying environment, ensuring the moisture content of a precursor, and reducing dehydration in a sintering process, thereby improving the moisture removal rate, removal amount and energy consumption in the sintering process, and further improving the spatial structure of the anode material; the rotating speed of the pulverizer is strictly controlled, so that the high-efficiency pulverization of the powder is guaranteed, and the micro-morphology is prevented from being damaged; the strict control of the particle size of the anode material is beneficial to preparing the electrode.
The invention uses chlorineMelting lithium into clear liquid A, injecting the clear liquid A into molten liquid B containing lithium salt, nickel salt, cobalt salt and aluminum salt, stacking the layered structure to form a spherical structure, strictly controlling the heating temperature of precursor molten liquid C to be 160-200 ℃, ensuring the synthesis rate, effectively controlling ion diffusion and atom doping, ensuring the crystallization of the layered nanosheets, and automatically stacking to form the microspheres. If the temperature is too low, LiCl 1/2H cannot be removed even though the atomic doping is not uniform2The 1/2 crystal water in O is easy to generate lattice distortion, and if the temperature is too high, the energy consumption is increased and the crystal water is directly agglomerated, so that regular microspheres cannot be formed.
Drawings
Fig. 1 is an XRD test chart of the cathode material with a hierarchical structure prepared in the first embodiment of the present invention;
FIG. 2 is a SEM test chart of a graded-structure cathode material prepared according to a first embodiment of the present invention;
FIG. 3 is a SEM test chart of a cathode material with a hierarchical structure prepared by the second embodiment of the present invention;
FIG. 4 is a SEM test chart of a cathode material with a hierarchical structure prepared in the third embodiment of the present invention;
FIG. 5 is a SEM test chart of a positive electrode material with a hierarchical structure prepared according to a fourth embodiment of the present invention;
FIG. 6 is an EDS test chart of a cathode material with a hierarchical structure prepared in example four of the present invention
FIG. 7 is a comparative graph of discharge curves at 1C rate of lithium ion batteries prepared according to four examples of the present invention;
fig. 8 is a graph comparing the discharge curves at 10C rate of the lithium ion batteries manufactured by the four examples of the present invention.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A hierarchical anode material for Li-ion battery has a chemical formula of LiNi0.8Co0.19Al0.01O1.90Cl0.1(ii) a The micro-morphology is a microsphere formed by stacking at least 10 single-layer nanosheets, and the preparation method specifically comprises the following steps:
weighing: weighing 100g of lithium nitrate, nickel nitrate, cobalt nitrate, aluminum nitrate and lithium chloride according to a molecular formula and a stoichiometric ratio;
water mixing: adding 1000g of distilled water into lithium nitrate, nickel nitrate, cobalt nitrate and aluminum nitrate weighed in the step I in a stirrer, and uniformly stirring at a rotating speed of 80r/min until a clear solution is obtained, namely obtaining an aqueous solution for later use;
mixing molten salt: LiCl was placed in a ceramic vessel and heated at 620 ℃ to clear liquid A; pouring the aqueous solution obtained in the second step into a ceramic container, placing the ceramic container in an air drying oven for heating for 24 hours at the temperature of 80 ℃ to obtain molten liquid B, taking out the molten liquid B, and placing the molten liquid B in a drying environment with the humidity of 1.2% for later use; then, injecting the clear liquid A into the molten liquid B, and then putting the clear liquid A into an air-blowing drying oven at 160 ℃ for heating for 4 hours to obtain a precursor molten liquid C;
and fourthly, sintering: putting the precursor molten liquid C obtained in the step (III) into a sintering furnace, heating to 750 ℃ in an air atmosphere, keeping for 8h, and cooling to obtain a solid of the anode material with a hierarchical structure;
crushing: putting the solid of the anode material with the hierarchical structure obtained in the step (iv) into a crusher to crush for 2min at 5000r/min, and sieving with a 200-mesh sieve to obtain the anode material LiNi with the hierarchical structure0.8Co0.19Al0.01O1.9Cl0.1；
LiNi obtained in this example0.8Co0.19Al0.01O1.9Cl0.1The XRD test pattern of the cathode material is shown in figure 1, and the SEM test pattern is shown in figure 2.
Example 2
A hierarchical anode material for Li-ion battery has a chemical formula of LiNi0.37Co0.6Al0.03O1.95Cl0.05(ii) a The micro-sphere with the micro-morphology formed by stacking at least 10 single-layer nanosheets comprises the following specific stepsThe method comprises the following steps:
weighing: weighing 500g of lithium nitrate, nickel nitrate, cobalt nitrate, aluminum nitrate and lithium chloride according to a molecular formula and a stoichiometric ratio;
water mixing: adding 3500g of ultrapure water into lithium nitrate, nickel nitrate, cobalt nitrate and aluminum nitrate weighed in the step I in a stirrer, and uniformly stirring at the rotating speed of 180r/min until a clear solution is obtained, namely an aqueous solution for later use;
mixing molten salt: LiCl was placed in a ceramic vessel and heated to 670 ℃ to clear liquid A; pouring the aqueous solution obtained in the second step into a ceramic container, placing the ceramic container in an air drying oven for heating for 10 hours at 160 ℃ to obtain a molten liquid B, taking out the molten liquid B, and placing the molten liquid B in a drying environment with the humidity of 1.5% for later use; then injecting the clear liquid A into the molten liquid B, and then putting the clear liquid A into an air-blowing drying box at 170 ℃ for heating for 2 hours to obtain a precursor molten liquid C;
and fourthly, sintering: putting the precursor molten liquid C obtained in the step (III) into a sintering furnace, heating to 800 ℃ in an oxygen atmosphere, keeping for 10h, and cooling to obtain a solid of the anode material with a hierarchical structure;
crushing: putting the solid of the anode material with the hierarchical structure obtained in the step (iv) into a crusher to crush for 1min at 5500r/min, and sieving with a 250-mesh sieve to obtain the anode material LiNi with the hierarchical structure0.37Co0.6Al0.03O1.95Cl0.05；
LiNi obtained in this example0.37Co0.6Al0.03O1.95Cl0.05The SEM test chart of the positive electrode material is shown in fig. 3.
Example 3
A hierarchical anode material for Li-ion battery has a chemical formula of LiNi0.35Co0.6Al0.05O1.9Cl0.1(ii) a The micro-morphology is a microsphere formed by stacking at least 10 single-layer nanosheets, and the preparation method specifically comprises the following steps:
weighing: according to the molecular formula, the total amount of lithium nitrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, aluminum nitrate nonahydrate and lithium chloride is 500 g.
Water mixing: adding 1500g of distilled water into the lithium nitrate, nickel nitrate hexahydrate, cobalt nitrate and aluminum nitrate weighed in the step I in a stirrer, and uniformly stirring at 200r/min until a clear solution is obtained, namely obtaining an aqueous solution for later use;
mixing molten salt: LiCl was placed in a ceramic vessel and heated to 670 ℃ to clear liquid A; pouring the aqueous solution obtained in the second step into a ceramic container, placing the ceramic container in a forced air drying oven for heating for 12 hours at 160 ℃ to obtain a molten liquid B, taking out the molten liquid B, and placing the molten liquid B in a drying environment with the humidity of 3% for later use; then, injecting the clear liquid A into the molten liquid B, and then putting the clear liquid A into an air-blowing drying oven at 180 ℃ to heat for 1h to obtain a precursor molten liquid C;
and fourthly, sintering: putting the precursor molten liquid C obtained in the step (III) into a sintering furnace, heating to 850 ℃ in an air atmosphere, keeping for 12h, and cooling to obtain a solid of the anode material with a hierarchical structure;
crushing: putting the solid of the anode material with the hierarchical structure obtained in the step (IV) into a grinder to be ground for 1min at 5700r/min, and sieving the solid with a 300-mesh sieve to obtain the anode material LiNi with the hierarchical structure0.35Co0.6Al0.05O1.9Cl0.1；
LiNi obtained in this example0.35Co0.6Al0.05O1.9Cl0.1The SEM test image of the positive electrode material is shown in fig. 4.
Example 4
A hierarchical anode material for Li-ion battery has a chemical formula of LiNi0.39Co0.6Al0.01O1.92Cl0.08(ii) a The micro-morphology is a microsphere formed by stacking at least 10 single-layer nanosheets, and the preparation method specifically comprises the following steps:
weighing: weighing 500g of lithium nitrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, aluminum nitrate nonahydrate and lithium chloride according to the molecular formula and the stoichiometric ratio;
water mixing: putting the lithium nitrate, nickel nitrate hexahydrate, cobalt nitrate and aluminum nitrate weighed in the step I into a stirrer, adding 2500g of deionized water, and stirring at the rotating speed of 600r/min until the solution is clear to obtain an aqueous solution for later use;
mixing molten salt: LiCl was placed in a ceramic vessel and heated at 650 ℃ to clear liquid A; pouring the aqueous solution obtained in the second step into a ceramic container, placing the ceramic container in a forced air drying oven for heating for 2 hours at 180 ℃ to obtain a molten liquid B, taking out the molten liquid B, and placing the molten liquid B in a drying environment with the humidity of 0.3% for later use; then, injecting the clear liquid A into the molten liquid B, and then putting the clear liquid A into an air-blowing drying oven at the temperature of 200 ℃ to heat for 1h to obtain a precursor molten liquid C;
and fourthly, sintering: putting the precursor molten liquid C obtained in the step (III) into a sintering furnace, heating to 950 ℃ in the air atmosphere, keeping for 16h, and cooling to obtain a solid of the anode material with the hierarchical structure;
crushing: putting the solid of the anode material with the hierarchical structure obtained in the step (iv) into a crusher to crush for 3min at 6000r/min, and sieving with a 300-mesh sieve to obtain the anode material LiNi with the hierarchical structure0.39Co0.6Al0.01O1.92Cl0.08；
LiNi obtained in this example0.39Co0.6Al0.01O1.92Cl0.08The SEM test picture of the cathode material is shown in FIG. 5, and the EDS elemental analysis picture is shown in FIG. 6.
Application example 1
Uniformly mixing the positive electrode material with the hierarchical structure prepared in the embodiment 1, the embodiment 2, the embodiment 3 and the embodiment 4 with conductive carbon black and a PVDF (polyvinylidene fluoride) adhesive in an NMP (N-methyl pyrrolidone) solvent according to the weight percentage of 9:0.5:0.5, coating the slurry on an aluminum foil, drying at 100 ℃ for 12 hours, and preparing a positive electrode sheet with phi 16mm by using a mold; preparing a CR2032 button cell in an inert atmosphere glove box, wherein the cathode of the cell is a lithium sheet and 1M LiPF6The electrolyte is formed by EC/DEC (volume ratio is 1: 1); the discharge was carried out at a rate of 1C, and calculated with 3.0V as a cut-off voltage, the specific capacity of the example was 176.33mAh/g, the specific capacity of the example was 173.33mAh/g, the specific capacity of the example was 165.62mAh/g, and the specific capacity of the example was 157.98 mAh/g. The discharge performance is compared in FIG. 7.
Application example 2
Uniformly mixing the positive electrode material with the hierarchical structure and the conductive carbon black prepared in the first, second, third and fourth embodiments, wherein the PVDF binder is 9:0.5:0.5 in weight percentage in NMP solvent, coating the slurry on an aluminum foil, drying at 100 ℃ for 12h, and preparing a positive electrode sheet with phi 16mm by using a mold; preparing a CR2032 button cell in an inert atmosphere glove box, wherein the cathode of the cell is a lithium sheet and 1M LiPF6The electrolyte is formed by EC/DEC (volume ratio is 1: 1); the discharge was carried out at a rate of 10C, and calculated with 3.0V as a cut-off voltage, the specific capacity of the example was 116.95mAh/g, the specific capacity of the example was 121.16mAh/g, the specific capacity of the example was 121.56mAh/g, and the specific capacity of the example was 119.44 mAh/g. The discharge performance is compared in FIG. 8.
Claims (9)
1. The utility model provides a hierarchical structure cathode material for lithium ion battery which characterized in that: the chemical formula of the anode material with the hierarchical structure is LiNixCoyAl1-x-yOzCl2-z(ii) a X is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.9, and z is more than or equal to 1.5 and less than or equal to 1.95; the micro-morphology of the anode material with the hierarchical structure comprises a primary structure and a secondary structure; the primary structure is a layered structure, and the secondary structure is a spherical structure; the layered structure is a nano sheet; the spherical structure is a micron sphere;
the preparation method of the hierarchical structure cathode material for the lithium ion battery comprises the following steps:
(1) mixing water: putting lithium salt, nickel salt, cobalt salt and aluminum salt into a stirrer, adding water, and stirring until the solution is clear to obtain an aqueous solution for later use;
(2) molten salt mixing: heating LiCl to a molten state to obtain a clear liquid A; secondly, placing the aqueous solution obtained in the step (1) in an air-blast drying oven at the temperature of 80-180 ℃ for heating for 2-24 h to obtain molten liquid B, taking out the molten liquid B and placing the molten liquid B in a drying environment for later use; thirdly, injecting the clear liquid A into the molten liquid B, and then placing the clear liquid A in an air-blast drying oven at 160-200 ℃ for heating for 1-4 h to obtain a precursor molten liquid C;
(3) and (3) sintering: putting the precursor molten liquid C obtained in the step (2) into a sintering furnace, heating to 750-950 ℃ in an aerobic environment, carrying out heat preservation treatment for 8-16 h, and cooling to obtain a solid of the anode material with the hierarchical structure;
(4) crushing: and (4) crushing and sieving the solid of the anode material with the hierarchical structure obtained in the step (3) to obtain the anode material with the hierarchical structure.
2. The lithium ion battery-use hierarchical structure positive electrode material according to claim 1, characterized in that: the micro-morphology is a microsphere formed by stacking at least 10 single-layer nanosheets.
3. The lithium ion battery-use hierarchical structure positive electrode material according to claim 1, characterized in that: the single-layer thickness of the nano sheet is 30 nm-180 nm.
4. The lithium ion battery-use hierarchical structure positive electrode material according to claim 1, characterized in that: in the step of mixing the molten salt, the heating temperature of LiCl is 620-700 ℃.
5. The lithium ion battery-use hierarchical structure positive electrode material according to claim 1, characterized in that: in the step III of mixing the molten salt, the humidity of the drying environment is less than or equal to 3%.
6. The lithium ion battery-use hierarchical structure positive electrode material according to claim 1, characterized in that: the product obtained in the water mixing step is water, lithium salt, nickel salt, cobalt salt and aluminum salt, wherein the mass ratio of water to solid is 3-10: 1 stirring to obtain the product.
7. The positive electrode material of claim 1, wherein the positive electrode material has a hierarchical structure, and the hierarchical structure is characterized in that: the stirring speed of the product obtained in the water mixing step is 80 r/min-600 r/min.
8. The lithium ion battery-use hierarchical structure positive electrode material according to claim 1, characterized in that: the lithium salt is lithium nitrate; the nickel salt is any one or a combination of nickel nitrate and nickel nitrate hexahydrate; the cobalt salt is any one or a combination of more of cobalt nitrate and cobalt nitrate hexahydrate; the aluminum salt is any one or a combination of more of aluminum nitrate and aluminum nitrate nonahydrate.
9. Use of the hierarchical positive electrode material for lithium ion batteries according to any of claims 1 to 3 in lithium ion batteries.
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