CN112652771B - Polyanion-doped single-crystal high-nickel positive electrode material and preparation method thereof - Google Patents
Polyanion-doped single-crystal high-nickel positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyanion-doped single-crystal high-nickel anode material and a preparation method thereof, and the polyanion-doped single-crystal high-nickel anode material comprises the following steps: s1, uniformly mixing the anion A, the lithium salt and the high-nickel single crystal ternary precursor in absolute ethyl alcohol to obtain a first mixture; s2, calcining the first mixture in a tube furnace to obtain a monoanionic doped single-crystal high-nickel anode material; and S3, respectively placing the anions B and the single-crystal high-nickel anode material obtained in the S2 into a tube furnace for gas phase doping to obtain the cathode material. According to the invention, a precursor doped with one kind of anions is calcined to obtain a single-anion-doped single-crystal high-nickel ternary cathode material, and then another kind of anions and the obtained single-anion-doped high-nickel single-crystal ternary cathode material are subjected to gas phase doping, so that the polyanion-doped high-nickel single-crystal cathode material is successfully obtained, the defect that the conventional method cannot effectively realize polyanion doping is overcome, the doping effect is excellent, and the rate capability of the single-crystal high-nickel ternary material is successfully improved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a polyanion-doped single crystal high-nickel anode material and a preparation method thereof.
Background
With the continuous development of society, traditional energy sources such as coal, petroleum, natural gas and the like are less and less, but the demand for energy sources is higher and higher in the current times. Therefore, the search for new green alternative energy has become an essential issue in the modern times. At present, new energy sources are available, such as: solar energy, wind energy, tidal energy, geothermal energy and the like depend on the influence of natural environment to a great extent, and have the characteristic of decentralization, so that a specific energy storage device is required for storing and converting energy. The lithium ion battery is used as an energy storage device, can realize free replacement between chemical energy and electric energy, has the characteristics of no public hazard, no memory effect and the like, and is a green and environment-friendly secondary battery.
Nickel-cobalt-manganese ternary material LiNixCoyMn1-x-yO2The lithium ion battery is a very common cathode material due to high energy density and low cost. With the rapid development of electric automobiles, the requirement on the energy density of the anode material is higher and higher, and the method for improving the content of the nickel element in the ternary material is the most direct and effective method. The higher the Ni content, the Li is inserted and extracted from the material under the same cut-off voltage+The more the ternary material is, the higher the charge-discharge specific capacity is. However, when the Ni content is more than 80%, secondary particle breakage is more likely to occur during charge and discharge, and the electrolyte enters into the particlesThe nickel-containing ternary material reacts with the nickel-containing ternary material to generate phase change, so that the structural stability and the cycle performance of the high-nickel ternary material are reduced, and the failure of the material is accelerated.
Because the single crystal high-nickel anode material has no crystal boundary in secondary particles, the generation of intergranular cracks can be well avoided, the side reaction of electrolyte and the anode material in the circulating process is prevented, and the structural stability and the circulating performance of the high-nickel ternary material are greatly improved. However, the grain size of the single crystal high nickel ternary material is usually about 2-5 μm, the grain size of the primary grain of the polycrystalline high nickel ternary material is usually about 200nm, and the grain size of the single crystal high nickel ternary material is much larger than that of the primary grain of the polycrystalline material, so Li+The transmission path in the single-crystal high-nickel ternary material is longer, so that the rate capability of the single-crystal high-nickel ternary positive electrode material is poorer.
The crystal structure of the NCM ternary material belongs to a layered structure of a hexagonal system, transition metal ions (Ni, Co and Mn) and Li are respectively positioned in the center of an oxygen octahedron, and TM layers and Li layers are alternately arranged in a TM-O-Li form in the c-axis direction. During charging and discharging, Li+The route of extraction or insertion from the Li layer is from the Li-O octahedral center to the intermediate tetrahedral sites to the adjacent Li-O octahedral center. In view of the particle structure characteristics of the NCM ternary material, the distance between the lithium layer and the oxygen layer can be increased by reducing the interaction force between the lithium layer and the oxygen layer by an anion doping method, and Li is reduced+A migration barrier of (2), accelerating Li+The transmission of (2) and the improvement of the rate capability of the single crystal high nickel ternary material.
For the ion doping method, the existing method mostly realizes anion doping by adding AB type substance, for example, patent CN110233250A discloses a high energy density single crystal particle ternary positive electrode material and its preparation method, which is roughly: and mixing a certain amount of lithium source, a ternary precursor and an AB type solid additive, wherein A is a cation and B is an anion, and sintering in a segmented manner after mixing to finally obtain the single crystal particle ternary cathode material doped with the cation A and the anion B. The introduction of the AB type solid additive is beneficial to enlarging primary particles, so that the tap density and the discharge capacity of the cathode material are higher. Chinese patent CN109279662A discloses a method for preparing a double-ion co-doped single crystal ternary lithium ion positive electrode material, which is approximately: adding a mixed salt solution of doped ions A, B, nickel, cobalt and manganese into a mixed alkali solution, stirring, filtering, washing and drying to obtain a precursor (hydroxide precursor) of the ternary cathode material, and blending and sintering the precursor of the ternary cathode material and lithium salt to obtain the double-ion co-doped single crystal ternary lithium ion cathode material. Wherein, the doping ion A is lanthanum, cerium, zirconium, tantalum or tungsten, and the doping ion B is aluminum, titanium, magnesium or calcium.
The positive ion doping is different from the negative ion doping, the positive ion doping is used for stabilizing the structure of the positive electrode material so as to improve the electrochemical performance of the material and improve the cycle performance of the material, the negative ion doping is used for replacing O in the positive electrode material, and the interaction force between the lithium layer and the oxygen layer is reduced to increase the distance between the lithium layer and the oxygen layer and accelerate Li (lithium) layer to increase the distance between the lithium layer and the oxygen layer while stabilizing the structure of the material+The transmission of (2) and the improvement of the rate capability of the single crystal high nickel ternary material. The mixed doping of the anions and the cations can weaken Jahn-Teller effect of the material and disproportionation and dissolution of Mn by means of cation doping, and the reversible capacity of the electrode can be improved by means of anion doping. The mixed doping can inhibit the Jahn-Teller effect and Mn dissolution of the material on the basis of ensuring that the material has higher lithium intercalation and deintercalation capacities, and improve the high-temperature cycle performance of the electrode.
However, for doping only with anions, the action mechanism of the single anion doping is single, and in most cases, the performance of one aspect of the positive electrode material can be improved, and even the performance of the other aspect is reduced while the performance of one aspect is improved. To this end, some researchers have tried polyanionic doping to overcome the drawbacks associated with monoanionic doping, using coupling between different ions to modify, for example: the binding force of some anions and lithium ions is weak, and the binding force of some anions and lithium ions can be reduced, so that the lithium ions can be rapidly de-intercalated, and the binding force of some anions and transition metal ions is strong, so that the lithium layer spacing can be increased, and the lithium ion migration channel can be widened. Theoretically, the common effect of multiple anions can achieve better rate improving effect, and can simultaneously ensure that other properties are not reduced. However, in practical studies, it was found that when the polyanion is doped, the doping amount of the anion is trace, and the final doping result is: only one kind of doping anion exists in the oxygen layer, and the obtained positive electrode material structure is also doped by single anion, so that the effective multi-anion doping cannot be carried out.
Disclosure of Invention
The invention aims to: in order to solve the existing problems, the invention provides a polyanion-doped single-crystal high-nickel anode material and a preparation method thereof.
The technical scheme adopted by the invention is as follows: a method for doping a single crystal high nickel anode material by polyanion is characterized by comprising the following steps:
s1, weighing a certain mass of simple substance, compound or organic matter containing the anion A, uniformly mixing the simple substance, the compound or the organic matter with lithium salt and the high-nickel single crystal ternary precursor in absolute ethyl alcohol, grinding for a certain time, and obtaining a first mixture after the absolute ethyl alcohol is completely volatilized;
s2, calcining the first mixture in a tube furnace to obtain a monoanionic doped single-crystal high-nickel anode material;
s3, weighing a certain mass of simple substance, compound or organic matter containing the anion B, and respectively placing the simple substance, compound or organic matter and the single crystal high nickel anode material obtained in S2 in a tube furnace for gas phase doping to obtain a polyanion-doped single crystal high nickel anode material; the anion A and the anion B are different, and the decomposition temperature of the simple substance, the compound or the organic matter containing the anion A is higher than that of the simple substance, the compound or the organic matter containing the anion B.
In the preparation method of the present invention, through long-term experimental studies by the inventors, it was found that the main reason of the doping failure when polyanion doping is performed is: there are many kinds of substances containing different anions A and B, and the decomposition temperatures of different substances are different, and at the same calcination temperature, due to the different decomposition temperatures, one kind of anion is often uniformly diffused while the other anion is volatilized, thereby causing the doping failure of multiple anions. Therefore, in order to overcome the problem, the invention firstly selects a simple substance, a compound or an organic substance which is not easy to decompose (or has relatively high decomposition temperature) and contains the anion A, firstly mixes the simple substance, the compound or the organic substance with the lithium salt and the high-nickel single crystal ternary precursor, then calcines the mixture at high temperature to obtain a single-anion-doped single crystal high-nickel anode material, and then introduces the simple substance, the compound or the organic substance containing the anion B in a gas phase doping manner to finally realize the doping of the anion A and the anion B. Compared with the traditional method of mixing the anion A and the anion B at the same time, the doping method has the main technical advantages that:
1. according to the invention, the anion A with higher decomposition temperature is doped at high temperature, and then the anion B with lower decomposition temperature is doped in a gas phase doping manner, so that the uniform doping of the anion A and the anion B is realized, the effect of simultaneously doping various ions is further achieved, the volatilization of the anion with lower decomposition temperature is avoided, the defect that the conventional manner cannot effectively realize the doping of multiple anions is overcome, the doping effect is excellent, and the multiplying power performance of the single-crystal high-nickel ternary material is successfully improved;
2. according to the invention, through gas phase doping, a dopant (namely, anion B with lower decomposition temperature) and an obtained single crystal high nickel anode material are respectively placed in a tube furnace, and the dopant is placed in an upper air inlet of the anode material, the dopant is changed into gas at high temperature, and is pushed by gas flow of nitrogen or argon and the like to realize gas phase doping with the anode material, and the structure of the anode material obtained by the method is different from that of the anode material formed by traditional polyanion doping; in the structure of the polyanion-doped single-crystal high-nickel anode material, the form is single-crystal particles, doped anions A and doped anions B appear in an oxygen layer, the doped anions are uniformly distributed, the original structure of the material is not changed by anion doping, the structure is stable, and the polyanion-doped single-crystal high-nickel anode material is successfully obtained.
In the present invention, the absolute ethyl alcohol is used to make the simple substance or compound containing the anion a or the organic substance, the lithium salt and the precursor in a liquid phase environment to achieve more uniform mixing, and is removed by volatilization at the later stage.
Further, the anion A is F-、Cl-、S2-One or more of (a).
Further, the anion B is F-、Cl-、S2-One or more of (a).
Further, the molar ratio of the anion A to the lithium salt to the high-nickel single crystal ternary precursor is (0.1-2): (105-120): 100. the specific proportion is obtained by adjusting according to actual requirements.
Furthermore, the addition amount of the anion B is 0.1-2% of the mass of the single anion doped single crystal high nickel cathode material obtained from S2. The specific proportion is obtained by adjusting according to actual requirements.
Preferably, the high-nickel single crystal ternary precursor is Ni0.8Co0.1Mn0.1(OH)2The single crystal high nickel anode material is Li (Ni)0.8Co0.1Mn0.1)O2。
Further, when the first mixture is calcined, calcining is carried out in an oxygen atmosphere, the heating rate is controlled to be 5 ℃/min and heated to 550 ℃, the temperature is kept for 5h, the heating rate is controlled to be 2 ℃/min and heated to be 700-1000 ℃, and the temperature is kept for 16-30h to obtain the monoanionic doped single crystal high nickel anode material.
Further, in S3, the calcination conditions were: the temperature is controlled to be between 250 ℃ and 600 ℃ in the inert gas atmosphere for heat treatment for 2 to 8 hours.
The invention also discloses a single-crystal high-nickel anode material which is prepared by the method. According to the single crystal high nickel anode material obtained by the invention, doping anions A and B exist in the oxygen layer to dope anions, so that a multi-anion doped single crystal high nickel anode material is obtained, the defects of single anion doping are overcome by multi-anion doping, the interaction force of the lithium layer and the oxygen layer is obviously reduced, the distance between the lithium layer and the oxygen layer is increased, and Li is enabled to be doped into the single crystal high nickel anode material+Is easier to be embedded and separated, thereby improving the rate capability of the single crystal high nickel ternary material.
The invention also comprises a lithium ion battery, wherein the anode material of the lithium ion battery is prepared from the single-crystal high-nickel anode material.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the invention, the anion A with higher decomposition temperature is doped at high temperature, and then the anion B with lower decomposition temperature is doped in a gas phase doping manner, so that the uniform doping of the anion A and the anion B is realized, the effect of simultaneously doping various ions is further achieved, the volatilization of the anion with lower decomposition temperature is avoided, the defect that the conventional manner cannot effectively realize the doping of multiple anions is overcome, the doping effect is excellent, and the multiplying power performance of the single-crystal high-nickel ternary material is successfully improved;
2. according to the invention, a single anion-doped single crystal high nickel ternary positive electrode material is obtained by calcining one kind of doped anion, lithium salt and single crystal high nickel ternary material precursor, and then the other kind of anion and the obtained single anion-doped high nickel single crystal ternary positive electrode material are respectively placed in the same tube furnace for gas phase doping, so that a polyanion-doped high nickel single crystal positive electrode material with uniform ion distribution is successfully obtained, the defects of the traditional doping mode are overcome, through polyanion doping, advantage complementation is realized by utilizing the coupling effect between different ions, the interaction force between a lithium layer and an oxygen layer is reduced, the distance between the lithium layer and the oxygen layer is increased, and the multiplying power performance of the single crystal high nickel ternary material is successfully improved.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) picture of an end product prepared in example 1 of the present invention;
FIG. 2 is a graph showing the change of specific discharge capacity of a battery assembled by the final product prepared in example 1 of the present invention and an unmodified material (comparative example) under different rates under a cut-off voltage of 2.8-4.3V under a cycle of 45 cycles;
fig. 3 is a graph showing the change of specific discharge capacity of 45 cycles at different rates in the range of 2.8 to 4.3V for the cut-off voltage of the battery assembled with the final product prepared in example 2 according to the present invention and the modified material (comparative example).
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Additionally, the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the following examples 1-4, the following material characterization analysis methods were used:
scanning Electron Microscope (SEM) testing: scanning electron microscope, instrument model: FEI Quanta, the netherlands.
Assembly and testing of CR2025 button cells: preparing NCM ternary cathode material (final product prepared in example), acetylene black and polyvinylidene fluoride (PVDF) into slurry according to the mass ratio of 8:1:1, and coating the slurry on an aluminum foilCutting the dried aluminum foil loaded with the slurry into small round pieces with the diameter of about 1cm by a cutting machine to be used as a positive electrode, taking a metal lithium piece as a negative electrode, taking Celgard2500 as a diaphragm, taking 1M carbonate solution as electrolyte (wherein, the solvent is mixed solution of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate with the volume ratio of 1:1:1, and the solute is LiPF6) And assembling the button cell CR2025 in an argon atmosphere glove box.
Comparative example
A single crystal high nickel ternary positive electrode material precursor is prepared by a hydroxide coprecipitation method, and comprises the following steps:
s1, mixing NiSO4·6H2O solid, CoSO4·7H2O solid, MnSO4·H2210.28g, 28.11g and 16.9g of O solid are weighed according to the molar ratio of Ni to Co to Mn to 8 to 1, and three sulfates are added into 500mL of deionized water to be dissolved to form the metal ion with the total concentration of 2 mol.L-1A metal salt solution of (a);
s2, weighing 100g of sodium hydroxide, adding 500mL of deionized water to prepare 2 mol. L-1The NaOH solution is prepared by measuring 50mL of 30 mass percent ammonia water solution and adding deionized water to prepare 2 mol.L-1The aqueous ammonia solution of (1);
s3, adding 1000mL of deionized water into a reaction kettle to serve as a coprecipitation reaction base solution, wherein stirring and water bath processes are required in the whole reaction stage, the water bath temperature is controlled to be about 55 ℃, the stirring speed is stabilized at 800r/min, argon protective gas is introduced before the reaction starts to ensure that the whole reaction is carried out in argon atmosphere, adding 30% ammonia water solution to control pH of the base solution to 11, pumping the metal salt solution, NaOH solution and ammonia water solution into a reaction kettle by a peristaltic pump, controlling the feeding speed of the metal salt solution and the ammonia water solution at 1mL/min, adjusting the feeding speed of the NaOH solution to stabilize the pH value of the reaction at 11, entering an aging stage after the feeding is finished, keeping the original temperature and the original rotating speed, continuously stirring for 2 hours, filtering and washing while the solution is hot after the aging is finished, then the precipitate is put into a vacuum drying oven with the temperature of 80 ℃ for drying for 24 hours, and finally the single crystal Ni is obtained.0.8Co0.1Mn0.1(OH)2And (3) precursor.
Will 10g of single-crystal Ni0.8Co0.1Mn0.1(OH)2Precursor and 4.998g LiOH H2Mixing O, placing the mixture into a tube, calcining the mixture in an oxygen atmosphere, controlling the heating rate to be 5 ℃/min, heating to 580 ℃, preserving heat for 8 hours, controlling the heating rate to be 2 ℃/min, heating to 700 ℃, preserving heat for 8 hours, and cooling the calcined material to obtain the single crystal high-nickel ternary cathode material (LiNi)0.8Co0.1Mn0.1O2)。
Example 1
A method for doping a single crystal high nickel anode material by polyanion is characterized by comprising the following steps:
s1, weighing 10g of single crystal Ni0.8Co0.1Mn0.1(OH)2Precursor, 4.998g LiOH. H2Uniformly mixing O and 0.15g LiCl by using absolute ethyl alcohol, grinding the mixture by using a mortar for 30min, and obtaining a first mixture after the absolute ethyl alcohol is completely volatilized;
s2, placing the first mixture in a tube furnace, calcining in an oxygen atmosphere, controlling the heating rate to be 5 ℃/min, heating to 580 ℃, preserving heat for 8h, then controlling the heating rate to be 2 ℃/min, heating to 700 ℃, preserving heat for 8h, cooling the calcined material to obtain the material doped with Cl-The single crystal high nickel ternary material of (2);
s3, weighing 0.15g of simple substance S and Cl doping obtained by S2-Respectively placing 10g of the single-crystal high-nickel ternary material in the same tube furnace, placing a monomer S in an upper air inlet of the single-crystal high-nickel ternary material, and treating for 2 hours at 250 ℃ in Ar atmosphere to obtain the polyanion-doped single-crystal high-nickel ternary cathode material.
The scanning electron microscope result of the final product is shown in fig. 1, and it can be seen from the figure that the final product is single crystal particles, the surface is relatively uniform, and the structure is stable.
The result of the charge-discharge cycle test of the final product under different multiplying factors is shown in figure 2, and the cut-off voltage of the assembled battery is 2.8-4.3V. The rate capability of the material is obviously increased after the polyanion is doped, which shows that the polyanion-doped single-crystal high-nickel cathode material is beneficial to reducing the voltage between the lithium layer and the oxygen layerActing force accelerates Li+The transmission of (2) improves the rate capability of the material.
Example 2
A method for doping a single crystal high nickel anode material by polyanion is characterized by comprising the following steps:
s1, weighing 10g of single crystal Ni0.8Co0.1Mn0.1(OH)2Precursor, 4.998g LiOH. H2O and 0.2g NH4Uniformly mixing the three materials by using absolute ethyl alcohol, grinding the mixture in a mortar for 30min, and obtaining a first mixture after the absolute ethyl alcohol is completely volatilized;
s2, placing the first mixture in a tube furnace, calcining in an oxygen atmosphere, controlling the heating rate to be 5 ℃/min, heating to 580 ℃, preserving heat for 15h, then controlling the heating rate to be 2 ℃/min, heating to 1000 ℃, preserving heat for 15h, cooling the calcined material to obtain the doped F-The single crystal high nickel ternary material of (2);
s3, weighing 0.15g thioacetamide and F doped crystal obtained from S2-Respectively placing 10g of the single-crystal high-nickel ternary material in the same tube furnace, placing a monomer S in an upper air inlet of the single-crystal high-nickel ternary material, and treating for 8 hours at 600 ℃ in Ar atmosphere to obtain the polyanion-doped single-crystal high-nickel ternary positive electrode material.
The result of the charge-discharge cycle test of the final product under different multiplying factors is shown in figure 3, and the cut-off voltage of the assembled battery is 2.8-4.3V. The rate capability of the material after doping polyanion is obviously improved, which shows that the polyanion-doped single crystal high nickel anode material is helpful to reduce the acting force between the lithium layer and the oxygen layer and quickens the Li+The transmission of (2) improves the rate capability of the material.
Example 3
A method for doping a single crystal high nickel anode material by polyanion is characterized by comprising the following steps:
s1, weighing 10g of single crystal Ni0.8Co0.1Mn0.1(OH)2Precursor, 4.998g LiOH. H2O and 0.1g KCl, uniformly mixing the three with absolute ethyl alcohol, and grinding the mixture with a mortar for 30min, obtaining a first mixture after absolute ethyl alcohol is completely volatilized;
s2, placing the first mixture in a tube furnace, calcining in an oxygen atmosphere, controlling the heating rate to be 5 ℃/min, heating to 580 ℃, preserving heat for 10h, then controlling the heating rate to be 2 ℃/min, heating to 800 ℃, preserving heat for 10h, cooling the calcined material to obtain the material doped with Cl-The single crystal high nickel ternary material of (2);
s3, weighing 0.15g LiF and Cl doping obtained from S2-Respectively placing 10g of the single-crystal high-nickel ternary material in the same tube furnace, placing a monomer S in an upper air inlet of the single-crystal high-nickel ternary material, and treating for 4 hours at 400 ℃ in Ar atmosphere to obtain the polyanion-doped single-crystal high-nickel ternary cathode material.
Example 4
A method for doping a single crystal high nickel anode material by polyanion is characterized by comprising the following steps:
s1, weighing 10g of single crystal Ni0.8Co0.1Mn0.1(OH)2Precursor, 4.998g LiOH. H2Uniformly mixing the O and the 0.2g of sulfur powder by using absolute ethyl alcohol, grinding the mixture by using a mortar for 30min, and obtaining a first mixture after the absolute ethyl alcohol is completely volatilized;
s2, placing the first mixture in a tube furnace, calcining in an oxygen atmosphere, controlling the heating rate to be 5 ℃/min, heating to 580 ℃, preserving heat for 12h, then controlling the heating rate to be 2 ℃/min, heating to 800 ℃, preserving heat for 12h, cooling the calcined material to obtain the material doped with S2-The single crystal high nickel ternary material of (2);
s3, weighing 0.15g NH4Cl and S2 doped with S2-Respectively placing 10g of the single-crystal high-nickel ternary material in the same tube furnace, placing a monomer S in an upper air inlet of the single-crystal high-nickel ternary material, and treating for 6 hours at 500 ℃ in Ar atmosphere to obtain the polyanion-doped single-crystal high-nickel ternary cathode material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A method for doping a single crystal high nickel anode material by polyanion is characterized by comprising the following steps:
s1, weighing a certain mass of substance containing the element A, uniformly mixing the substance with lithium salt and the high-nickel single crystal ternary precursor in absolute ethyl alcohol, grinding for a certain time, and obtaining a first mixture after the absolute ethyl alcohol is completely volatilized; the substance containing the element A is selected from one or more of a compound of F, a compound of Cl, a simple substance or a compound of S;
s2, placing the first mixture in a tube furnace, calcining in an oxygen atmosphere, controlling the heating rate to be 5 ℃/min and heating to 550 ℃, keeping the temperature for 5h, controlling the heating rate to be 2 ℃/min and heating to be 700-minus-one 1000 ℃, and keeping the temperature for 16-30h to obtain the monoanionic doped single-crystal high-nickel anode material;
s3, weighing a certain mass of substance containing B element, and respectively placing the substance and the single crystal high nickel anode material obtained in S2 in a tube furnace for gas phase doping, wherein the calcining conditions are as follows: controlling the temperature in an inert gas atmosphere at 250-600 ℃ for heat treatment for 2-8h to obtain a polyanion-doped single crystal high nickel anode material; wherein the substance containing the B element is selected from one or more of a compound of F, a compound of Cl, a simple substance or a compound of S, and the A element and the B element are different.
2. The method of polyanionic-doped single-crystal high-nickel cathode material according to claim 1, wherein the molar ratio of the substance containing the element a, the lithium salt, and the ternary precursor of the high-nickel single crystal is (0.1-2): (105-120): 100.
3. the method according to claim 2, wherein the amount of the substance containing B element is 0.1-2% by mass of the monoanionic-doped single-crystal high nickel positive electrode material obtained in S2.
4. The method of claim 1, wherein the high nickel single crystal ternary precursor is Ni0.8Co0.1Mn0.1(OH)2The single crystal high nickel anode material is LiNi0.8Co0.1Mn0.1O2。
5. A polyanion-doped single-crystal high-nickel cathode material, which is prepared by the method of any one of the above claims 1 to 4.
6. A lithium ion battery comprises a positive electrode material, and is characterized in that the positive electrode material of the lithium ion battery is the polyanion-doped single-crystal high-nickel positive electrode material in claim 5.
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