CN114477314A - A kind of preparation method and application of nickel-cobalt-manganese ternary positive electrode material - Google Patents

Abstract

The invention relates to the technical field of preparation of battery anode materials, and particularly discloses a preparation method and application of a nickel-cobalt-manganese ternary anode material. The method comprises the following steps: (1) adding a precipitator into the solution containing nickel ions, cobalt ions and manganese ions to obtain reaction mother liquor. (2) Carrying out hydrothermal reaction on the reaction mother liquor, and separating out a solid product after the hydrothermal reaction is finished to obtain a precursor material Ni_xCo_yMn_(1‑x‑y)(HO)₂Wherein x is more than or equal to 0.6 and less than or equal to 0.9, and y is more than or equal to 0.05 and less than or equal to 0.2. (3) Subjecting the precursor material and a lithium source to different temperature stages under an oxygen atmosphereAnd (4) carrying out sectional calcination to obtain the nickel-cobalt-manganese ternary cathode material (NCM). According to the invention, a novel ternary material preparation process is constructed by utilizing the intrinsic structure of a specific material, the better ion diffusion channel can well inhibit the cation mixed-arrangement effect, the lithium-nickel mixed-arrangement effect of the ternary material is reduced, and the rate capability of the ternary material is effectively improved.

Description

A kind of preparation method and application of nickel-cobalt-manganese ternary positive electrode material

technical field

The invention relates to the technical field of preparation of battery cathode materials, in particular to a preparation method and application of a nickel-cobalt-manganese ternary cathode material.

Background technique

The disclosure of information in this Background section is for enhancement of understanding of the general background of the invention and should not necessarily be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.

The cathode material is the main limiting factor for the electrochemical performance of lithium batteries, and its material properties directly determine the energy density, service life and safety of the battery, which in turn affects the overall performance of the battery. At the same time, since the cathode material accounts for 30~40% of the cost of lithium battery materials, its cost also directly determines the overall cost of the battery. Therefore, the cathode material plays a pivotal role in lithium batteries and directly leads the lithium battery. The development trend and trend of the battery industry.

The current mainstream commercial lithium-ion battery cathode materials include lithium iron phosphate, lithium manganate and nickel-cobalt-manganese ternary cathode materials. Among them, the good high and low temperature performance, high energy density and excellent cycle performance of ternary cathode materials occupy the dominant position of cathode materials, and research in the fields of high nickel and high voltage leads the technological change. With the improvement of the cruising range standard for new energy vehicles, traditional lithium iron phosphate power batteries have gradually given way to ternary cathode material batteries.

The expensive price of cobalt in ternary materials will increase the cost of batteries, and low-cobalt and high-nickel materials are the mainstream direction. However, with the increase of nickel content and the decrease of cobalt content, the problem of poor cycle stability of materials has become the biggest problem. Seriously The cation mix-up phenomenon can lead to a sharp deterioration of the thermal and structural stability of the material, and the accumulation of irreversible phase transitions, resulting in defects such as low initial charge-discharge efficiency and low cycle life. The reduction of the intrinsic conductivity, stability and service life of the material caused by this cation mixing effect has become a difficulty that must be solved for the current ternary cathode materials to enter the market.

Despite the support of clear market demand, ternary cathode materials have serious cation mixing effect, irreversible phase transition and material microcracks during cycling, which lead to the rate performance and cycle stability of ternary materials. Decline. In addition, due to the high prices of lithium and cobalt, the price of cobalt has been unstable in recent years, and the amplitude of surge and decline can reach 200%.

SUMMARY OF THE INVENTION

In view of the above problems, the present invention provides a preparation method and application of a nickel-cobalt-manganese ternary positive electrode material. The present invention constructs a new ternary material preparation process by utilizing the intrinsic structure of the specific material, and better ion diffusion channels can well suppress the cation mixing effect, reduce the lithium nickel mixing effect of the ternary material, thereby effectively improving the The rate performance of the ternary material. In order to achieve the above objects, the present invention discloses the following technical solutions.

In a first aspect of the present invention, a method for preparing a nickel-cobalt-manganese ternary positive electrode material is disclosed, comprising the following steps:

(1) Add a precipitant to the solution containing nickel ions, cobalt ions and manganese ions to obtain a reaction mother liquor.

(2) The reaction mother liquor is subjected to hydrothermal reaction, and after completion, the solid product is separated to obtain the precursor material Ni _x Co _y Mn _(1-xy) (HO) ₂ , wherein 0.6≤x≤0.9, 0.05≤y ≤0.2.

(3) The precursor material and the lithium source are calcined in stages at different temperature stages in an oxygen atmosphere, and after completion, a nickel-cobalt-manganese ternary cathode material (NCM) is obtained.

Further, in step (1), the nickel ions are provided by at least one of nickel nitrate, nickel acetate, nickel carbonate, nickel hydroxide and the like. The cobalt ions are provided by at least one of cobalt nitrate, cobalt acetate, cobalt carbonate, cobalt hydroxide and the like. The manganese ions are provided by at least one of manganese nitrate, manganese acetate, manganese carbonate, manganese hydroxide and the like.

Further, in step (1), the ratios of the nickel ions, cobalt ions, and manganese ions are configured according to the atomic number ratio of each metal element in the precursor material in step (2).

Further, in step (1), the precipitating agent includes any one of urea, ammonia water, ammonium fluoride and the like. Optionally, the molar ratio of the precipitant to metal ions ranges from 1:1 to 1:2, and the metal ions refer to the sum of nickel ions, cobalt ions, and manganese ions. In the present invention, the functions of the precipitating agent include promoting the co-deposition of transition metal ions and adjusting the pH value of the solution to an alkaline range.

Further, in step (1), the solution is a mixed solution formed by ethanol and water. Optionally, the volume ratio of ethanol and water ranges from 1:3 to 1:4.

Further, in step (2), the temperature of the hydrothermal reaction is 150-200° C., and the reaction time is 5-15 h. During the hydrothermal reaction, the nickel ions, cobalt ions, and manganese ions form α-type nickel-cobalt-manganese trimetallic hydroxide, that is, the precursor material Ni _x Co _y Mn _(1-xy) (HO ) ₂ , this precursor material has a large interlayer spacing and can be retained in the final cathode material, effectively improving the structural stability and electrochemical performance of the cathode material.

Further, in step (3), the molar ratio of the precursor material and the lithium source is 1:1.02~1:1.05. Optionally, the lithium source includes at least one of lithium hydroxide solid, lithium acetate solid, lithium nitrate solid, lithium carbonate solid, and the like.

Further, in step (3), the precursor material and the lithium source are uniformly mixed by ball milling or liquid phase dispersion, and then the segmented calcination is performed. During the calcination process, the oxidized precursor particles react with the lithium source to form primary particles, and the further agglomeration of the primary particles forms secondary particles, that is, the positive electrode material. The ion diffusion channel that retains the precursor of the secondary particle structure provides a strong support for the improvement of the rate performance of the cathode material.

Further, in step (3), the segmented calcination includes: first calcining at 350-450°C for 150-200min, then heating up to 700-850°C and continuing to calcine for 1100-1300min, wherein the precursor is heated at 300-500°C for 1100-1300min. Pre-sintering is beneficial to the synthesis of well-ordered layered NCM cathode materials, and high temperature calcination at 700~900 °C determines the Li ⁺ /Ni ²⁺ mixing degree and crystal structure integrity of the synthesized NCM cathode materials. .

In the second aspect of the present invention, the application of the nickel-cobalt-manganese ternary cathode material for lithium ion batteries prepared by the above method in energy storage devices is disclosed.

Compared with the prior art, the present invention has the following beneficial and unique effects:

(1) The nickel-cobalt-manganese ternary cathode material of the present invention has a secondary particle structure with larger ion transport channels, which effectively improves the rate performance of the ternary cathode material. This is because: by preparing α-type nickel-cobalt-manganese trimetallic hydroxide with large interlayer spacing (chemical formula Ni _x Co _y Mn _(1-xy) (HO) ₂ ) as a precursor, the petaloid layer The skeleton of ion transfer is constructed in the middle, and the nickel-cobalt-manganese ternary cathode material is obtained by mixing with lithium source at high temperature, so that the obtained ternary cathode material has a lower lithium-nickel mixing effect, and effectively alleviates low cobalt and high nickel. The cation mixing effect existing in the material improves the cycle life and conductivity of the material, so that the nickel-cobalt-manganese ternary cathode material prepared by the present invention has a higher rate performance while maintaining a higher capacity.

(2) The nickel-cobalt-manganese ternary cathode material prepared by the present invention builds the structure of ionic nickel-cobalt-manganese in different valence states inside the material lattice by segmented calcination, resulting in the increase of the valence state of transition metal ions in the final cathode material. High or low, holes or electrons are generated, the energy band structure of the material is changed, and the intrinsic electronic conductivity is improved. At the same time, the mixing degree of Li/Ni in the positive electrode material is reduced, which supports the crystal lattice, stabilizes the structure of the positive electrode material, and effectively improves the electrochemical cycle performance and thermal stability of the nickel-cobalt-manganese ternary positive electrode material prepared by the invention.

(3) The α-type nickel-cobalt-manganese trimetallic layered hydroxide obtained by design is used as a precursor. Since the precursor has a large interlayer spacing, it can accommodate more anions and water molecules in the large interlayer, making the precursor After being calcined at high temperature, the body can still retain the characteristics of its large interlayer spacing, which provides a channel for the migration of lithium ions in the electrode material during the charging and discharging process, improves the ion diffusion rate of the positive electrode material, and makes the nickel-cobalt-manganese ternary positive electrode material prepared by the present invention. The rate performance and cycle performance have been significantly improved, greatly improving the practicability of cathode materials. The test results show that the nickel-cobalt-manganese ternary cathode material prepared in the embodiment of the present invention has stable structure, excellent cycle performance, high thermal stability and rate performance, and stable low rate performance after high current charge and discharge.

Description of drawings

The accompanying drawings forming a part of the present invention are used to provide further understanding of the present invention, and the exemplary embodiments of the present invention and their descriptions are used to explain the present invention, and do not constitute an improper limitation of the present invention. Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, wherein:

FIG. 1 is an SEM image of the α-type nickel-cobalt-manganese layered hydroxide synthesized in the following first example.

FIG. 2 is a SEM image of the nickel-cobalt-manganese cathode material synthesized in the following first example.

FIG. 3 is a test chart of the cycle performance of the nickel-cobalt-manganese cathode materials synthesized in the following first and second examples under different current densities.

specific embodiment

The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In the following examples, the experimental methods without specific conditions are usually in accordance with conventional conditions or in accordance with the conditions suggested by the manufacturer.

Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. The reagents or raw materials used in the present invention can be purchased through conventional channels. Unless otherwise specified, the reagents or raw materials used in the present invention are used in a conventional manner in the art or in accordance with product instructions. In addition, any methods and materials similar or equivalent to those described can be used in the methods of the present invention. The methods and materials described in this disclosure are for illustrative purposes only. The present invention will now be further described with reference to the accompanying drawings and specific embodiments of the description.

first embodiment

A method for preparing a nickel-cobalt-manganese ternary positive electrode material, comprising the following steps:

(1) According to the molar ratio of nickel, cobalt and manganese ions of 6:2:2, weigh 0.4852 g of Ni(NO ₃ ) ₂ ·6H ₂ O crystal, and weigh out Co(NO ₃ ) ₂ ·6H ₂ O crystal 0.4852g, measure 0.5965g of Mn(NO ₃ ) ₂ solution with a mass fraction of 50%. The above three kinds of raw materials and 0.6 g of urea were added to a mixed solvent (48 ml of ethanol + 12 ml of water), and the crystals were completely dissolved by stirring to obtain a reaction mother liquor.

(2) Transfer the reaction mother liquor obtained in step (1) to the lining of the reactor, and react in a homogeneous reaction furnace at 180 °C for 480 min. After completion, use suction filtration and centrifugation to clean the solid product, and then The solid product was dried in a forced air oven at 70°C for 12h. The dried solid was ball-milled in a ball mill at 800 rpm for 8 hours, and the ground powder was passed through a 500-mesh sieve to obtain the precursor Ni ₆ Co ₂ Mn ₂ (HO) ₂ powder.

(3) Weigh 0.9635 g of the precursor powder and 0.4406 g of the lithium hydroxide monohydrate powder, and mix them evenly and fully by using absolute ethanol for liquid phase dispersion. After drying for 6 hours, the mixture is spread on a porcelain boat. Oxygen with a purity of 99.9% was introduced into the tube, first calcined at 450 °C for 180 min, then raised to 735 °C for 1200 min, and then naturally cooled to room temperature and taken out. The sintered nickel-cobalt-manganese ternary material was ball-milled in a ball mill for 24 hours and passed through an 800-mesh sieve to obtain a nickel-cobalt-manganese ternary cathode material powder (referred to as NCM622).

Second Embodiment

A method for preparing a nickel-cobalt-manganese ternary positive electrode material, comprising the following steps:

(1) According to the molar ratio of nickel, cobalt and manganese ions of 8:1:1, weigh 1.7400g of Ni(NO ₃ ) ₂ ·6H ₂ O crystal, and weigh out Co(NO ₃ ) ₂ ·6H ₂ O crystal 0.2177 g, 0.2627 g of Mn(NO ₃ ) ₂ solution with a mass fraction of 50% was measured. The above three kinds of raw materials and 0.6 g of urea were added to a mixed solvent (48 ml of ethanol + 12 ml of water), and the crystals were completely dissolved by stirring to obtain a reaction mother liquor.

(2) Transfer the reaction mother liquor obtained in step (1) to the lining of the reactor, and react in a homogeneous reaction furnace at 180 °C for 480 min. After completion, use suction filtration and centrifugation to clean the solid product, and then The solid product was dried in a forced air oven at 50°C for 24h. The dried solid was ball-milled in a ball mill at 800 rpm for 8 hours, and the ground powder was passed through a 500-mesh sieve to obtain the precursor Ni ₈ Co ₁ Mn ₁ (HO) ₂ powder.

(3) Weigh 1.0149 g of the precursor powder and 0.4406 g of the lithium hydroxide monohydrate powder, and mix them evenly and fully by using absolute ethanol for liquid phase dispersion. After drying for 6 hours, the mixture is spread on a porcelain boat. Oxygen with a purity of 99.9% was introduced into the tube, first calcined at 450 °C for 180 min, then raised to 735 °C for 1200 min, and then naturally cooled to room temperature and taken out. The sintered nickel-cobalt-manganese ternary material was ball-milled in a ball mill for 24 hours and passed through an 800-mesh sieve to obtain a nickel-cobalt-manganese ternary cathode material powder (referred to as NCM811).

Third Embodiment

A method for preparing a nickel-cobalt-manganese ternary positive electrode material, comprising the following steps:

(1) According to the molar ratio of nickel, cobalt and manganese ions of 9:0.5:0.5, weigh 1.7400g of Ni(NO ₃ ) ₂ ·6H ₂ O crystal, and weigh out Co(NO ₃ ) ₂ ·6H ₂ O crystal 0.0967g, measure 0.1190g of Mn(NO ₃ ) ₂ solution with a mass fraction of 50%. The above three kinds of raw materials and 0.6 g of urea were added to a mixed solvent (48 ml of ethanol + 12 ml of water), and the crystals were completely dissolved by stirring to obtain a reaction mother liquor.

(2) Transfer the reaction mother liquor obtained in step (1) to the lining of the reactor, and react in a homogeneous reaction furnace at 180 °C for 480 min. After completion, use suction filtration and centrifugation to clean the solid product, and then The solid product was dried in a forced air oven at 50 °C for 20 h. The dried solid was ball-milled in a ball mill at 800 rpm for 8 hours, and the ground powder was passed through a 500-mesh sieve to obtain the precursor Ni ₉ Co _0.5 Mn _0.5 (HO) ₂ powder.

(3) Weigh 1.1013 g of the precursor powder and 0.4406 g of the lithium hydroxide monohydrate powder, and mix them evenly and fully by using absolute ethanol for liquid phase dispersion. After drying for 6 hours, the mixture is spread on a porcelain boat. Oxygen with a purity of 99.9% was introduced into the tube, and the above-mentioned porcelain boat was placed in a muffle furnace, first calcined at 450 °C for 180 min, then raised to 735 °C for 1200 min, and then naturally cooled to room temperature and taken out. The sintered nickel-cobalt-manganese ternary material is ball-milled in a ball mill for 24 hours and then passed through an 800-mesh sieve to obtain nickel-cobalt-manganese ternary positive electrode material powder.

Fourth Embodiment

A method for preparing a nickel-cobalt-manganese ternary positive electrode material, comprising the following steps:

(1) According to the molar ratio of nickel, cobalt and manganese ions of 7:1:2, weigh Ni(CH ₃ COO) ₂ ·4H ₂ O crystal, and weigh Co(CH ₃ COO) ₂ ·4H ₂ O crystal , Measure the Mn(CH ₃ COO) ₂ ·4H ₂ O solution with a mass fraction of 50%. Add the above three raw materials and ammonium fluoride (the molar ratio of the ammonium fluoride to nickel, cobalt, and manganese ions is 1:2) into the mixed solvent (36ml ethanol+12ml water), and stir to completely dissolve the crystals , get the reaction mother liquor.

(2) Transfer the reaction mother liquor obtained in step (1) to the lining of the reactor, react in a homogeneous reaction furnace at 150 ° C for 900 min, use suction filtration and centrifugation to clean the solid product after completion, and then The solid product was dried in a forced air oven at 50 °C for 20 h. The dried solid was ball-milled in a ball mill at 800 rpm for 8 hours, and the ground powder was passed through a 500-mesh sieve to obtain the precursor Ni ₉ Co _0.5 Mn _0.5 (HO) ₂ powder.

(3) Weigh the precursor powder and lithium acetate solid prepared in step (2) in a molar ratio of 1:1.02, and mix them evenly and fully by using absolute ethanol for liquid phase dispersion. After drying for 6 hours, spread the mixture on a porcelain boat. middle. Oxygen with a purity of 99.9% was introduced into the tube, and the above-mentioned porcelain boat was placed in a muffle furnace, first calcined at 350 °C for 200 min, then raised to 700 °C for 1300 min, and then naturally cooled to room temperature and taken out. The sintered nickel-cobalt-manganese ternary material is ball-milled in a ball mill for 24 hours and then passed through an 800-mesh sieve to obtain nickel-cobalt-manganese ternary positive electrode material powder.

Fifth Embodiment

A method for preparing a nickel-cobalt-manganese ternary positive electrode material, comprising the following steps:

(1) According to the molar ratio of nickel, cobalt and manganese ions of 8:1.5:0.5, weigh Ni(OH) ₂ crystals, Co(OH) ₂ crystals, and measure 50% Mn(OH) ₂ solutions. The above three kinds of raw materials and ammonia water (the molar ratio of the ammonia water to nickel, cobalt, and manganese ions are in the range of 1:1) are added into a mixed solvent (36ml ethanol+12ml water), and the crystals are completely dissolved by stirring to obtain a reaction mother liquor. .

(2) Transfer the reaction mother liquor obtained in step (1) to the lining of the reaction kettle, react in a homogeneous reaction furnace at 200 ° C for 300 min, use suction filtration and centrifugation to clean the solid product after completion, and then The solid product was dried in a forced air oven at 50 °C for 20 h. The dried solid was ball-milled in a ball mill at 800 rpm for 8 hours, and the ground powder was passed through a 500-mesh sieve to obtain the precursor Ni ₉ Co _0.5 Mn _0.5 (HO) ₂ powder.

(3) Weigh the precursor powder and lithium nitrate solid prepared in step (2) according to the molar ratio of 1:1.05, and mix them evenly and fully by using absolute ethanol for liquid phase dispersion. After drying for 6 hours, the mixture is spread on a porcelain boat. middle. Oxygen with a purity of 99.9% was introduced into the tube, and the above-mentioned porcelain boat was placed in a muffle furnace, first calcined at 400 °C for 150 min, then raised to 850 °C for 1100 min, and then naturally cooled to room temperature and taken out. The sintered nickel-cobalt-manganese ternary material is ball-milled in a ball mill for 24 hours and then passed through an 800-mesh sieve to obtain nickel-cobalt-manganese ternary positive electrode material powder.

Performance Testing

The nickel-cobalt-manganese ternary cathode material powders prepared in the first and second examples above are respectively mixed with PVDF and acetylene black in a mass ratio of 8:1:1, and then an appropriate amount of N-methylpyrrolidone is added to the obtained mixture to the mixture. It can be slightly flowing, fully stirred until uniform, and the obtained paste-like product is coated on aluminum foil with a thickness of 12 μm, and then placed in a vacuum drying oven at 60 °C for drying for 12 hours to obtain NCM positive pole pieces.

The NCM positive pole piece was cut into a circular pole piece with a diameter of 14 mm, 6 pole pieces of similar quality were weighed, and vacuum dried for 12 h. In the glove box, use the NCM pole piece as the positive pole, the metal lithium piece as the negative pole, use the ceramic separator as the diaphragm, and use the purchased commercial high-nickel ternary material special electrolyte as the electrolyte to assemble 2032 button batteries, each of which is assembled 6 pieces The battery was tested for electrochemical performance using the blue CT2001 battery test, and the test temperature was constant at 25°C. The electrochemical test voltage range is 3~4.3V, and the rate test is tested at 1C, 2C, 3C, 4C, 5C, 10C and 1C.

The microstructures of the precursor material and cathode material (NCM622) prepared in the first example are shown in Figure 1 and Figure 2, respectively, and the electrochemical performance test of the NCM cathode material is shown in Figure 3. It can be seen from Figure 1 that the prepared precursor material exhibits an obvious petal spherical structure, and the large interlayer spacing of the petal structure can be seen intuitively, and then these interlayer spacings can be used to obtain its high diffusion rate. Ion diffusion channels through anions and water molecules. Through the two-stage high-temperature sintering calcination method, the precursor in the pre-sintering stage is conducive to the synthesis of the well-ordered layered structure cathode material, and in the high-temperature calcination stage, it determines the Li ⁺ /Ni ²⁺ mixing degree of the synthesized cathode material and crystal structure integrity. It can be seen from the microstructure of the NCM811 cathode material shown in FIG. 2 that the NCM811 cathode material is formed by agglomeration and accumulation of primary particles. The secondary particles are agglomerated into spherical particles with a diameter of about 6 μm, and the electrodes are made of uniform powders for electrochemical performance testing. The rate test results are shown in Figure 3. The activated button battery is charged at different rates. The discharge test shows that the battery capacity retention rate of NCM622 and NCM811 materials at 5C rate reaches more than 65% of that under 1C state, and the retention rate under 10C reaches about 40% of that under 1C state. And under the condition of low rate (1C) charging after high rate charging and discharging, the battery capacity is maintained at about 93% (NCM811) and 99% (NCM622) of the initial 1C, and its structure remains stable during high current charging and discharging. . This is due to the complete crystal structure brought by the staged calcination procedure and the ion diffusion channels preserved in the precursor pre-calcination stage.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still understand the foregoing embodiments. The technical solutions described are modified, or some technical features thereof are equivalently replaced. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. A preparation method of a nickel-cobalt-manganese ternary cathode material is characterized by comprising the following steps:

(1) adding a precipitator into the solution containing nickel ions, cobalt ions and manganese ions to obtain reaction mother liquor;

(2) carrying out hydrothermal reaction on the reaction mother liquor, and separating out a solid product after the hydrothermal reaction is finished to obtain a precursor material Ni_xCo_yMn_(1-x-y)(HO)₂Wherein x is more than or equal to 0.6 and less than or equal to 0.9, and y is more than or equal to 0.05 and less than or equal to 0.2;

(3) and carrying out sectional calcination on the precursor material and the lithium source at different temperature stages in an oxygen atmosphere to obtain the nickel-cobalt-manganese ternary cathode material.

2. The method for preparing a nickel-cobalt-manganese ternary cathode material according to claim 1, wherein in the step (1), the nickel ions are provided by at least one of nickel nitrate, nickel acetate, nickel carbonate and nickel hydroxide;

or, in the step (1), the cobalt ions are provided by at least one of cobalt nitrate, cobalt acetate, cobalt carbonate and cobalt hydroxide;

or in the step (1), the manganese ions are provided by at least one of manganese cobalt nitrate, manganese acetate, manganese carbonate and manganese hydroxide.

3. The method for preparing a nickel-cobalt-manganese ternary cathode material according to claim 1, wherein in the step (1), the ratio of the nickel ions, the cobalt ions and the manganese ions is configured according to the atomic number ratio of each metal element in the precursor material in the step (2).

4. The method for preparing the nickel-cobalt-manganese ternary cathode material according to claim 1, wherein in the step (1), the precipitating agent comprises any one of urea, ammonia water and ammonium fluoride; preferably, the molar ratio of the precipitant to the metal ion is in the range of 1: 1 to 1: 2, the metal ions refer to the sum of nickel ions, cobalt ions and manganese ions.

5. The method for preparing the nickel-cobalt-manganese ternary cathode material according to claim 1, wherein in the step (1), the solution is a mixed solution of ethanol and water; preferably, the volume ratio of ethanol to water is in the range of 1: 4 to 1: 3.

6. the method for preparing the nickel-cobalt-manganese ternary cathode material according to claim 1, wherein in the step (2), the temperature of the hydrothermal reaction is 150-200 ℃ and the reaction time is 5-15 h.

7. The method for preparing a nickel-cobalt-manganese ternary positive electrode material according to claim 1, wherein in the step (3), the molar ratio of the precursor material to the lithium source is 1: 1.02-1: 1.05; preferably, the lithium source comprises at least one of lithium hydroxide solids, lithium carbonate, lithium acetate, lithium nitrate.

8. The method for preparing the nickel-cobalt-manganese ternary cathode material according to claim 1, wherein in the step (3), the precursor material and the lithium source are uniformly mixed by ball milling or liquid phase dispersion, and then the step calcination is performed.

9. The method for producing a nickel-cobalt-manganese ternary positive electrode material according to any one of claims 1 to 8, wherein in the step (3), the stepwise calcination includes: calcining at 350-450 ℃ for 150-200 min, then heating to 700-850 ℃ and continuing calcining for 1100-1300 min.

10. The use of the nickel-cobalt-manganese ternary positive electrode material of the lithium ion battery obtained by the preparation method according to any one of claims 1 to 9 in an energy storage device.

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