CN111987305A - Method for preparing high-capacity lithium-rich manganese-based positive electrode material through ammoniation-free coprecipitation - Google Patents
Method for preparing high-capacity lithium-rich manganese-based positive electrode material through ammoniation-free coprecipitation Download PDFInfo
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Abstract
The invention discloses a method for preparing a high-capacity lithium-rich manganese-based positive electrode material by coprecipitation, which comprises the following steps: (1) preparing a lithium-rich manganese-based positive electrode material precursor; (2) ball milling lithium mixing and spray pelletizing; (3) and (3) preparing the lithium-rich manganese-based anode material by high-temperature solid-phase sintering. The preparation method disclosed by the invention is simple in process, short in reaction time, low in energy consumption, green and environment-friendly, and beneficial to large-scale production, and the lithium-rich manganese-based cathode material prepared by the method has the advantages of uniform appearance, higher capacity, better cycling stability and the like.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a method for preparing a high-capacity lithium-rich manganese-based positive electrode material by non-ammoniation coprecipitation.
Background
Compared withLithium cobalt oxide, which is a positive electrode material of lithium ion batteries and is gradually commercialized in the early nineties of the twentieth century, has double energy density (up to 900Wh/kg) and higher capacity (up to 300mAh/g), and the huge energy and capacity advantages promote the new energy automobile industry to list the lithium manganese cobalt positive electrode material as a main direction for the development of future high-energy power batteries. The lithium-rich manganese-based cathode material can be expressed as solid solution form xLi2MnO3·(1-x)LiMO2(M may be one or a combination of Ni, Co and Mn), or may be expressed as Li [ Li ] in a layered formz(NixCoyMn1-x-y)1-z]O2Therefore, it can be known that part of the transition metal in the lithium-rich manganese-based layered positive electrode material is replaced by lithium metal, and lithium ions participating in the reaction per unit mass are increased in the process of charging and discharging the material, so that the layered positive electrode material has high capacity. And the content of the metal manganese element in the lithium-rich manganese-based anode material is higher than that of other transition metal elements, so that the use of noble metal cobalt and noble metal nickel is reduced, and the raw material cost of the material is reduced. Therefore, the lithium-rich manganese-based positive electrode material has the advantages of high capacity and energy, low cost, no toxicity, high thermal stability and the like.
The synthesis method of the lithium-rich manganese-based cathode material mainly comprises a sol-gel method, a solid phase method and a coprecipitation method. The lithium-rich manganese-based cathode material prepared by the sol-gel method generally has good electrochemical performance and the rate capability of the material is good. However, the shape of the material prepared by the method is difficult to control, the tap density of the material is low, a large amount of organic acid or alcohol with higher cost is used in the synthesis process, the preparation cost of the material is increased, and the sol-gel method is difficult to realize large-scale production. The solid phase method requires very uniform mixing of raw materials, increases equipment investment, and has long sintering process time and high energy consumption, thereby increasing the preparation cost of the material. The lithium-rich manganese-based anode material prepared by the solid phase method has relatively poor electrochemical performance and poor rate capability. At present, the coprecipitation method for preparing the lithium-rich manganese-based cathode material is the only method with industrial large-scale significance, and the coprecipitation method comprises hydroxyl coprecipitation and carbonate coprecipitation according to a precipitator. Preparation of lithium-rich by carbonate coprecipitationThe manganese-based positive electrode material has relatively good electrochemical performance, but the synthesis process is unstable, and the consistency of the precipitated product is difficult to ensure. The preparation process of the lithium-rich manganese-based positive electrode material by hydroxide coprecipitation is the same as that of the ternary precursor, the obtained precursor is often subjected to phase separation due to oxidation of manganese, and more Li is generated in the final sintered product2MnO2The lithium-rich manganese-based anode material prepared by the method is compact and has poor rate capability. Therefore, the industrial large-scale preparation method of the relatively mature lithium-rich manganese-based cathode material needs to be deeply researched.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a high-capacity lithium-rich manganese-based positive electrode material for a lithium ion battery by non-ammoniation coprecipitation, and provides a new preparation method for industrial large-scale production of the lithium-rich manganese-based positive electrode material.
The rapid and ammoniation-free coprecipitation method provided by the invention adopts the following technical scheme:
a method for preparing a high-capacity lithium-rich manganese-based positive electrode material by ammoniation-free coprecipitation comprises the following steps:
(1) preparing a precursor of the lithium-rich manganese-based positive electrode material: uniformly mixing nickel salt, manganese salt and cobalt salt to prepare an aqueous solution A, preparing a precipitator into an aqueous solution B, adding deionized water into a reaction kettle to serve as reaction base liquid, then adding the aqueous solution B to adjust the pH of the base liquid to 7.5-12, simultaneously controlling the temperature of liquid in the reaction kettle to be 50-60 ℃, injecting the aqueous solution A and the aqueous solution B into the reaction kettle at a certain speed, continuously stirring at a constant speed, continuously introducing protective gas, after coprecipitation reaction, standing, washing, filtering, drying and grinding the precipitate to obtain a lithium-rich manganese-based anode material precursor;
(2) ball-milling lithium mixing and spray pelletizing: adding a lithium-rich manganese-based positive electrode material precursor and a lithium source into a nodular graphite tank for ball milling, then performing spray granulation on suspension after ball milling through a spray dryer, and collecting dry powder after spray is finished;
(3) preparation of lithium-rich manganese-based positive electrode material by high-temperature solid-phase sinteringMaterial preparation: sintering and cooling the dry powder, then grinding and screening to obtain the lithium-rich manganese-based anode material Li1+z(NixMnyCo1-x-y)1-zO2Or in the form of a solid solution zLi2MnO3·(1-z)LiNixMnyCo1-x-yO2Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than 0 and less than 1.
The further technical scheme is that the nickel salt is selected from one or more of nickel sulfate, nickel nitrate, nickel acetate and nickel chloride, the manganese salt is selected from one or more of nickel sulfate, manganese nitrate, manganese acetate and manganese chloride, and the cobalt salt is selected from one or more of cobalt sulfate, cobalt nitrate, cobalt acetate and cobalt chloride.
The further technical scheme is that the molar ratio of the nickel salt, the manganese salt and the cobalt salt is Ni: mn: co ═ x (1-z) ]: [ z + (1-z) × y ]: [ (1-z) (1-x-y) ], wherein the concentration of the aqueous solution A is 0.5-3 mol/L, and the concentration of the aqueous solution B is 1-6 mol/L.
More preferably, the concentration of the aqueous solution A is 2mol/L, and the concentration of the aqueous solution B is 4 mol/L.
The further technical scheme is that the adding speed of the aqueous solution A and the aqueous solution B is 1-5 mL/min, and the stirring speed is 500-1500 rpm.
The further technical scheme is that in the reaction process in the step (1), the pH value of the solution is controlled to be constant by adjusting the pumping amount of the aqueous solution A and the aqueous solution B, the coprecipitation reaction time is 0.5-2 hours, and the precipitate stands for 2-5 hours.
The further technical proposal is that the precipitator is selected from sodium hydroxide or sodium carbonate.
The further technical proposal is that the lithium source is selected from one or more of lithium hydroxide, lithium nitrate, lithium acetate and lithium sulfate.
The further technical scheme is that the step (2) is specifically that the precursor and a lithium source are mixed according to the ratio of 1: adding the mass ratio of [1.05 x (1+ z) ] into a ball milling tank, adding 2-8% of lithium source in excess, adopting planetary ball milling, wherein the ball milling speed is 300-600 rpm, the ball milling time is 1-5 hours, carrying out spray granulation on suspension after ball milling by a spray dryer, setting the inlet temperature to be 250 ℃, the blowing speed to be 10-45L/min, the feeding peristaltic speed to be 5-25 rpm, and collecting dry powder after spraying.
The further technical scheme is that wet ball milling is adopted in the ball milling, a solvent is deionized water, and the solid content is 10-30%.
The further technical scheme is that the step (3) is specifically that the mixture obtained in the step (2) is placed in a tube furnace for sintering in an oxygen atmosphere, the sintering system is as follows, the mixture is heated to 500 ℃ from room temperature at the heating rate of 5 ℃/min, and the temperature is kept for 5 hours; then heating to 800-950 ℃, and also heating at the speed of 5 ℃/min for 12-20 hours; then naturally cooling to room temperature, grinding and screening the obtained powder material, and collecting the lithium-rich manganese-based positive electrode material Li1+z(NixMnyCo1-x-y)1-zO2Or in the form of a solid solution zLi2MnO3·(1-z)LiNixMnyCo1-x-yO2Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than 0 and less than 1.
Furthermore, the specific general formula of the lithium-rich manganese-based positive electrode material obtained by the method can be as follows: in solid solution form, 0.5Li2MnO3·0.5LiNi0.325 Co0.325Mn0.35O2、0.5Li2MnO3·0.5LiNi0.5 Co0.2Mn0.3O2、0.5Li2MnO3·0.5LiNi0.6Mn0.2Co0.2O2、0.4Li2MnO3·0.6LiNi0.5Co0.2Mn0.3O2And 0.4Li2MnO3·0.6LiNi0.6 Co0.2Mn0.2O2And the like.
Compared with the prior art, the invention has the following beneficial effects: the preparation method disclosed by the invention has the advantages that the coprecipitation reaction time is extremely short, only 0.5-2 hours, the synthesis efficiency of the precursor is improved to a great extent, the requirement on equipment is reduced, and the preparation cost of the material is reduced; the coprecipitation process saves the use of complexing agent ammonia water, reduces the pollution of ammonia to the environment, simultaneously saves the waste gas treatment process, and is a green and environment-friendly preparation method; the lithium-rich manganese-based cathode material for the lithium ions prepared by the method has high capacity and energy density, good cycle stability and thermal stability, low cost, high capacity and excellent performance, has a wide application prospect, and provides a new preparation method for industrial large-scale production of the lithium-rich manganese-based cathode material.
Drawings
FIG. 1 is a lithium-rich manganese-based 0.5Li of example 12MnO3·0.5LiNi0.325 Co0.325Mn0.35O2SEM image of the positive electrode material;
FIG. 2 is a lithium-rich manganese-based 0.5Li sample of example 12MnO3·0.5LiNi0.325 Co0.325Mn0.35O2A first charge-discharge curve chart of the anode material;
FIG. 3 is a lithium-rich manganese-based 0.5Li of example 12MnO3·0.5LiNi0.325 Co0.325Mn0.35O2Cycle performance diagram of the positive electrode material;
FIG. 4 is a lithium-rich manganese-based 0.5Li of example 22MnO3·0.5LiNi0.5Co0.2Mn0.3O2Cycle performance diagram of the positive electrode material;
FIG. 5 is a lithium-rich manganese-based 0.5Li sample 32MnO3·0.5LiNi0.6Mn0.2Co0.2O2Cycle performance diagram of the positive electrode material;
FIG. 6 is a lithium rich manganese based 0.4Li of example 42MnO3·0.6LiNi0.5Co0.2Mn0.3O2Cycle performance diagram of the positive electrode material;
FIG. 7 is a lithium rich manganese based 0.4Li of example 52MnO3·0.6LiNi0.6Co0.2Mn0.2O2Cycle performance diagram of the positive electrode material.
Detailed Description
The invention is explained in detail below with reference to the drawings and examples:
example 1:
(1) the method for preparing the lithium-rich manganese-based positive electrode material precursor by rapid and ammoniation-free coprecipitation comprises the following steps:
nickel sulfate, manganese sulfate and cobalt sulfate are mixed according to the mass ratio of Ni: mn: co ═ 0.13: 0.54: 0.13 is added into deionized water to prepare 2mol/L uniform solution A250 ml; sodium hydroxide was weighed to prepare 300ml of a 4mol/L homogeneous solution B as a precipitant. 300ml of deionized water is added into the reaction kettle, the temperature in the reaction kettle is controlled to be 50 ℃ by heating a circulating water area, and the pH value of the reaction bottom liquid is adjusted to be 11.5 by dropwise adding the solution B. Pumping the solution A into the reaction base solution at the speed of 1ml/min, continuously stirring the reaction base solution at the speed of 1000r/min, and continuously introducing nitrogen as protective gas. The pumping speed of the solution B is required to be adjusted according to the ph value of the reaction solution in the feeding process, so as to ensure that the ph value of the reaction solution is kept to be 11.5 +/-0.1. After the charging is finished and the reaction is carried out for 1 hour, the precipitate is kept stand for 2 hours, and then washing, filtering, drying and grinding are carried out to obtain the lithium-rich manganese-based precursor Ni0.1625Mn0.675Co0.1625(OH)2。
(2) Ball-milling lithium mixing and spray pelletizing:
the lithium-rich manganese-based precursor Ni0.1625Mn0.675Co0.1625(OH)2And lithium carbonate according to Li: m ═ 1.575: 1 is weighed and placed in a ball milling tank, wherein M is the sum of the mass of transition metals Ni, Mn and Co, and the mass excess of lithium carbonate is 5%. Adding deionized water for wet ball milling, and controlling the solid content of the ball milling liquid to be 15%. The ball milling time is 2 hours, the ball milling rotating speed is 500r/min, and the suspension is obtained after full mixing.
And (3) carrying out spray granulation on the suspension by a spray dryer, wherein the temperature of an air inlet is set to be 250 ℃, the feeding speed is 15r/min, and the needle passing speed is 60 seconds/time. The collected powder was dried in a forced air drying oven at 80 ℃ for 12 hours to obtain an intermediate product.
(3) The preparation of the lithium-rich manganese-based anode material by high-temperature solid-phase sintering comprises the following steps:
and (3) sintering the intermediate product obtained in the step (2) in an oxygen atmosphere by using a tube furnace. Firstly, heating from room temperature to 500 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for 5 hoursThen, the temperature is raised to 880 ℃ from 500 ℃ at the same temperature raising speed of 5 ℃/min, the constant temperature calcination is carried out for 15 hours, the mixture is naturally cooled to room temperature, the sintered powder is ground and screened, and then the powder is dried to obtain the lithium-rich manganese-based positive electrode material 0.5Li for the lithium ion battery2MnO3·0.5LiNi0.325 Co0.325Mn0.35O2。
FIG. 1 shows the prepared lithium-rich manganese-based positive electrode material 0.5Li2MnO3·0.5LiNi0.325Co0.325Mn0.35O2SEM image of (d). The anode material is in a required shape, the particle size is 2-10 mu m, the secondary particles are uniform in appearance and mainly formed by stacking regular primary particles of 200-800 nm, the surfaces of the secondary particles are not completely compact, holes which are communicated from the surfaces to the interior of the particles exist, the contact between the material and an electrolyte can be increased, and the rate capability of the material is improved. FIGS. 2 and 3 are 0.5 Li-rich manganese-based positive electrode materials2MnO3·0.5LiNi0.325Co0.325Mn0.35O2Electrochemical performance diagram of (1). FIG. 2 is a first charge-discharge curve diagram of the lithium-rich manganese-based positive electrode material, wherein the first charged specific capacity is close to 350mAh/g, and the first discharged specific capacity reaches 286 mAh/g. Fig. 3 is a cycle stability diagram of the lithium-rich manganese-based positive electrode material at a rate of 0.1C, after 100 charge and discharge cycles, the material has a specific discharge capacity of 252mAh/g, a capacity retention rate of 88%, and a charge and discharge coulombic efficiency of almost 100%. This shows that the lithium-rich manganese-based positive electrode material 0.5Li prepared by the rapid and ammoniation-free coprecipitation method provided by the invention2MnO3·0.5LiNi0.325Co0.325Mn0.35O2The material has the advantage of high capacity at a small multiplying power, and the material has excellent cycling stability.
Example 2
(1) The method for preparing the lithium-rich manganese-based positive electrode material precursor by rapid and ammoniation-free coprecipitation comprises the following steps:
nickel nitrate, manganese nitrate and cobalt nitrate are mixed according to the mass ratio of Ni: mn: co ═ 0.2: 0.52: 0.08 is added into deionized water to prepare 250ml of uniform solution A with the concentration of 2 mol/L; weighing sodium carbonate to prepare300ml of 4mol/L homogeneous solution B is used as a precipitant. 300ml of deionized water is added into the reaction kettle, the temperature in the reaction kettle is controlled to be 50 ℃ by heating a circulating water area, and the pH value of the reaction bottom liquid is adjusted to be 8.5 by dropwise adding the solution B. Pumping the solution A into the reaction base solution at the speed of 1ml/min, continuously stirring the reaction base solution at the speed of 1000r/min, and continuously introducing nitrogen as protective gas. The pumping speed of the solution B is required to be adjusted according to the ph value of the reaction solution in the feeding process so as to ensure that the ph value of the reaction solution is kept to be 8.5 +/-0.1. After the charging is finished and the reaction is carried out for 1 hour, the precipitate is kept stand for 2 hours, and then washing, filtering, drying and grinding are carried out to obtain the lithium-rich manganese-based precursor [ Ni ]0.25Mn0.65Co0.1]CO3。
(2) Ball-milling lithium mixing and spray pelletizing:
the lithium-rich manganese-based precursor [ Ni ]0.25Mn0.65Co0.1]CO3With lithium hydroxide according to Li: m ═ 1.575: 1 is weighed and placed in a ball milling tank, wherein M is the sum of the mass of transition metals Ni, Mn and Co, and the mass excess of lithium hydroxide is 5 percent. Adding deionized water for wet ball milling, and controlling the solid content of the ball milling liquid to be 15%. The ball milling time is 2 hours, the ball milling rotating speed is 500r/min, and the suspension is obtained after full mixing.
And (3) carrying out spray granulation on the suspension by a spray dryer, wherein the temperature of an air inlet is set to be 250 ℃, the feeding speed is 15r/min, and the needle passing speed is 60 seconds/time. The collected powder was dried in a forced air drying oven at 80 ℃ for 12 hours to obtain an intermediate product.
(3) The preparation of the lithium-rich manganese-based anode material by high-temperature solid-phase sintering comprises the following steps:
and (3) sintering the intermediate product obtained in the step (2) in an oxygen atmosphere by using a tube furnace. Firstly, heating to 500 ℃ from room temperature at a heating rate of 5 ℃/min, preserving heat for 5 hours, then heating to 870 ℃ from 500 ℃ at the same heating rate of 5 ℃/min, calcining at constant temperature for 15 hours, naturally cooling to room temperature, grinding and screening sintered powder, and then drying to obtain the lithium-rich manganese-based positive electrode material 0.5Li for the lithium ion battery2MnO3·0.5LiNi0.5 Co0.2Mn0.3O2。
FIG. 4 is a lithium-rich manganese-based positive electrode material 0.5Li2MnO3·0.5LiNi0.5 Co0.2Mn0.3O2Cycling stability performance plot at 0.1C magnification.
Example 3
The difference from example 2 is: nickel, manganese and cobalt salt are mixed according to the mass ratio of Ni: mn: co ═ 0.24: 0.48: 0.08 mixing; the sintering temperature of the second stage is 850 ℃ during solid phase sintering.
Other steps are the same as embodiment 2 and are not described herein.
FIG. 5 is a lithium-rich manganese-based positive electrode material 0.5Li2MnO3·0.5LiNi0.6Mn0.2Co0.2O2Cycling stability performance plot at 0.1C magnification.
Example 4
The difference from example 2 is: nickel, manganese and cobalt salt are mixed according to the mass ratio of Ni: mn: co 0.25: 0.48: 0.1 mixing; the lithium-rich manganese-based precursor [ Ni ]0.3Mn0.58Co0.12]CO3With lithium hydroxide according to Li: m ═ 1.47: 1, mixing;
other steps are the same as embodiment 2 and are not described herein.
FIG. 6 shows a lithium-rich manganese-based positive electrode material 0.4Li2MnO3·0.6LiNi0.5Co0.2Mn0.3O2Cycling stability performance plot at 0.1C magnification.
Example 5
The difference from example 2 is: nickel, manganese and cobalt salt are mixed according to the mass ratio of Ni: mn: co ═ 0.3: 0.43: 0.1 mixing; the lithium-rich manganese-based precursor [ Ni ]0.36Mn0.52Co0.12]CO3With lithium hydroxide according to Li: m ═ 1.47: 1, mixing; the sintering temperature of the second stage is 850 ℃ during solid phase sintering.
Other steps are the same as embodiment 2 and are not described herein.
FIG. 7 shows a lithium-rich manganese-based positive electrode material 0.4Li2MnO3·0.6LiNi0.6 Co0.2Mn0.2O2Cycling stability performance plot at 0.1C magnification.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (10)
1. A method for preparing a high-capacity lithium-rich manganese-based positive electrode material by ammoniation-free coprecipitation is characterized by comprising the following steps of:
(1) preparing a precursor of the lithium-rich manganese-based positive electrode material: uniformly mixing nickel salt, manganese salt and cobalt salt to prepare an aqueous solution A, preparing a precipitator into an aqueous solution B, adding deionized water into a reaction kettle to serve as reaction base liquid, then adding the aqueous solution B to adjust the pH of the base liquid to 7.5-12, simultaneously controlling the temperature of liquid in the reaction kettle to be 50-60 ℃, injecting the aqueous solution A and the aqueous solution B into the reaction kettle at a certain speed, continuously stirring at a constant speed, continuously introducing protective gas, after coprecipitation reaction, standing, washing, filtering, drying and grinding the precipitate to obtain a lithium-rich manganese-based anode material precursor;
(2) ball-milling lithium mixing and spray pelletizing: adding a lithium-rich manganese-based positive electrode material precursor and a lithium source into a nodular graphite tank for ball milling, then performing spray granulation on suspension after ball milling through a spray dryer, and collecting dry powder after spray is finished;
(3) preparing a lithium-rich manganese-based positive electrode material by high-temperature solid-phase sintering: sintering and cooling the dry powder, then grinding and screening to obtain the lithium-rich manganese-based anode material Li1+z(NixMnyCo1-x-y)1-zO2Or in the form of a solid solution zLi2MnO3·(1-z)LiNixMnyCo1-x-yO2Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than 0 and less than 1.
2. The method for preparing the high-capacity lithium-rich manganese-based cathode material by non-ammoniation coprecipitation according to claim 1, wherein the nickel salt is selected from one or more of nickel sulfate, nickel nitrate, nickel acetate and nickel chloride, the manganese salt is selected from one or more of nickel sulfate, manganese nitrate, manganese acetate and manganese chloride, and the cobalt salt is selected from one or more of cobalt sulfate, cobalt nitrate, cobalt acetate and cobalt chloride.
3. The method for preparing the high-capacity lithium-rich manganese-based positive electrode material by non-ammoniation coprecipitation according to claim 1, wherein the molar ratio of the nickel salt to the manganese salt to the cobalt salt is Ni: mn: co ═ x (1-z) ]: [ z + (1-z) × y ]: [ (1-z) (1-x-y) ], wherein the concentration of the aqueous solution A is 0.5-3 mol/L, and the concentration of the aqueous solution B is 1-6 mol/L.
4. The method for preparing the high-capacity lithium-rich manganese-based positive electrode material through non-ammoniation coprecipitation according to claim 1, wherein the addition speed of the aqueous solution A and the aqueous solution B is 1-5 mL/min, and the stirring speed is 500-1500 rpm.
5. The method for preparing the high-capacity lithium-rich manganese-based positive electrode material through ammoniation-free coprecipitation according to claim 1, wherein in the reaction process in the step (1), the pH value of the solution is controlled to be constant by adjusting the pumping amount of the aqueous solution A and the pumping amount of the aqueous solution B, the coprecipitation reaction time is 0.5-2 hours, and the precipitate is kept stand for 2-5 hours.
6. The method for preparing a high-capacity lithium-rich manganese-based positive electrode material by non-ammoniation co-precipitation according to claim 1, wherein the precipitant is selected from sodium hydroxide or sodium carbonate.
7. The method for preparing a high capacity lithium-rich manganese-based positive electrode material without ammoniation coprecipitation according to claim 1, wherein the lithium source is selected from one or more of lithium hydroxide, lithium nitrate, lithium acetate and lithium sulfate.
8. The method for preparing the high-capacity lithium-rich manganese-based positive electrode material by non-ammoniation co-precipitation according to claim 1, wherein the step (2) is specifically that the precursor and a lithium source are mixed according to a ratio of 1: adding the mass ratio of [1.05 x (1+ z) ] into a ball milling tank, adding 2-8% of lithium source in excess, adopting planetary ball milling, wherein the ball milling speed is 300-600 rpm, the ball milling time is 1-5 hours, carrying out spray granulation on suspension after ball milling by a spray dryer, setting the inlet temperature to be 250 ℃, the blowing speed to be 10-45L/min, the feeding peristaltic speed to be 5-25 rpm, and collecting dry powder after spraying.
9. The method for preparing the high-capacity lithium-rich manganese-based positive electrode material through ammoniation-free coprecipitation according to claim 8, wherein the ball milling is performed by a wet ball milling method, a solvent is deionized water, and the solid content is 10-30%.
10. The method for preparing the high-capacity lithium-rich manganese-based cathode material by non-ammoniation coprecipitation according to claim 1, wherein the step (3) is to sinter the mixture obtained in the step (2) in an oxygen atmosphere of a tube furnace, wherein the mixture is heated from room temperature to 500 ℃ at a heating rate of 5 ℃/min, and is kept for 5 hours; then heating to 800-950 ℃, and also heating at the speed of 5 ℃/min for 12-20 hours; then naturally cooling to room temperature, grinding and screening the obtained powder material, and collecting the lithium-rich manganese-based positive electrode material Li1+z(NixMnyCo1-x-y)1-zO2Or in the form of a solid solution zLi2MnO3·(1-z)LiNixMnyCo1-x-yO2Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than 0 and less than 1.
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