CN109244390B - Phosphorus-doped lithium-rich manganese-based positive electrode material for lithium ion battery and preparation method thereof - Google Patents

Phosphorus-doped lithium-rich manganese-based positive electrode material for lithium ion battery and preparation method thereof Download PDF

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CN109244390B
CN109244390B CN201810955731.XA CN201810955731A CN109244390B CN 109244390 B CN109244390 B CN 109244390B CN 201810955731 A CN201810955731 A CN 201810955731A CN 109244390 B CN109244390 B CN 109244390B
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phosphorus
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CN109244390A (en
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王振波
王敏君
玉富达
隋旭磊
赵磊
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Harbin Institute of Technology
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

The invention discloses a preparation method of a phosphorus-doped lithium-rich manganese-based positive electrode material for a lithium ion battery, which specifically comprises the steps of preparing a precipitator solution, preparing a metal salt solution, preparing a phosphorus-doped nickel-cobalt-manganese carbonate precursor and preparing the phosphorus-doped lithium-rich manganese-based positive electrode material; dissolving a pyrophosphoric acid compound serving as a phosphorus source in a precipitator solution, obtaining a phosphorus-doped nickel-cobalt-manganese compound precursor by adopting a coprecipitation method, and finally obtaining the phosphorus-doped lithium-rich manganese-based positive electrode material by high-temperature sintering; the preparation method disclosed by the invention is simple, and the prepared anode material is not only doped with phosphorus on the surface, but also uniformly doped with phosphorus in the material, so that the material is stable in performance and long in service life, and meanwhile, the capacity, the first effect, the multiplying power and the cycling stability of the material are obviously improved.

Description

Phosphorus-doped lithium-rich manganese-based positive electrode material for lithium ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of material synthesis, in particular to a preparation method of a phosphorus-doped lithium-rich manganese-based positive electrode material for a lithium ion battery.
Background
Energy and environmental protection are two major problems facing human beings at present, and the development of green and pollution-free new energy and energy storage equipment is a hot spot of research at present. Lithium batteries are receiving increasing attention because of their high energy density and environmentally friendly use. Along with the development of traffic equipment such as electric automobiles and the like, higher and higher requirements are put forward on the service performance of lithium batteries, so that the use requirements of the traditional lithium ion battery anode materials are difficult to meet. The lithium-rich manganese-based positive electrode material of the lithium ion battery is taken as an advanced electrode material, and is considered to be the most likely positive electrode material of the next generation of high-performance lithium ion battery due to the high specific capacity (more than 250mAh/g) and the wide working voltage window (2-4.8V). However, the use of the lithium-rich manganese-based cathode material is severely limited due to the obvious defects of low rate capability, poor cycle stability and the like. Phosphorus doping has received increasing attention as an effective method for improving lithium-rich materials.
However, the existing phosphorus doping methods have obvious defects, wherein the methods mainly comprise synthesis by sol-gel, hydrothermal method and the like, but the synthesis methods are not suitable for industrial production, and the development and popularization are obviously limited; in addition, the method is to mix related phosphorus compounds after synthesizing precursors, and then to prepare the phosphorus compounds through high-temperature sintering, and the method has the disadvantages of complicated process, surface doping only and uneven doping effect.
Therefore, the technical personnel in the field need to solve the problem of providing the phosphorus-doped lithium-rich manganese-based cathode material for the lithium ion battery and the preparation method thereof, wherein the preparation process is simple and convenient.
Disclosure of Invention
In view of the above, the invention provides a phosphorus-doped lithium-rich manganese-based positive electrode material for a lithium ion battery and a preparation method thereof, the preparation process is simple, the operation is simple and convenient, the yield is high, and the prepared positive electrode material is doped with uniform phosphorus.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a phosphorus-doped lithium-rich manganese-based positive electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) preparation of a precipitant solution: dissolving a precipitator in deionized water to prepare a solution with the molar concentration of 0.5-2 mol/L; adding pyrophosphate compound, stirring to completely dissolve to obtain precipitant solution;
(2) preparing a metal salt solution: dissolving a manganese salt compound, a nickel salt compound and a cobalt salt compound in deionized water to prepare a metal salt solution with the concentration of 0.5-2 mol/L;
(3) preparing a phosphorus-doped nickel-cobalt-manganese carbonate precursor: dropwise adding a metal salt solution and a precipitator solution into deionized water under the stirring condition, and performing precipitation reaction to obtain a phosphorus-doped nickel-cobalt-manganese compound precursor;
(4) preparing a phosphorus-doped lithium-rich manganese-based positive electrode material: uniformly mixing the phosphorus-doped nickel-cobalt-manganese compound precursor with lithium salt, presintering, and sintering at high temperature to obtain the phosphorus-doped lithium-rich manganese-based positive electrode material.
The beneficial effects of the preferred technical scheme are as follows: in the preparation method disclosed by the invention, a pyrophosphoric acid compound is taken as a phosphorus source and dissolved in a precipitator solution, a phosphorus-doped nickel-cobalt-manganese compound precursor can be obtained by adopting a coprecipitation method, and finally, the phosphorus-doped lithium-rich manganese-based positive electrode material can be obtained by high-temperature sintering; the preparation method disclosed by the invention is simple, and the prepared anode material is not only doped with phosphorus on the surface, but also uniformly doped with phosphorus in the material, so that the material is stable in performance and long in service life, and meanwhile, the capacity, the first effect, the multiplying power and the cycling stability of the material are obviously improved.
Preferably, the pyrophosphate compound in the step (1) comprises one or a mixture of sodium pyrophosphate and potassium pyrophosphate; the molar ratio of the pyrophosphate compound to the precipitant is 1-10: 100.
the beneficial effects of the preferred technical scheme are as follows: the method selects the pyrophosphate compound as the phosphorus source, utilizes the fact that the pyrophosphate has higher precipitation coefficient, and the aqueous solution is alkaline and can well coexist with the precipitator. In the doping process, if the doping proportion is too low, the improvement on the material performance is not obvious, and if the doping proportion is too high, the material performance is reduced, and the doping proportion selected by the invention is reasonable, so that the material has excellent doping performance.
Preferably, the manganese salt compound of step (2) comprises manganese sulfate, manganese chloride, manganese acetate or manganese nitrate, the nickel salt compound comprises nickel sulfate, nickel chloride, nickel acetate or nickel nitrate, and the cobalt salt compound comprises cobalt sulfate, cobalt chloride, cobalt acetate or cobalt nitrate.
Preferably, the precipitant in step (1) is sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide.
Preferably, the precipitant in the step (1) is sodium carbonate or potassium carbonate, and the pH value of the reaction system is controlled to be 7-8 by controlling the dropping speed of the metal salt solution and the precipitant solution in the step (3).
Preferably, the precipitant in the step (1) is sodium hydroxide or potassium hydroxide, and the pH value of the reaction system in the step (3) is controlled to be 11-13 by controlling the dropping speed of the metal salt solution and the precipitant solution.
Preferably, the stirring speed in the step (3) is 800-1500 r/min, the reaction temperature is 50-70 ℃, and the reaction time is 10-30 h; and washing the suspension obtained by the reaction with deionized water, filtering and drying to obtain the phosphorus-doped nickel-cobalt-manganese carbonate precursor.
Preferably, the molar ratio of the phosphorus-doped nickel-cobalt-manganese compound precursor to the lithium salt in the step (4) is 1: 1-1: 2, and the lithium salt includes one or more of lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate and lithium carbonate.
Preferably, the pre-firing process in the step (4) is specifically as follows: heating to 400-550 ℃ at a heating rate of 3-5 ℃/min, and then pre-sintering for 3-5 h; the high-temperature sintering process specifically comprises the following steps: continuously heating to 700-900 ℃ at the heating rate of 3-5 ℃/min, and sintering for 10-20 h.
The lithium ion battery positive electrode material is characterized by being prepared by the preparation method.
The beneficial effects of the preferred technical scheme are as follows: the lithium ion battery anode material disclosed by the invention not only dopes phosphorus on the surface of the material, but also uniformly dopes phosphorus in the material, so that the rate capability, the cycle stability and the like of the lithium ion battery anode material are obviously improved.
According to the technical scheme, compared with the prior art, the invention discloses a phosphorus-doped lithium-rich manganese-based positive electrode material for a lithium ion battery and a preparation method thereof, and the phosphorus-doped lithium-rich manganese-based positive electrode material has the following beneficial effects:
(1) the invention uses pyrophosphate compound as phosphorus source, and adopts simple coprecipitation method to prepare the whole phosphorus-doped lithium ion battery anode material, thereby not only simplifying phosphorus-doped step, but also improving phosphorus-doped effect;
(2) the prepared lithium ion battery anode material has the advantages that the discharge capacity, the first coulombic efficiency, the multiplying power and the circulation stability are obviously improved, wherein the discharge capacity is 294mAh/g, the first coulombic efficiency is 90 percent, the 1C multiplying power is 242mAh/g, and the capacity is kept 88 percent after 100 cycles of circulation.
(3) The preparation method provided by the invention is simple and feasible in process and low in cost, can greatly improve the comprehensive performance of the lithium-rich manganese-based material, and has an excellent development prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an electron microscopy mapping chart of the phosphorus-doped lithium-rich manganese-based cathode material prepared in example 1;
fig. 2 is an EDS diagram of the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 1;
FIG. 3 is a first-turn charge-discharge curve of the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 1;
FIG. 4 is a graph of rate performance of the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 1;
fig. 5 is a cycle performance curve of the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 1.
FIG. 6 is a graph of rate performance of the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 2;
fig. 7 is a cycle performance curve of the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 2.
FIG. 8 is a graph of rate performance of the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 3;
fig. 9 is a cycle performance curve of the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 3.
FIG. 10 is a graph of rate performance of the phosphorus doped lithium rich manganese based positive electrode material prepared in example 4;
fig. 11 is a cycle performance curve of the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 4.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a phosphorus-doped lithium-rich manganese-based positive electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) preparation of a precipitant solution: dissolving sodium carbonate in deionized water to prepare a solution with the molar concentration of 2 mol/L; adding sodium pyrophosphate, and stirring to completely dissolve to obtain precipitant solution; wherein the molar ratio of the sodium pyrophosphate to the precipitant is 2: 100, respectively;
(2) preparing a metal salt solution: firstly, according to a molar ratio of 4:1:1 weighing manganese sulfate monohydrate, nickel sulfate hexahydrate and cobalt sulfate heptahydrate; then dissolving the mixture in deionized water to prepare 2mol/L metal salt solution;
(3) preparing a phosphorus-doped nickel-cobalt-manganese carbonate precursor: dropwise adding a metal salt solution and a precipitator solution into 200mL of deionized water under the stirring condition of 800r/min, controlling the dropwise adding speed to keep the pH value of a reaction system at 8, controlling the reaction system to react at 55 ℃ for 12h, washing the suspension obtained by the reaction for 5 times by using the deionized water, and performing suction filtration and drying to obtain the phosphorus-doped nickel-cobalt-manganese compound precursor (Mn4/6Ni1/6Co1/6)CO3；
(4) Preparing a phosphorus-doped lithium-rich manganese-based positive electrode material: uniformly mixing a phosphorus-doped nickel-cobalt-manganese compound precursor with lithium carbonate according to a molar ratio of 1:1.15, then placing the mixture in a muffle furnace, heating the mixture to 450 ℃ at a heating rate of 5 ℃/min, and then presintering the mixture for 5 hours; and continuously heating to 800 ℃ at the heating rate of 5 ℃/min, sintering for 12h, and slowly cooling to room temperature to obtain the phosphorus-doped lithium-rich manganese-based positive electrode material.
Example 2
A preparation method of a phosphorus-doped lithium-rich manganese-based positive electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) preparation of a precipitant solution: dissolving potassium carbonate in deionized water to prepare a solution with the molar concentration of 1 mol/L; adding sodium pyrophosphate, and stirring to completely dissolve to obtain precipitant solution; wherein the molar ratio of the sodium pyrophosphate to the precipitant is 5: 100, respectively;
(2) preparing a metal salt solution: firstly, weighing manganese nitrate tetrahydrate, nickel nitrate hexahydrate and cobalt nitrate hexahydrate according to a molar ratio of 4:1: 1; then dissolving the mixture in deionized water to prepare 1mol/L metal salt solution;
(3) preparing a phosphorus-doped nickel-cobalt-manganese carbonate precursor: under the stirring condition of 900r/min, dropwise adding a metal salt solution and a precipitator solution into 200mL of deionized water, controlling the dropwise adding speed to keep the pH value of a reaction system at 7.5, then reacting for 15h at 50 ℃, washing a suspension obtained by the reaction for 5 times by using the deionized water, and then performing suction filtration and drying to obtain a phosphorus-doped nickel-cobalt-manganese compound precursor;
(4) preparing a phosphorus-doped lithium-rich manganese-based positive electrode material: uniformly mixing a phosphorus-doped nickel-cobalt-manganese compound precursor with lithium nitrate according to a molar ratio of 1:2, then placing the mixture in a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min, and then pre-sintering for 3 hours; and continuously heating to 700 ℃ at the heating rate of 5 ℃/min, sintering for 12h, and slowly cooling to room temperature to obtain the phosphorus-doped lithium-rich manganese-based positive electrode material.
Example 3
A preparation method of a phosphorus-doped lithium-rich manganese-based positive electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) preparation of a precipitant solution: dissolving potassium hydroxide in deionized water to prepare a solution with the molar concentration of 1 mol/L; adding potassium pyrophosphate, stirring until the potassium pyrophosphate is completely dissolved, and obtaining a precipitator solution; wherein the molar ratio of the sodium pyrophosphate to the precipitant is 3: 100, respectively;
(2) preparing a metal salt solution: firstly, according to a molar ratio of 6: 3: 1 weighing manganese chloride tetrahydrate, nickel chloride hexahydrate and cobalt chloride hexahydrate; then dissolving the mixture in deionized water to prepare 1mol/L metal salt solution;
(3) preparing a phosphorus-doped nickel-cobalt-manganese carbonate precursor: under the condition of stirring at 1300r/min, dropwise adding a metal salt solution and a precipitator solution into 200mL of deionized water, controlling the dropwise adding speed to keep the pH value of a reaction system at 11, then reacting for 24 hours at 70 ℃, washing a suspension obtained by the reaction for 5 times by using the deionized water, and then performing suction filtration and drying to prepare a phosphorus-doped nickel-cobalt-manganese compound precursor;
(4) preparing a phosphorus-doped lithium-rich manganese-based positive electrode material: mixing a phosphorus-doped nickel-cobalt-manganese compound precursor and lithium hydroxide according to the weight ratio of 1: 2mol ratio, then placing the mixture in a muffle furnace, heating the mixture from room temperature to 550 ℃ at the heating rate of 3 ℃/min, and then presintering the mixture for 5 hours; and continuously heating to 900 ℃ at the heating rate of 3 ℃/min, sintering for 15h, and slowly cooling to room temperature to obtain the phosphorus-doped lithium-rich manganese-based positive electrode material.
Example 4
A preparation method of a phosphorus-doped lithium-rich manganese-based positive electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) preparation of a precipitant solution: dissolving sodium hydroxide in deionized water to prepare a solution with the molar concentration of 0.5 mol/L; adding sodium pyrophosphate, and stirring to completely dissolve to obtain precipitant solution; wherein the molar ratio of the sodium pyrophosphate to the precipitant is 10: 100, respectively;
(2) preparing a metal salt solution: firstly, according to a molar ratio of 6: 3: 1 weighing manganese acetate tetrahydrate, nickel acetate tetrahydrate and cobalt acetate tetrahydrate; then dissolving the mixture in deionized water to prepare 0.5mol/L metal salt solution;
(3) preparing a phosphorus-doped nickel-cobalt-manganese carbonate precursor: under the stirring condition of 1500r/min, dropwise adding a metal salt solution and a precipitator solution into 200mL of deionized water, controlling the dropwise adding speed to keep the pH value of a reaction system at 13, then reacting for 30h at 60 ℃, washing a suspension obtained by the reaction for 5 times by using the deionized water, and then performing suction filtration and drying to obtain a phosphorus-doped nickel-cobalt-manganese compound precursor;
(4) preparing a phosphorus-doped lithium-rich manganese-based positive electrode material: mixing a phosphorus-doped nickel-cobalt-manganese compound precursor and lithium acetate according to the proportion of 1: uniformly mixing the raw materials according to a molar ratio of 1.95, then placing the mixture into a muffle furnace, heating the mixture from room temperature to 500 ℃ at a heating rate of 3 ℃/min, and then pre-sintering the mixture for 5 hours; and continuously heating to 850 ℃ at the heating rate of 3 ℃/min, sintering for 20h, and slowly cooling to room temperature to obtain the phosphorus-doped lithium-rich manganese-based positive electrode material.
The performance of the phosphorus-doped lithium-rich manganese-based positive electrode materials prepared in the above examples 1 to 4 was tested.
Firstly, electron microscope mapping image detection is carried out on the phosphorus-doped lithium-rich manganese-based cathode material prepared in the embodiment 1, and the result is shown in fig. 1; the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 1 was subjected to EDS elemental analysis, and the results are shown in fig. 2.
The distribution of the individual elements in the material can be seen from the results in fig. 1, where P is present in the material as can be seen from the mapping plot of P, successfully achieving P doping. From the results of fig. 2, it can be known that the phosphorus-doped lithium-rich manganese-based cathode material contains P, which indicates that P doping is successfully achieved.
Secondly, the phosphorus-doped lithium-rich manganese-based positive electrode materials prepared in examples 1 to 4 are subjected to charge and discharge performance, rate performance and cycle performance detection, and the results are shown in fig. 3 to 11.
The results of the tests shown in FIGS. 3 to 5 show that: the discharge capacity of the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in the embodiment 1 is 294mAh/g, the first coulombic efficiency is 90%, the 1C multiplying power is 242mAh/g, and the capacity is kept 84% after 200 cycles.
As can be seen from the detection results of fig. 6 and 7: the initial capacity of the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 2 is 285mAh/g, the capacity is 237mAh/g at a rate of 1C, the capacity is 182mAh/g at a rate of 3C, and the capacity is maintained at 77% after 300 cycles.
As can be seen from the results of fig. 8 and 9, the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 3 has an initial capacity of 289mAh/g, a capacity of 231mAh/g at a rate of 1C, and a capacity of 170mAh/g at a rate of 3C, and the capacity is maintained at 75% after 300 cycles.
As can be seen from the results of fig. 10 and 11, the initial capacity of the phosphorus-doped lithium-rich manganese-based positive electrode material prepared in example 4 was 285mAh/g, the capacity was 224mAh/g at a 1C rate, the capacity was 158mAh/g at a 3C rate, and the capacity was maintained at 94% after 100 cycles.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

1. A preparation method of a phosphorus-doped lithium-rich manganese-based positive electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) preparation of a precipitant solution: dissolving a precipitator in deionized water to prepare a solution with the molar concentration of 0.5-2 mol/L; adding pyrophosphate compound, stirring to completely dissolve to obtain precipitant solution; the precipitant is sodium carbonate and potassium carbonate; the molar ratio of the pyrophosphate compound to the precipitant is 1-10: 100, respectively;
(2) preparing a metal salt solution: dissolving a manganese salt compound, a nickel salt compound and a cobalt salt compound in deionized water to prepare a metal salt solution with the concentration of 0.5-2 mol/L;
(3) preparing a phosphorus-doped nickel-cobalt-manganese carbonate precursor: dropwise adding a metal salt solution and a precipitator solution into deionized water under the stirring condition, and performing precipitation reaction to obtain a phosphorus-doped nickel-cobalt-manganese compound precursor;
(4) preparing a phosphorus-doped lithium-rich manganese-based positive electrode material: uniformly mixing the phosphorus-doped nickel-cobalt-manganese compound precursor with lithium salt, presintering, and sintering at high temperature to obtain the phosphorus-doped lithium-rich manganese-based positive electrode material.
2. The method for preparing the phosphorus-doped lithium-rich manganese-based positive electrode material for the lithium ion battery according to claim 1, wherein the pyrophosphate compound in the step (1) comprises one or a mixture of sodium pyrophosphate and potassium pyrophosphate.
3. The method for preparing the phosphorus-doped lithium-rich manganese-based positive electrode material for the lithium ion battery according to claim 1, wherein the manganese salt compound in the step (2) comprises manganese sulfate, manganese chloride, manganese acetate or manganese nitrate, the nickel salt compound comprises nickel sulfate, nickel chloride, nickel acetate or nickel nitrate, and the cobalt salt compound comprises cobalt sulfate, cobalt chloride, cobalt acetate or cobalt nitrate.
4. The preparation method of the phosphorus-doped lithium-rich manganese-based positive electrode material for the lithium ion battery according to claim 1, wherein in the step (3), the pH value of the reaction system is controlled to be 7-8 by controlling the dropping speed of the metal salt solution and the precipitant solution.
5. The preparation method of the phosphorus-doped lithium-rich manganese-based positive electrode material for the lithium ion battery according to claim 1, wherein the stirring speed in the step (3) is 800-1500 r/min, the reaction temperature is 50-70 ℃, and the reaction time is 10-30 h; and washing the suspension obtained by the reaction with deionized water, filtering and drying to obtain the phosphorus-doped nickel-cobalt-manganese carbonate precursor.
6. The preparation method of the phosphorus-doped lithium-rich manganese-based positive electrode material for the lithium ion battery according to claim 1, wherein the molar ratio of the phosphorus-doped nickel-cobalt-manganese compound precursor to the lithium salt in the step (4) is 1: 1-1: 2, and the lithium salt comprises one or more of lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate and lithium carbonate.
7. The preparation method of the phosphorus-doped lithium-rich manganese-based positive electrode material for the lithium ion battery according to claim 1, wherein the pre-sintering process in the step (4) is specifically as follows: heating to 400-550 ℃ at a heating rate of 3-5 ℃/min, and then pre-sintering for 3-5 h; the high-temperature sintering process specifically comprises the following steps: continuously heating to 700-900 ℃ at the heating rate of 3-5 ℃/min, and sintering for 10-20 h.
8. A lithium ion battery positive electrode material, characterized by being prepared by the preparation method of any one of claims 1 to 7.
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CN111916725B (en) * 2019-05-08 2023-05-02 中国石油化工股份有限公司 Phosphorus-doped high-nickel cathode material for lithium battery and preparation process thereof
CN110429268A (en) * 2019-08-19 2019-11-08 国联汽车动力电池研究院有限责任公司 A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof
CN112744872A (en) * 2019-10-30 2021-05-04 北京大学 Liquid-phase phosphorus element doping modification preparation method of high-nickel anode material
CN110713215B (en) * 2019-12-12 2020-04-17 桑顿新能源科技(长沙)有限公司 Phosphorus-doped core-shell ternary cathode material, preparation method thereof and lithium ion battery
CN111453776B (en) * 2020-02-14 2021-04-30 北京大学 Phosphorus and tungsten co-doping modification preparation method of lithium-rich manganese-based cathode material of lithium ion battery
CN112054194B (en) * 2020-08-07 2021-12-17 西安理工大学 Phosphorus-modified lithium ion battery positive electrode material and preparation method and application thereof
CN115799487A (en) * 2023-02-08 2023-03-14 国联汽车动力电池研究院有限责任公司 Boron-phosphorus co-doped modified lithium-rich manganese-based positive electrode material, and preparation method and application thereof

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