CN112624201A - Preparation method of lithium-rich cathode material - Google Patents

Preparation method of lithium-rich cathode material Download PDF

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CN112624201A
CN112624201A CN202011378053.9A CN202011378053A CN112624201A CN 112624201 A CN112624201 A CN 112624201A CN 202011378053 A CN202011378053 A CN 202011378053A CN 112624201 A CN112624201 A CN 112624201A
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lithium
rich manganese
manganese
ion conductor
rich
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CN112624201B (en
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蔡伟平
陈志勇
范鑫铭
王潇晗
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Guangdong Mic Power New Energy Co Ltd
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    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
    • C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
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    • 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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Abstract

The invention relates to the technical field of preparation of lithium ion battery anode materials, and discloses a preparation method of a lithium-rich anode material, which comprises the following steps: providing a lithium-rich manganese-based raw material slurry, drying the lithium-rich manganese-based raw material slurry, and then sintering to obtain a lithium-rich manganese-based precursor Li1+xMn1‑x‑yMyO3，0<x<0.5，0<y<0.5; providing a fast ion conductor precursor, dissolving the fast ion conductor precursor in ultrapure water by a chemical deposition method, stirring, adding ammonia water and a lithium-rich manganese-based precursor, and stirring and mixingThen, obtaining a mixed solution; and performing water bath evaporation operation on the mixed solution to obtain a lithium-rich manganese-based anode material crystal coated by the fast ion conductor, and performing annealing treatment after drying operation on the lithium-rich manganese-based anode material crystal coated by the fast ion conductor to obtain the lithium-rich manganese-based anode material. The preparation method has simple process, and the prepared lithium-rich manganese-based positive electrode material has good consistency, high capacity and good performance.

Description

Preparation method of lithium-rich cathode material
Technical Field
The invention relates to the technical field of preparation of lithium ion battery anode materials, in particular to a preparation method of a lithium-rich anode material.
Background
The lithium ion battery is one of the most potential energy storage devices, and is widely applied to the life of people, with the development and progress of science and technology, people put forward higher requirements on the energy density of the lithium ion battery, and a lithium-rich manganese-based positive electrode material (LLO for short) is one of the positive electrode materials of the lithium ion battery, and is generally more than 250mAh/g due to higher specific discharge capacity, so that the lithium ion battery is a positive electrode material of the lithium ion battery which is focused and researched by people.
However, the surface of the lithium-rich manganese-based positive electrode material is easy to change in structure and component in the circulation process, and ions of the lithium-rich manganese-based positive electrode material have the problems of low conductivity, poor rate capability and capacity and voltage attenuation, so that the performance and stability of the lithium-rich manganese-based positive electrode material are greatly influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides the preparation method of the lithium-rich base anode material, which is simple to operate, can improve the cycling stability and the rate performance of the material and simultaneously improve the specific discharge capacity of the material, and the prepared lithium-rich manganese base anode material has good consistency, high capacity and good performance.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a lithium-rich cathode material comprises the following steps:
providing lithium-rich manganese-based raw material slurry, drying the lithium-rich manganese-based raw material slurry, and then sintering to obtain a lithium-rich manganese-based precursor Li1+xMn1-x-yMyO3，0<x<0.5，0<y<0.5；
Providing a fast ion conductor precursor, dissolving the fast ion conductor precursor in ultrapure water by a chemical deposition method, stirring, adding ammonia water and the lithium-rich manganese-based precursor, and stirring and mixing to obtain a mixed solution;
and performing water-bath evaporation operation on the mixed solution to obtain a lithium-rich manganese-based anode material crystal coated by the fast ion conductor, and performing annealing treatment after drying operation on the lithium-rich manganese-based anode material crystal coated by the fast ion conductor to obtain the lithium-rich manganese-based anode material.
In one embodiment, in the operation of providing the lithium-rich manganese-based raw material slurry, a lithium-containing compound and a precipitant are added into deionized water to obtain a first stock solution, a manganese-containing compound is added into deionized water to obtain a second stock solution, the first stock solution is added into the second stock solution to obtain a blending solution, the pH of the blending solution is adjusted to 5.1 to 6.3 to obtain an acidic blending solution, and a dopant is added into the acidic blending solution to obtain the lithium-rich manganese-based raw material slurry.
In one embodiment, the lithium-containing compound is at least one of lithium carbonate, lithium hydroxide, lithium acetate, and lithium nitrate.
In one embodiment, the manganese-containing compound is at least one of manganese nitrate, manganese sulfate, and manganese acetate.
In one embodiment, the precipitating agent is at least one of ammonium carbonate and citric acid.
In one embodiment, the fast ion conductor precursor includes lithium carbonate and zirconium nitrate.
In one embodiment, the fast ion conductor precursor includes lithium carbonate and titanium nitrate.
In one embodiment, during the sintering operation, the first-stage sintering operation is performed by controlling the temperature rise speed to be 2 ℃/min-4 ℃/min, the sintering temperature to be 400-600 ℃, the sintering time to be 3-8 h, and then the second-stage sintering operation is performed by controlling the temperature rise speed to be 2 ℃/min-4 ℃/min, the sintering temperature to be 800-900 ℃, and the sintering time to be 10-20 h.
In one embodiment, in the water bath evaporation operation of the mixed solution, the water bath evaporation temperature is controlled to be 60-90 ℃, and the water bath evaporation time is 5-20 h.
In one embodiment, after the mixed solution is subjected to water bath evaporation to obtain the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor is further subjected to cleaning operation.
Compared with the prior art, the invention has at least the following advantages:
the invention provides lithium-manganese-based precursor slurry, obtains a lithium-rich manganese-based precursor after drying and sintering operation, then can obtain a mixed solution which is uniformly mixed by premixing the fast ion conductor precursor and the lithium-rich manganese-based precursor, is favorable for ensuring the normal operation of subsequent water-bath evaporation operation, can uniformly attach the fast ion conductor precursor to the surface of the lithium-rich manganese-based precursor to generate a fast ion conductor when performing the water-bath evaporation operation, and coats the fast ion conductor on the surface of the lithium-rich manganese-based precursor, thereby being favorable for avoiding the direct contact between electrolyte and the lithium-rich manganese-based precursor, inhibiting the reaction between the electrolyte and the lithium-rich manganese-based precursor, playing a role of stabilizing a lithium-rich manganese structure, being favorable for improving the cycling stability of the lithium-rich manganese-based anode material obtained by subsequent preparation, and providing a lithium ion fast channel by the generated fast ion conductor, the lithium-rich manganese-based anode material is beneficial to the migration of lithium ions in the charging and discharging processes, and the ionic conductivity of the lithium-rich manganese-based anode material is improved, namely the multiplying power performance of the lithium-rich manganese-based anode material is improved. The preparation method has simple process, and the prepared lithium-rich manganese-based positive electrode material has good consistency, high capacity and good performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a flow chart illustrating steps of a method for preparing a lithium-rich cathode material according to an embodiment of the present invention;
FIG. 2 is a graph showing a comparison of charge and discharge performance at different rates in example 3 of the present invention and comparative example 1;
fig. 3 is a graph comparing charge and discharge performance at a current density of 0.5C for example 3, comparative example 1 and comparative example 2 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one embodiment, referring to fig. 1, a method for preparing a lithium-rich cathode material includes the following steps:
s110, providing lithium-rich manganese-based raw material slurry, drying the lithium-rich manganese-based raw material slurry, and then sintering to obtain a lithium-rich manganese-based precursor Li1+xMn1-x-yMyO3，0<x<0.5，0<y<0.5。
The lithium-rich manganese-based precursor Li with good performance is synthesized by providing lithium-rich manganese-based raw material slurry prepared in proportion and controlling the time and the temperature of drying and sintering operation1+xMn1-x-yMyO3，0<x<0.5，0<y<And 0.5, wherein the M element is an element ion doped to replace a manganese ion on the surface of the rich lithium manganese, so that the dissolution of the manganese ion is inhibited, and the effect of stabilizing the rich lithium manganese-based precursor is achieved, thereby being beneficial to improving the cycle stability of the rich lithium manganese-based anode material obtained by subsequent preparation.
In one embodiment, in the operation of providing the lithium-rich manganese-based raw material slurry, a lithium-containing compound and a precipitator are added into deionized water to obtain a first stock solution, a manganese-containing compound is added into deionized water to obtain a second stock solution, the first stock solution is added into the second stock solution to obtain a blending solution, the pH of the blending solution is adjusted to 5.1-6.3 to obtain an acidic blending solution, and a dopant is added into the acidic blending solution to obtain the lithium-rich manganese-based raw material slurry. It can be understood that the lithium-containing compound and the precipitant are accurately weighed according to a certain stoichiometric ratio, the lithium-containing compound and the precipitant are dissolved in deionized water to obtain a first stock solution which is thoroughly dissolved and mixed, meanwhile, the manganese-containing compound is accurately weighed according to a certain stoichiometric ratio, the manganese-containing compound is dissolved in deionized water to obtain a second stock solution which is thoroughly dissolved, so that the first stock solution and the second stock solution which are good in dispersibility are respectively obtained, the subsequent lithium-containing compound and the manganese-containing compound are favorably combined better to form a uniform and stable complex, the first stock solution is added into the second stock solution, the pH is adjusted to 5.1-6.3, the blending solution is in a weak acid environment, the manganese source and the lithium source are favorably combined fully to form the uniform and stable complex, and the charge-discharge capacity and the stability of the lithium-rich manganese-based anode material prepared subsequently are favorably improved, and then adding a doping agent into the acidic blending solution to obtain a final lithium-rich manganese-based raw material slurry, specifically, adding the prepared acidic blending solution into a liquid containing tank of a spiral channel type rotating bed, starting up the reactor, adjusting the rotating speed of the spiral channel type rotating bed by using a frequency converter, starting a pump, slowly adding the doping agent into the reactor after the liquid flow in the reactor is stable, reacting at normal temperature and normal pressure to obtain the final lithium-rich manganese-based raw material slurry, dispersing a lithium-containing compound and a manganese-containing compound into deionized water respectively, and reacting step by step to obtain the lithium-rich manganese-based raw material slurry. Preferably, the doping agent is at least one of nickel, titanium, magnesium, aluminum and chromium, and the dosage of the doping agent is 1-10% (mass) of the acidic blending liquid. That is to say, the M element is at least one of nickel, titanium, magnesium, aluminum and chromium, so that the dissolution of manganese ions can be effectively inhibited, the effect of stabilizing the lithium-rich manganese-based precursor is well achieved, the cyclic stability of the lithium-rich manganese-based anode material obtained by subsequent preparation is favorably improved, the dosage of the dopant is moderate, and the waste or the deficiency of the dopant is avoided.
In one embodiment, the lithium-containing compound is at least one of lithium carbonate, lithium hydroxide, lithium acetate, and lithium nitrate. It can be understood that lithium carbonate, lithium hydroxide, lithium acetate and lithium nitrate are all lithium-containing compounds commonly used in industry and are easy to obtain, wherein lithium carbonate is a commonly used lithium ion battery raw material, lithium hydroxide can be used as a raw material for preparing a lithium compound, and lithium acetate and lithium nitrate can provide abundant lithium ions.
In one embodiment, the manganese-containing compound is at least one of manganese nitrate, manganese sulfate and manganese acetate. It can be understood that manganese nitrate, manganese sulfate and manganese acetate are all manganese-containing compounds commonly used in industry, so that abundant manganese ions can be provided, and the manganese-containing compound is easy to obtain and suitable for industrial production.
In one embodiment, the precipitating agent is at least one of ammonium carbonate and citric acid. It can be understood that the precipitant adopts at least one of ammonium carbonate and citric acid, which is beneficial to promoting the lithium-containing compound and the manganese-containing compound to be fully combined and form a uniform and stable complex, and is beneficial to improving the charge and discharge capacity and stability of the lithium-rich manganese-based cathode material prepared subsequently.
In one embodiment, during the sintering operation, the temperature rise speed is controlled to be 2 ℃/min to 4 ℃/min, the sintering temperature is controlled to be 400 ℃ to 600 ℃, the sintering time is controlled to be 3h to 8h, the first-stage sintering operation is carried out, the temperature rise speed is controlled to be 2 ℃/min to 4 ℃/min, the sintering temperature is 800 ℃ to 900 ℃, the sintering time is 10h to 20h, and the second-stage sintering operation is carried out. It can be understood that, in the sintering operation of the dried lithium-rich manganese-based raw material slurry, sintering is carried out in two stages by controlling the temperature rise speed and the sintering time of the sintering, firstly, controlling the temperature rise speed to be 2 ℃/min-4 ℃/min, controlling the sintering temperature to be 400-600 ℃, controlling the sintering time to be 3-8 h, then, controlling the temperature rise speed to be 2 ℃/min-4 ℃/min, the sintering temperature to be 800-900 ℃, and the sintering time to be 10-20 h, and sintering operation is carried out in two stages, so that the sintering temperature can be gradually raised, the sintering time can be gradually increased, namely, the sintering temperature is raised from 400-600 ℃ to 800-900 ℃, and thus, the sintering operation can be carried out better and faster, because certain moisture exists in the dried lithium-rich manganese-based raw material slurry, the sintering temperature is firstly controlled to be 400-600 ℃, sintering is carried out at a lower temperature, the phenomenon that local heating is too high and scorching occurs can be avoided, so that normal operation of sintering operation is guaranteed, the sintering time is controlled to be 3-8 h, after moisture is completely removed, heating operation is carried out, the sintering temperature is increased to 800-900 ℃, sintering is continued for 10-20 h, the sintering speed can be accelerated, and complete sintering is guaranteed, so that the dried lithium-rich manganese-based raw material slurry is sintered better and faster, and the lithium-rich manganese-based precursor with good performance is obtained.
S120, providing a fast ion conductor precursor, dissolving the fast ion conductor precursor in ultrapure water by a chemical deposition method, stirring, adding ammonia water and the lithium-rich manganese-based precursor, and stirring and mixing to obtain a mixed solution.
The ion conductor precursor is fully dissolved in the ultrapure water by a chemical deposition method, the solution is uniformly stirred, then the ammonia water and the lithium-rich manganese-based precursor are added, and the stirring and mixing operation is performed to obtain the mixed solution, so that the fast ion conductor precursor, the ammonia water and the lithium-rich manganese-based precursor are premixed, the mixed solution which is uniformly mixed and has good dispersibility is obtained, the subsequent generation of the fast ion conductor is facilitated, the fast ion conductor can be better coated outside the lithium-rich manganese-based precursor, and the lithium-rich manganese-based anode material with a stable structure is ensured to be obtained.
In one embodiment, the fast ion conductor precursor includes lithium carbonate and zirconium nitrate. The method can be understood that the precursor of the fast ion conductor comprises lithium carbonate and zirconium nitrate, and lithium zirconate is generated after combination, namely, the fast ion conductor formed in the subsequent water-bath evaporation operation is lithium zirconate, the lithium zirconate is a material with wider industrial application, and the lithium zirconate with multiple monoclinic phases has higher lithium atom density and good thermal stability and electrical conductivity, so that the lithium zirconate also has a plurality of applications in the field of lithium batteries.
In one embodiment, the fast ion conductor precursor includes lithium carbonate and titanium nitrate. It can be understood that the precursor of the fast ion conductor comprises lithium carbonate and titanium nitrate, lithium titanate is generated after combination, that is, the fast ion conductor formed in the subsequent water bath evaporation operation is lithium titanate, the lithium titanate has no volume change in the charge-discharge reaction, the cycle performance is excellent, the fast ion conductor is known as a zero-strain material, the lithium titanate is adopted as the fast ion conductor, a fast lithium ion channel can be provided, the migration of lithium ions in the charge-discharge process is facilitated, the ionic conductivity of the prepared rich lithium manganese base anode material is greatly improved, in addition, the volume of the lithium titanate has no change, the structural stability of the prepared rich lithium manganese base anode material is further improved, and the quality of a finished product is better.
S130, performing water bath evaporation operation on the mixed solution to obtain a lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, and performing annealing treatment after drying operation on the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor to obtain the lithium-rich manganese-based positive electrode material.
It should be noted that, by performing water bath evaporation operation on the mixed solution, in the water bath heating process, the fast ion conductor precursor in the mixed solution is combined to generate the fast ion conductor and is attached to the surface of the lithium-rich manganese-based precursor, and the water bath evaporation can make the mixed solution heated uniformly, that is, the fast ion conductor precursor, the ammonia water and the lithium-rich manganese-based precursor are heated uniformly, so as to avoid sintering phenomenon due to over-high local heating, and meanwhile, avoid insufficient local heating and low temperature which affect the generation of the fast ion conductor, therefore, the water bath evaporation is beneficial to ensuring the stable generation of the fast ion conductor and ensuring that the fast ion conductor is better attached to the surface of the lithium-rich manganese-based precursor, the heating effect is good, and the fast ion conductor is attached to the surface of the lithium-rich manganese-based precursor, on one hand, the direct contact between the electrolyte and the lithium-rich manganese-based precursor is, the function of stabilizing the structure of the lithium-rich manganese-based precursor is achieved, so that the cycling stability of the lithium-rich manganese-based precursor is improved; on the other hand, the fast ion conductor can provide a fast lithium ion channel, and is beneficial to the migration of lithium ions in the charging and discharging process, so that the ionic conductivity of the prepared lithium-rich manganese-based anode material is greatly improved, namely the multiplying power performance of the lithium-rich manganese-based anode material is improved.
In one embodiment, in the water bath evaporation operation of the mixed solution, the water bath evaporation temperature is controlled to be 60-90 ℃, and the water bath evaporation time is controlled to be 5-20 h. It can be understood that the adoption of water bath evaporation is beneficial to ensuring uniform heating, ensuring the formation and coating of the fast ion conductor outside the lithium-rich manganese-based precursor, controlling the water bath evaporation temperature to be 60-90 ℃, can avoid the over-high or over-low heating temperature, ensure the normal operation of the reaction, when the temperature is higher than 90 ℃, the phenomenon of local overhigh heating is easy to occur due to overhigh water bath evaporation temperature, the formation of a fast ion conductor and the normal operation of coating the fast ion conductor outside the lithium-rich manganese-based precursor are influenced, the quality of a finished product is influenced, when the temperature is lower than 60 ℃, the water bath evaporation temperature is too low, the formation of the fast ion conductor and the coating speed outside the lithium-rich manganese-based precursor are slow, even the situation that the fast ion conductor cannot be formed occurs, therefore, the evaporation temperature of the water bath is preferably controlled to be 60-90 ℃, the evaporation time of the water bath is preferably controlled to be 5-20 h, therefore, the formation of the fast ion conductor and the process of coating the fast ion conductor outside the lithium-rich manganese-based precursor are ensured to be complete and complete.
In one embodiment, after the mixed solution is subjected to water bath evaporation to obtain the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor is further subjected to cleaning operation. It can be understood that after the lithium-rich manganese-based anode material crystal coated by the fast ion conductor is obtained, the lithium-rich manganese-based anode material crystal coated by the fast ion conductor is also cleaned, ammonia water and other impurities on the surface of the lithium-rich manganese-based anode material crystal coated by the fast ion conductor can be removed, and the lithium-rich manganese-based anode material crystal coated by the fast ion conductor is prevented from containing too many impurities, so that the purity of the lithium-rich manganese-based anode material prepared subsequently is improved, and the quality of the finished product of the lithium-rich manganese-based anode material is greatly improved.
Compared with the prior art, the invention has at least the following advantages:
the invention provides lithium-manganese-based precursor slurry, obtains a lithium-rich manganese-based precursor after drying and sintering operation, then can obtain a mixed solution which is uniformly mixed by premixing the fast ion conductor precursor and the lithium-rich manganese-based precursor, is favorable for ensuring the normal operation of subsequent water-bath evaporation operation, can uniformly attach the fast ion conductor precursor to the surface of the lithium-rich manganese-based precursor to generate a fast ion conductor when performing the water-bath evaporation operation, and coats the fast ion conductor on the surface of the lithium-rich manganese-based precursor, thereby being favorable for avoiding the direct contact between electrolyte and the lithium-rich manganese-based precursor, inhibiting the reaction between the electrolyte and the lithium-rich manganese-based precursor, playing a role of stabilizing a lithium-rich manganese structure, being favorable for improving the cycling stability of the lithium-rich manganese-based anode material obtained by subsequent preparation, and providing a lithium ion fast channel by the generated fast ion conductor, the lithium-rich manganese-based anode material is beneficial to the migration of lithium ions in the charging and discharging processes, and the ionic conductivity of the lithium-rich manganese-based anode material is improved, namely the multiplying power performance of the lithium-rich manganese-based anode material is improved. The preparation method has simple process, and the prepared lithium-rich manganese-based positive electrode material has good consistency, high capacity and good performance.
The following is a detailed description of the embodiments.
Example 1
Adding a lithium-containing compound and ammonium carbonate into deionized water to obtain a first stock solution, adding a manganese-containing compound into deionized water to obtain a second stock solution, adding the first stock solution into the second stock solution to obtain a blended solution, adjusting the pH of the blended solution to 5.1 to obtain an acidic blended solution, adding a doping agent into the acidic blended solution to obtain a lithium-rich manganese-based raw material slurry, drying the lithium-rich manganese-based raw material slurry, sintering, controlling the temperature rise speed to be 2 ℃/min, the sintering temperature to be 400 ℃, the sintering time to be 3h, carrying out first-stage sintering, controlling the temperature rise speed to be 2 ℃/min, the sintering temperature to be 800 ℃, the sintering time to be 10h, and carrying out second-stage sintering to obtain a lithium-rich manganese-based precursor Li1+xMn1-x-yMyO3，0<x<0.5，0<y<0.5；
Providing a fast ion conductor precursor, wherein the fast ion conductor precursor comprises lithium carbonate and zirconium nitrate, dissolving the fast ion conductor precursor in ultrapure water by a chemical deposition method, stirring, adding ammonia water and the lithium-rich manganese-based precursor, and stirring and mixing to obtain a mixed solution;
and (3) performing water bath evaporation operation on the mixed solution, controlling the water bath evaporation temperature to be 60 ℃ and the water bath evaporation time to be 5h to obtain a lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, performing cleaning operation on the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, drying the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, and then performing annealing treatment to obtain the lithium-rich manganese-based positive electrode material of the embodiment 1.
Example 2
Adding a lithium-containing compound and ammonium carbonate into deionized water to obtain a first stock solution, adding a manganese-containing compound into deionized water to obtain a second stock solution, adding the first stock solution into the second stock solution to obtain a blended solution, adjusting the pH of the blended solution to 5.8 to obtain an acidic blended solution, adding a doping agent into the acidic blended solution to obtain a lithium-rich manganese-based raw material slurry, drying the lithium-rich manganese-based raw material slurry, sintering, controlling the temperature rise speed to be 3 ℃/min, the sintering temperature to be 500 ℃, the sintering time to be 5h, carrying out first-stage sintering, controlling the temperature rise speed to be 3 ℃/min, the sintering temperature to be 850 ℃, the sintering time to be 15h, and carrying out second-stage sintering to obtain a lithium-rich manganese-based precursor Li1+xMn1-x-yMyO3，0<x<0.5，0<y<0.5；
Providing a fast ion conductor precursor, wherein the fast ion conductor precursor comprises lithium carbonate and zirconium nitrate, dissolving the fast ion conductor precursor in ultrapure water by a chemical deposition method, stirring, adding ammonia water and the lithium-rich manganese-based precursor, and stirring and mixing to obtain a mixed solution;
and (3) performing water bath evaporation operation on the mixed solution, controlling the water bath evaporation temperature to be 75 ℃, and the water bath evaporation time to be 12 hours to obtain a lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, performing cleaning operation on the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, drying the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, and then performing annealing treatment to obtain the lithium-rich manganese-based positive electrode material of the embodiment 2.
Example 3
Adding a lithium-containing compound and ammonium carbonate into deionized water to obtain a first stock solution, and adding a manganese-containing compound into deionized water to obtainAdding the first stock solution into the second stock solution to obtain a blended solution, adjusting the pH of the blended solution to 6.3 to obtain an acidic blended solution, adding a doping agent into the acidic blended solution to obtain a lithium-rich manganese-based raw material slurry, drying the lithium-rich manganese-based raw material slurry, sintering, controlling the temperature rise speed to be 4 ℃/min, the sintering temperature to be 600 ℃, the sintering time to be 8h, carrying out first-stage sintering, controlling the temperature rise speed to be 4 ℃/min, the sintering temperature to be 900 ℃, the sintering time to be 20h, and carrying out second-stage sintering to obtain a lithium-rich manganese-based precursor Li1+xMn1-x-yMyO3，0<x<0.5，0<y<0.5；
Providing a fast ion conductor precursor, wherein the fast ion conductor precursor comprises lithium carbonate and zirconium nitrate, dissolving the fast ion conductor precursor in ultrapure water by a chemical deposition method, stirring, adding ammonia water and the lithium-rich manganese-based precursor, and stirring and mixing to obtain a mixed solution;
and (3) performing water bath evaporation operation on the mixed solution, controlling the water bath evaporation temperature to be 90 ℃, and the water bath evaporation time to be 20 hours to obtain a lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, performing cleaning operation on the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, drying the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, and then performing annealing treatment to obtain the lithium-rich manganese-based positive electrode material of the embodiment 3.
Example 4
Adding a lithium-containing compound and ammonium carbonate into deionized water to obtain a first stock solution, adding a manganese-containing compound into deionized water to obtain a second stock solution, adding the first stock solution into the second stock solution to obtain a blending solution, adjusting the pH of the blending solution to 6.3 to obtain an acidic blending solution, adding a doping agent into the acidic blending solution to obtain a lithium-rich manganese-based raw material slurry, drying the lithium-rich manganese-based raw material slurry, sintering, controlling the temperature rise speed to be 4 ℃/min, the sintering temperature to be 600 ℃, and controlling the sinteringThe time is 8h, a first-stage sintering operation is carried out, the temperature rise speed is controlled to be 4 ℃/min, the sintering temperature is controlled to be 900 ℃, the sintering time is controlled to be 20h, and a second-stage sintering operation is carried out to obtain a lithium-rich manganese-based precursor Li1+xMn1-x-yMyO3，0<x<0.5，0<y<0.5；
Providing a fast ion conductor precursor, wherein the fast ion conductor precursor comprises lithium carbonate and titanium nitrate, dissolving the fast ion conductor precursor in ultrapure water by a chemical deposition method, stirring, adding ammonia water and the lithium-rich manganese-based precursor, and stirring and mixing to obtain a mixed solution;
and (3) performing water bath evaporation operation on the mixed solution, controlling the water bath evaporation temperature to be 90 ℃, and the water bath evaporation time to be 20 hours to obtain a lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, performing cleaning operation on the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor, and performing annealing treatment after drying operation on the lithium-rich manganese-based positive electrode material crystal coated by the fast ion conductor to obtain the lithium-rich manganese-based positive electrode material of the embodiment 4.
Comparative example 1
Adding a lithium-containing compound and ammonium carbonate into deionized water to obtain a first stock solution, adding a manganese-containing compound into deionized water to obtain a second stock solution, adding the first stock solution into the second stock solution to obtain a blended solution, adjusting the pH of the blended solution to 6.3 to obtain a lithium-rich manganese-based raw material slurry, drying the lithium-rich manganese-based raw material slurry, and then performing sintering operation, wherein the temperature rise speed is controlled to be 4 ℃/min, the sintering temperature is controlled to be 600 ℃, the sintering time is controlled to be 8h, the first-stage sintering operation is performed, the temperature rise speed is controlled to be 4 ℃/min, the sintering temperature is 900 ℃, the sintering time is 20h, and the second-stage sintering operation is performed to obtain the lithium-rich manganese-based anode material of the comparative example 1.
Comparative example 2
Adding a lithium-containing compound and ammonium carbonate into deionized water to obtain a first stock solution, adding a manganese-containing compound into deionized water to obtain a second stock solution, adding the first stock solution into the second stock solution to obtain a blended solution, adjusting the pH of the blended solution to 6.3 to obtain an acidic blended solution, adding a doping agent into the acidic blended solution to obtain a lithium-rich manganese-based raw material slurry, drying the lithium-rich manganese-based raw material slurry, sintering, controlling the temperature rise speed to be 4 ℃/min, the sintering temperature to be 600 ℃, the sintering time to be 8h, carrying out first-stage sintering, controlling the temperature rise speed to be 4 ℃/min, the sintering temperature to be 900 ℃, the sintering time to be 20h, and carrying out second-stage sintering to obtain the lithium-rich manganese-based positive electrode material of the comparative example 2.
Experiment: preparing electrodes from the lithium-rich manganese-based positive electrode materials obtained in the embodiments 1 to 4 and the comparative examples 1 and 2, assembling the electrodes to obtain a lithium ion battery, and testing: (1) charge and discharge performance under different multiplying powers; (2) charge and discharge performance at a current density of 0.5C. The test results show that the lithium ion batteries of the embodiments of the invention have excellent charge and discharge performance at different multiplying powers and excellent cycle performance at a current density of 0.5C, compared with comparative example 1 and comparative example 2, and are shown in fig. 2 and fig. 3 in detail. In order to avoid the data in the graph being too dense and difficult to distinguish, only the data of example 3 and the data of comparative example 2 are selected in fig. 2, and the result is shown in fig. 2. The effects of other examples are similar to those of example 3, and are not repeated, and fig. 3 only selects the data of example 3 to be plotted with the data of comparative example 1 and comparative example 2, and the result is shown in fig. 3. The effects of the other embodiments are similar to those of embodiment 3, and are not described again.
Fig. 2 is a graph comparing the charge and discharge performance of example 3 of the present invention and comparative example 2 at different rates. Wherein M-LLO represents the lithium ion battery of comparative example 2; ST-LLO represents the lithium ion battery of example 3. As can be seen from fig. 2, the lithium ion batteries of examples 1 to 4 have better charge and discharge performance and significantly improved rate performance, compared to comparative example 2.
Fig. 3 is a graph comparing charge and discharge performance at a current density of 0.5C for the batteries of example 3, comparative example 1 and comparative example 2 of the present invention. Wherein 1 represents the lithium ion battery of comparative example 1; 2 represents the lithium ion battery of comparative example 2; and 3 represents the lithium ion battery of example 3. As can be seen from fig. 3, the charge and discharge performance of the lithium ion batteries of examples 1 to 4 is better than that of comparative examples 1 and 2 at a current density of 0.5C, which proves that the cycle performance of the cathode material prepared by the method of the present invention is better under the condition of the current density of 0.5C, the specific discharge capacity after 100 cycles is maintained at 190mAh/g, the cycle performance of the lithium-rich manganese-based cathode material coated on the surface of the fast ion conductor is obviously improved, the preparation process is simple, and the production benefit is improved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The preparation method of the lithium-rich cathode material is characterized by comprising the following steps of:
providing lithium-rich manganese-based raw material slurry, drying the lithium-rich manganese-based raw material slurry, and then sintering to obtain a lithium-rich manganese-based precursor Li1+xMn1-x-yMyO3，0<x<0.5，0<y<0.5；
Providing a fast ion conductor precursor, dissolving the fast ion conductor precursor in ultrapure water by a chemical deposition method, stirring, adding ammonia water and the lithium-rich manganese-based precursor, and stirring and mixing to obtain a mixed solution;
and performing water-bath evaporation operation on the mixed solution to obtain a lithium-rich manganese-based anode material crystal coated by the fast ion conductor, and performing annealing treatment after drying operation on the lithium-rich manganese-based anode material crystal coated by the fast ion conductor to obtain the lithium-rich manganese-based anode material.
2. The preparation method of the lithium-rich cathode material according to claim 1, wherein in the operation of providing the lithium-rich manganese-based raw material slurry, a lithium-containing compound and a precipitant are added to deionized water to obtain a first stock solution, a manganese-containing compound is added to deionized water to obtain a second stock solution, the first stock solution is added to the second stock solution to obtain a blended solution, the pH of the blended solution is adjusted to 5.1 to 6.3 to obtain an acidic blended solution, and a dopant is added to the acidic blended solution to obtain the lithium-rich manganese-based raw material slurry.
3. The method according to claim 2, wherein the lithium-containing compound is at least one of lithium carbonate, lithium hydroxide, lithium acetate, and lithium nitrate.
4. The method for preparing a lithium-rich cathode material according to claim 2, wherein the manganese-containing compound is at least one of manganese nitrate, manganese sulfate and manganese acetate.
5. The method according to claim 2, wherein the precipitant is at least one of ammonium carbonate and citric acid.
6. The method of claim 1, wherein the fast ion conductor precursor comprises lithium carbonate and zirconium nitrate.
7. The method according to claim 1, wherein the fast ion conductor precursor comprises lithium carbonate and titanium nitrate.
8. The method for preparing a lithium-rich cathode material according to claim 6 or 7, wherein in the sintering operation, a first-stage sintering operation is performed while controlling a temperature rise rate to 2 ℃/min to 4 ℃/min, a sintering temperature to 400 ℃ to 600 ℃, and a sintering time to 3h to 8h, and a second-stage sintering operation is performed while controlling a temperature rise rate to 2 ℃/min to 4 ℃/min, a sintering temperature to 800 ℃ to 900 ℃, and a sintering time to 10h to 20 h.
9. The method for preparing the lithium-rich cathode material according to claim 1, wherein the water bath evaporation temperature is controlled to be 60 ℃ to 90 ℃ and the water bath evaporation time is controlled to be 5h to 20h in the water bath evaporation operation of the mixed solution.
10. The method for preparing the lithium-rich manganese-based positive electrode material as claimed in claim 1, wherein the mixed solution is subjected to water bath evaporation to obtain a fast ion conductor coated lithium-rich manganese-based positive electrode material crystal, and then the fast ion conductor coated lithium-rich manganese-based positive electrode material crystal is subjected to cleaning operation.
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