CN114447290A - Modification method and application of lithium-rich manganese-based positive electrode material of lithium ion battery - Google Patents

Modification method and application of lithium-rich manganese-based positive electrode material of lithium ion battery Download PDF

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CN114447290A
CN114447290A CN202111570863.9A CN202111570863A CN114447290A CN 114447290 A CN114447290 A CN 114447290A CN 202111570863 A CN202111570863 A CN 202111570863A CN 114447290 A CN114447290 A CN 114447290A
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lithium
positive electrode
electrode material
ion battery
rich manganese
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CN114447290B (en
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李喜飞
郝猷琛
刘�文
王晶晶
李文斌
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Xian University of Technology
Shaanxi Coal and Chemical Technology Institute Co Ltd
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    • H01M10/05—Accumulators with non-aqueous electrolyte
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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 discloses a method for modifying a lithium-rich manganese-based positive electrode material of a lithium ion battery, which comprises the steps of dissolving a complexing agent in deionized water under certain conditions to obtain a complexing solution; adding a proper amount of positive electrode material into the solution, fully stirring and dispersing, sealing at normal temperature and keeping for a period of time at constant temperature, thus obtaining the in-situ growth, compact and thin-layer Prussian-blue-like coated and modified lithium ion battery positive electrode material which has good cycle stability, excellent rate performance and reliable safety, and the preparation method has the characteristics of low cost, simple operation, environmental friendliness and the like, and can be applied to industrial production on a large scale; the invention also discloses an application of the Prussian-like blue coating modified lithium-rich manganese-based positive electrode material of the lithium ion battery prepared by the modification method of the lithium-rich manganese-based positive electrode material in the aspect of preparing the lithium ion battery.

Description

Modification method and application of lithium-rich manganese-based positive electrode material of lithium ion battery
Technical Field
The invention belongs to the technical field of energy storage and conversion, and mainly relates to a method for modifying a lithium-rich manganese-based positive electrode material of a lithium ion battery.
The invention also relates to the application of the lithium-rich manganese-based cathode material of the lithium ion battery in the aspect of preparing the lithium ion battery.
Background
The lithium ion battery as an efficient energy storage device plays an important role in the utilization and popularization of clean energy, and particularly becomes a hot spot for the disputed research and development of various countries in the world under the background of 'double carbon'. The energy-saving battery has the characteristics of small volume, light weight, high specific energy, no memory effect, long cycle life and the like, and is widely applied to the fields of mobile equipment, electric automobiles and the like. As a power source of various electric equipment, the performance of the lithium ion battery directly determines the service life and the endurance mileage of the equipment. In order to further develop the electric automobile with long endurance capacity, the lithium-rich manganese-based anode with higher theoretical specific capacity becomes a core and a key material which needs to be overcome for the next generation of high-performance lithium ion battery.
Aiming at the problem of rapid capacity attenuation of a lithium-rich manganese-based positive electrode, coating modification is a common technical scheme, and the method is mainly a protection method for forming a uniform coating layer on the surface of target material particles, wherein the coating modification is a material with excellent physical and chemical properties. Researchers use the Prussian-like blue to coat the anode material, and the result shows that the Prussian-like blue coated and modified anode material has higher capacity, good rate performance and excellent cycle performance.
The existing preparation method of the coated modified lithium-rich manganese-based positive electrode material of the lithium ion battery mainly comprises a high-energy ball milling method, a sol-gel method and the like, for example, Chinese patent CN202010847189.3, which has the problems of rough coating effect, complex process steps and the like, and although the rate performance of the positive electrode material is improved, the positive electrode material does not show good effect in the aspect of cycle life. Therefore, the development of a preparation method which is low in cost, simple in process, environment-friendly and remarkably prolonged in cycle life is imperative.
Disclosure of Invention
The invention aims to provide a method for modifying a lithium-rich manganese-based positive electrode material of a lithium ion battery, which solves the problem of capacity attenuation caused by different inducements of the lithium-rich manganese-based positive electrode material of the lithium ion battery under high multiplying power and low multiplying power.
The invention also aims to provide a modification method of the lithium-rich manganese-based cathode material of the lithium ion battery, and application of the obtained Prussian-like blue coated modified lithium-rich manganese-based cathode material of the lithium ion battery in preparation of the lithium ion battery.
The technical scheme adopted by the invention is that the method for modifying the lithium-rich manganese-based anode material of the lithium ion battery is implemented according to the following steps:
step 1, dispersing a complexing agent in deionized water, and fully stirring and dissolving to obtain a complexing solution;
step 2, adding the lithium-rich manganese-based positive electrode material into the solution according to the dosage ratio, stirring to disperse positive electrode particles, and then sealing and maintaining the complexing solution soaked with the positive electrode material at a constant temperature;
and 3, filtering the product obtained in the step 2, washing the product for multiple times by using deionized water and absolute ethyl alcohol, and then preserving the heat of a filter cake in a vacuum drying oven to obtain the Prussian-like blue coated lithium ion battery anode material.
The first technical scheme of the invention is also characterized in that:
wherein the complexing agent in the step 1 is ferrocyanide;
wherein the complexing agent is K4Fe(CN)6、Na4Fe(CN)6、Li4Fe(CN)6Or at least one of its corresponding hydrates;
wherein the lithium-rich manganese-based positive electrode material in the step 2 is as follows: xLi with a layered structure2MnO3-(1-x)LiMO2A material;
wherein the mol ratio of the complexing agent to the lithium-rich manganese-based positive electrode material in the step 2 is 1: 10-1: 1; the concentration of the complexing solution is 0.05-0.5 mol/L;
wherein in the step 2, the mixture is stirred for 3-10 min, the constant temperature is 20-60 ℃, and the mixture is sealed for 6-24 h;
cleaning with deionized water and absolute ethyl alcohol for at least 3 times in the step 3, keeping the temperature in a vacuum drying oven at 60 ℃, and keeping the temperature for 6-12 hours;
wherein the thickness of the Prussian-like blue coating layer in the step 3 is 0.5-5 nm, and the molar ratio of substances is 0.01-0.10% of the amount of substances of the positive electrode material.
The second technical scheme of the invention is that the Prussian-like blue coated modified lithium-rich manganese-based positive electrode material of the lithium ion battery prepared by the method is applied to the preparation of the lithium ion battery.
The method comprises the following steps: grinding and fully mixing a Prussian blue-like coated modified lithium ion lithium-rich manganese-based positive electrode material, conductive carbon black (a conductive agent), polyvinylidene fluoride (PVDF binder) and a small amount of N-methyl pyrrolidone (NMP) to form uniform slurry, coating the uniform slurry on an aluminum foil substrate to serve as a test electrode, wherein the electrolyte is 1M LiPF6DMC: EC: EMC (V: V: V: 1:1), and a lithium metal sheet is used as a counter electrode to manufacture a button cell; the experimental results show that: prussian blue-like coated lithium-rich manganese-based positive electrode material Li1.2Mn0.54Ni0.13Co0.13O2After 100 times of charge and discharge tests under low multiplying power (50mA/g), the capacity can still reach 220mA h/g, and the capacity retention rate is 91.4%; after 300 times of charge and discharge tests under high multiplying power (250mA/g), the capacity is kept at 155mA h/g, and the capacity retention rate is 87.8%;
the invention has the advantages that
The coating layer in the functional Prussian-blue-like coated lithium ion battery lithium-rich manganese-based positive electrode material prepared by the invention is compact and uniform and has good stability, on one hand, the overflow of lattice oxygen and the side reaction of an electrolyte and a positive electrode interface can be effectively inhibited under low multiplying power, and on the other hand, the functional Prussian-blue-like coated lithium ion battery lithium-rich manganese-based positive electrode material is also effective for capacity attenuation caused by electrochemical polarization behavior under high multiplying power. Under different multiplying powers, the interface stability can be effectively optimized, the cycle life of the lithium ion battery is prolonged, and the electrochemical performance of the lithium ion battery is improved;
the method for preparing the functional Prussian-blue-like coated lithium ion battery lithium-rich manganese-based anode material fully utilizes the strong complexation between the complexing agent and metal ions, and takes metal atoms on the surface of the lithium-rich manganese-based anode as a metal source to perform in-situ complexation with the complexing agent to construct a conformal interface film. On one hand, a compact, uniform and good-stability Prussian-like blue coating layer is formed on the surface of the lithium-rich manganese-based positive electrode material, so that the side reaction of an electrolyte and a positive electrode interface can be effectively reduced under low multiplying power, meanwhile, the overflow of oxygen is inhibited, and the reversibility of lattice oxygen is improved; on the other hand, the electrochemical polarization behavior of the lithium-rich manganese-based anode under high multiplying power is weakened, the cycle reversibility of the lithium-rich manganese-based anode material under high multiplying power and low multiplying power is obviously improved, the cycle life of the battery is greatly prolonged, and the electrochemical performance of the lithium-rich manganese-based anode of the lithium ion battery under different multiplying power is improved;
the Prussian blue-like coating modified lithium ion battery lithium-rich manganese-based positive electrode material is synthesized in one step through in-situ complexation, the method is simple in process, low in cost, environment-friendly and suitable for large-scale application, and the defects of complex process, high cost, rough coating effect, poor controllability and the like in the traditional coating modification method are overcome;
the Prussian-blue-like coated and modified lithium-rich manganese-based positive electrode material of the lithium ion battery is synthesized in one step through in-situ complexing reaction, and the spontaneous complexing reaction at the contact interface of positive electrode particles and a complexing solution simplifies the process, mildens the conditions and realizes large-scale preparation;
the Prussian-like blue coated modified lithium-rich manganese-based positive electrode material for the lithium ion battery, which is prepared by the invention, is applied to the lithium ion battery, shows higher reversible capacity, good rate performance and excellent cycle performance, and greatly prolongs the cycle life of the lithium ion battery under different rates.
Drawings
FIG. 1 shows Li before and after Prussian-like blue coating modification in an embodiment of a method for modifying a lithium-rich manganese-based cathode material of a lithium ion battery1.2Mn0.54Ni0.13Co0.13O2Scanning electron microscope images of the anode material;
FIG. 2 shows an embodiment of a method for modifying a lithium-rich manganese-based cathode material for a lithium ion battery, in which Prussian-like blue is coated and modified to obtain Li1.2Mn0.54Ni0.13Co0.13O2XPS refinement of Fe 2p and Mn 2p of positive electrode material at different potentialsA drawing;
FIG. 3 shows an example of a method for modifying a lithium-rich manganese-based positive electrode material for a lithium ion battery according to the present invention, in which Prussian-like blue is coated and modified to obtain Li1.2Mn0.54Ni0.13Co0.13O2A high-resolution scanning transmission electron microscope image of the anode material;
FIG. 4 shows Li before and after Prussian-like blue coating modification in an embodiment of a method for modifying a lithium-rich manganese-based cathode material of a lithium ion battery according to the present invention1.2Mn0.54Ni0.13Co0.13O2A cycle performance diagram of the anode material under low multiplying power;
FIG. 5 shows Li before and after Prussian-like blue coating modification in an embodiment of a method for modifying a lithium-rich manganese-based cathode material of a lithium ion battery according to the present invention1.2Mn0.54Ni0.13Co0.13O2A cycle performance diagram of the anode material under high magnification;
FIG. 6 shows Li before and after Prussian-like blue coating modification in an embodiment of a method for modifying a lithium-rich manganese-based cathode material of a lithium ion battery according to the present invention1.2Mn0.54Ni0.13Co0.13O2And circulating a corresponding polarization diagram under high magnification of the anode material.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
According to the technical scheme, a certain amount of complexing agent is dispersed in a certain amount of deionized water, the lithium-rich manganese-based positive electrode material is immersed in the solution, the complexing agent can be fully contacted with the lithium-rich manganese-based positive electrode, and then metal elements contained in the lithium-rich manganese-based positive electrode are used as metal centers for complexing, so that a Prussian blue-like coating layer is obtained;
the invention mainly researches the Prussian-like blue coated anode material Li1.2Mn0.54Ni0.13Co0.13O2The preparation method and the application mainly solve the problems of short cycle life and poor rate capability of the lithium-rich manganese-based anode of the lithium ion battery.
Example 1
Step 1, adding K4Fe(CN)6Dispersing in deionized water with concentration controlled at 0.1mol/L, stirring for 10min to dissolve completely to obtain potassium ferrocyanide solution;
step 2, taking 0.3g of lithium-rich manganese-based positive electrode material Li1.2Mn0.54Ni0.13Co0.13O2Adding the solution (the molar ratio of the complexing agent to the anode is 1:5), stirring for 5min to ensure that the solution is fully contacted with the anode particles, and then standing the complexing solution soaked with the anode material at a constant temperature of 20 ℃ for 24h to obtain a Prussian-like blue coated modified lithium-rich manganese-based anode material;
step 3, filtering the product obtained in the step 2, washing the product for 3 times by using absolute ethyl alcohol, and then keeping the temperature of a filter cake in a vacuum drying oven at 60 ℃ for 12 hours to obtain a Prussian-like blue coated lithium-rich manganese-based positive electrode material;
0.64g of Prussian-blue-like coated modified Li prepared as described above was weighed1.2Mn0.54Ni0.13Co0.13O2Adding 0.08g of conductive carbon black serving as a conductive agent and 0.08g of PVDF serving as a binder into a positive electrode material, dropwise adding a small amount of NMP, grinding and uniformly mixing to form uniform slurry, coating the uniform slurry on an aluminum foil serving as a test electrode, and using 1M LiPF6DMC: EC: EMC (V: V ═ 1:1:1), test charge and discharge performance (current density 50mA/g and 250mA/g, respectively);
coating modified Li prepared in this example1.2Mn0.54Ni0.13Co0.13O2The material characteristics and the electrochemical properties of the cathode material are shown in the following figures 1-6:
FIG. 1 is a scanning electron micrograph from which it can be seen that Li has not been modified by coating1.2Mn0.54Ni0.13Co0.13O2The anode material has a sphere-like structure consisting of primary particles with the size of 200-500nm, and the particles with fine surfaces are generally considered as residual lithium. Li after in-situ complexing treatment1.2Mn0.54Ni0.13Co0.13O2The shape and the size of the positive electrode material particles are not obviously changed, the characteristic of conformal coating of a coating layer is verified, and meanwhile, the disappeared fine residual lithium particles are caused by water washing;
FIG. 2 is a class diagramXPS fine spectrograms of Fe 2p and Mn 2p at different potentials after modification by coating of the Russian blue, and the XPS fine spectrograms show that after in-situ complexation, the Prussian blue-like coating layer contains [ Fe (CN) ]6]4-The lithium manganese oxide can participate in redox reaction, and the potential of the reaction is consistent with that of the lithium manganese oxide-based anode, so that part of overload current can be shared in the reaction process of the anode, and the problem of polarization under high multiplying power is further relieved;
FIG. 3 shows modified Prussian-like blue Li1.2Mn0.54Ni0.13Co0.13O2A high-resolution transmission electron microscope image of the cathode material indicates that the amorphous Prussian blue-like ultrathin, compact and uniform coating is carried out on the surface of the cathode material;
FIG. 4 shows Li before and after coating modification1.2Mn0.54Ni0.13Co0.13O2The long cycle performance diagram of the cathode material under low multiplying power shows that the modified Li is coated by the Prussian-like blue1.2Mn0.54Ni0.13Co0.13O2When the anode material is discharged at a constant current at room temperature (50mA/g), the specific capacity can still be kept at 220mA h/g after 100 times of circulation, and the capacity retention rate of the anode material is up to 91.2 percent and is obviously superior to that of an unmodified material (78 percent);
FIG. 5 shows Li before and after coating modification1.2Mn0.54Ni0.13Co0.13O2The long cycle performance diagram of the anode material under high multiplying power shows that the Prussian-like blue is adopted to coat the modified Li1.2Mn0.54Ni0.13Co0.13O2When the anode material is discharged at a constant current (250mA/g) at room temperature, the specific capacity can still be maintained at 155mA h/g after the anode material is cycled for 300 times, the corresponding capacity retention rate is 87.8%, and the capacity retention rate of an unmodified material under the same condition is only 50.5%;
FIG. 6 is Li before and after coating modification1.2Mn0.54Ni0.13Co0.13O2The polarization pattern corresponding to long cycle under high magnification of the anode material is obviously different before and after modification after 50 cycles, the polarization of the unmodified material is continuously enlarged, and the Prussian-blue-like coated and modified Li1.2Mn0.54Ni0.13Co0.13O2The anode material is maintained at a lower polarization level, which shows that the existence of the Prussian-like blue coating layer obviously reduces the polarization behavior under high rate, thereby maintaining stable long-cycle performance;
example 2
Step 1, adding K4Fe(CN)6Dispersing in deionized water with concentration of 0.5mol/L, stirring for 10min to dissolve completely to obtain potassium ferrocyanide solution;
step 2, taking 0.3g of lithium-rich manganese-based positive electrode material Li1.2Mn0.54Ni0.13Co0.13O2Adding the solution (the molar ratio of the complexing agent to the anode is 1:1), stirring for 5min to ensure that the solution is fully contacted with anode particles, and then standing the complexing solution soaked with the anode material at a constant temperature of 40 ℃ for 12h to obtain a Prussian-like blue coated modified lithium-rich manganese-based anode material;
step 3, filtering the product obtained in the step 2, washing the product for 3 times by using absolute ethyl alcohol, and then keeping the temperature of a filter cake in a vacuum drying oven at 60 ℃ for 12 hours to obtain a Prussian-like blue coated lithium-rich manganese-based positive electrode material;
0.64g of Prussian-blue-like coated modified Li prepared as described above was weighed1.2Mn0.54Ni0.13Co0.13O2Adding 0.08g of conductive carbon black serving as a conductive agent and 0.08g of PVDF serving as a binder into a positive electrode material, dropwise adding a small amount of NMP, grinding and uniformly mixing to form uniform slurry, coating the uniform slurry on an aluminum foil serving as a test electrode, and using 1M LiPF6DMC: EC: EMC (V: V ═ 1:1:1), test charge and discharge performance (current density 50mA/g and 250mA/g, respectively);
in the embodiment, the concentration of the complexing agent and the constant temperature are improved, so that the complexing reaction is accelerated, and the thickness of the coating layer can be improved by the relatively large-dosage-ratio complexing agent. Tests prove that when the lithium-rich manganese-based positive electrode material coated and modified in the embodiment is subjected to constant current discharge at room temperature (50mA/g), the specific capacity can still be kept at 212mAh/g after 100 times of circulation, which is better than 177.8mAh/g of an unmodified material; meanwhile, the capacity of the modified material after 300 cycles under high multiplying power (250mA/g) is 132.4mAh/g, and the capacity of the unmodified material is 101.1 mAh/g. The result shows that the amount of the complexing agent and the reaction temperature are controlled based on the complexation reaction of the complexing agent and the metal atom center, compared with example 1, the prussian blue-like coated modified lithium-rich manganese-based positive electrode in the embodiment has the effect of prolonging the cycle life, but the thickness of the coating layer has a great influence on the electrochemical performance, and the thicker the coating layer is, the better the coating layer is.
Comparative example 1
To illustrate the important role of the complexing agent, this comparative example is essentially identical to example 1, except that no K is added during the implementation4Fe(CN)6The other operations as a complexing agent were exactly the same as in example 1. And (3) carrying out suction filtration and drying on the lithium-rich manganese-based positive electrode material soaked in the deionized water to obtain the contrast material.
The morphology of the comparative material was similar to that of the sample obtained in example 1, and the clean surface indicated that the fine residual lithium particles on the surface of the unmodified material could be removed by washing with water.
The lithium-rich manganese-based positive electrode material obtained in comparative example 1 was subjected to the deionized water immersion treatment to prepare an electrode and tested in the same manner as in example 1. The lithium-rich manganese-based positive electrode without the prussian-like blue coating has a significant difference compared with example 1. Under low multiplying power (50mA/g), the capacity of the comparative example material is 197.9mA h/g after 100 cycles, the stability of the comparative example material is obviously weaker than that of the example 1 material, the capacity retention rate is only 81.6 percent and is slightly higher than 78 percent of that of an unmodified material, and the effect of pure deionized water cleaning on the modification of the lithium-rich manganese-based positive electrode is very limited. More obviously, under a high multiplying power (250mA/g), the capacity of the comparative example material is almost attenuated to 0 after being circulated for 300 times, which shows that the lithium-rich manganese-based cathode material soaked by pure deionized water has no great modification effect and is not beneficial to the performance of the material. The comparison example eliminates the modification influence of deionized water cleaning on the lithium-rich manganese-based positive electrode material, and proves that the Prussian-like blue coating layer formed through the in-situ complexing reaction is the important reason for realizing long cycle life of the lithium-rich manganese-based positive electrode under high multiplying power and low multiplying power.
Comparative example 2
To more visually illustrate the effect of the complexing agent, this comparisonExample substantially the same as in example 1, except that process step (1) was carried out with the addition of a small amount of K4Fe(CN)6The other operations as a complexing agent were exactly the same as in example 1. The specific process of the step (1) is as follows: will K4Fe(CN)6Dispersing in deionized water with concentration controlled at 0.025mol/L, stirring for 10min to dissolve completely to obtain potassium ferrocyanide solution. The procedure was then exactly the same as in example 1. And (3) carrying out suction filtration and drying on the lithium-rich manganese-based positive electrode material soaked in the deionized water to obtain the contrast material.
Comparative example 2 the greatest difference compared to comparative example 1 is the addition of a small amount of K4Fe(CN)6And constructing a Prussian blue-like coating layer on the surface of the lithium-rich manganese-based positive electrode as a complexing agent. Even though the amount of complexing agent was compared to 1/5, which was the only amount used in example 1, the difference was very significant compared to comparative example 1, in which no complexing agent was added.
The material obtained in comparative example 2 was used to assemble a battery using the same procedure as in example 1, and the electrochemical properties thereof were tested. Compared with comparative example 1, the material of comparative example 2 has the modification effect basically the same as that of comparative example 1 at low multiplying power, and is slightly better than that of the modified lithium-rich manganese-based positive electrode. The difference performance under high multiplying power is very outstanding, the capacity of the material in the comparative example is rapidly attenuated to 0 under high multiplying power, the specific capacity of 113mA h/g of the material in the comparative example 2 is kept after 300 cycles, the specific capacity is not attenuated to 0, the specific capacity is remarkably superior to 86.8mA h/g of an unmodified material, and the outstanding modification effect of the Prussian-like blue coating layer constructed by the in-situ complexation reaction on the attenuation of the lithium-rich manganese-based positive electrode under high multiplying power and low multiplying power is explained again.

Claims (9)

1. The method for modifying the lithium-rich manganese-based positive electrode material of the lithium ion battery is characterized by comprising the following steps of:
step 1, dispersing a complexing agent in deionized water, and fully stirring and dissolving to obtain a complexing solution;
step 2, adding the lithium-rich manganese-based positive electrode material into the solution according to the dosage ratio, stirring to disperse positive electrode particles, and then sealing and maintaining the complexing solution soaked with the positive electrode material at a constant temperature;
and 3, filtering the product obtained in the step 2, washing the product for multiple times by using deionized water and absolute ethyl alcohol, and then preserving the heat of a filter cake in a vacuum drying oven to obtain the Prussian-like blue coated lithium ion battery anode material.
2. The method for modifying the lithium-rich manganese-based positive electrode material of the lithium ion battery according to claim 1, wherein the complexing agent in the step 1 is ferrocyanide.
3. The method for modifying the lithium-rich manganese-based positive electrode material of the lithium ion battery according to claim 2, wherein the complexing agent is K4Fe(CN)6、Na4Fe(CN)6、Li4Fe(CN)6Or at least one of its corresponding hydrates.
4. The method for modifying the lithium-rich manganese-based positive electrode material of the lithium ion battery according to claim 1, wherein the lithium-rich manganese-based positive electrode material in the step 2 is: xLi with a layered structure2MnO3-(1-x)LiMO2A material.
5. The method for modifying the lithium-rich manganese-based positive electrode material of the lithium ion battery according to claim 1, wherein the molar ratio of the complexing agent to the lithium-rich manganese-based positive electrode material in the step 2 is 1: 10-1: 1; the concentration of the complexing solution is 0.05-0.5 mol/L.
6. The method for modifying the lithium-rich manganese-based positive electrode material of the lithium ion battery according to claim 1, wherein the stirring in the step 2 is carried out for 3-10 min at a constant temperature of 20-60 ℃ and the sealing is carried out for 6-24 h.
7. The method for modifying the lithium-rich manganese-based positive electrode material of the lithium ion battery according to claim 1, wherein in the step 3, deionized water and absolute ethyl alcohol are washed for at least 3 times, the temperature in a vacuum drying box is 60 ℃, and the temperature is kept for 6-12 hours.
8. The method for modifying the lithium-rich manganese-based positive electrode material of the lithium ion battery according to claim 1, wherein the thickness of the Prussian-like blue coating layer in the step 3 is 0.5-5 nm, and the molar ratio of substances is 0.01-0.10% of the amount of substances in the positive electrode material.
9. The application of the Prussian-like blue coated modified lithium-rich manganese-based positive electrode material of the lithium ion battery, which is prepared by the modification method of the lithium-rich manganese-based positive electrode material of the lithium ion battery of claims 1-8, in the preparation of the lithium ion battery.
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