CN112271284A - Modified nickel-rich ternary material and preparation method and application thereof - Google Patents
Modified nickel-rich ternary material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries, and particularly discloses a modified nickel-rich ternary material and a preparation method and application thereof. The modified nickel-rich ternary material comprises a nickel-rich ternary material substrate and a coating layer coated on the surface of the substrate, wherein the coating layer is of a single-layer structure or a double-layer structure, and the single-layer structure is a lithium nickel manganese oxide layer; the double-layer structure consists of an inner lithium manganate layer and an outer lithium nickel manganate layer, and the content omega of the coating layer in the modified nickel-rich ternary material is as follows in percentage by mass: omega is more than or equal to 0.5 percent and less than or equal to 5 percent. The modified nickel-rich ternary material provided by the invention has excellent electrochemical performance under a high-voltage condition, and has excellent capacity, cycle performance and stability.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a modified nickel-rich ternary material and a preparation method and application thereof.
Background
The nickel cobalt lithium manganate serving as the ternary cathode material is considered as the most widely applied cathode material of the power battery at present, but the problems of poor interface stability, recession of the internal structure of secondary particles and the like of the ternary cathode material limit the rapid development of the ternary cathode material, and along with the increase of Ni content, the energy density is continuously improved, the stability is reduced, and the large-scale application of the cathode material is seriously hindered. Therefore, doping and cladding are the most studied for nickel-rich ternary materials. Although the electrochemical performance of the nickel-rich ternary material is improved to a certain extent by the doping and coating method, the dissolution amount of transition metal ions in the ternary material is large under the high oxidation state environment, so that the performance of the ternary material under high voltage (not less than 4.5V) is still not ideal.
At present, in the prior art, a nickel cobalt lithium manganate material with a high nickel content is coated by a nickel cobalt lithium manganate material with a low nickel content to try to modify a ternary material. Although the high-nickel ternary material is coated by the low-nickel ternary material with higher stability, the side reaction of the electrolyte and the electrode material is reduced, and Ni is prevented2+、Co3+、Mn4+The dissolution of metal ions, but because the low-nickel ternary material and the high-nickel ternary material belong to the same series of materials, the voltage platform is oneAlso, the low nickel coating layer is also intolerant to high voltages under high voltage conditions, and does not effectively inhibit the occurrence of side reactions under high voltage conditions.
In addition, the prior art also uses Li in a sol-gel method2MnO3Preparation of LiNi for the housing0.5Co0.2Mn0.3O2-Li2MnO3Core-shell structure, albeit Li2MnO3The capacity retention rate of the electrode of the coated ternary material is 24.1 percent higher than that of the uncoated ternary material, but due to Li2MnO3The electron conductivity of the material is poor, the discharge platform is continuously reduced in the circulation process, and in addition, due to Li2MnO3The occurrence of irreversible decomposition side reactions of (a) and (b) generates a large amount of impurity phases, which still affect the performance of the electrochemical properties of the bulk material and are difficult to meet the performance requirements under high voltage conditions.
Disclosure of Invention
The invention provides a modified nickel-rich ternary material and a preparation method and application thereof, aiming at the problem that the electrochemical performance of the existing nickel-rich ternary material is not ideal enough under the condition of high voltage.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a modified nickel-rich ternary material comprises a nickel-rich ternary material substrate and a coating layer coated on the surface of the substrate, wherein the coating layer is of a single-layer structure or a double-layer structure, and the single-layer structure is a lithium nickel manganese oxide layer; the double-layer structure consists of an inner lithium manganate layer and an outer lithium nickel manganate layer, and the content omega of the coating layer in the modified nickel-rich ternary material is as follows in percentage by mass: omega is more than or equal to 0.5 percent and less than or equal to 5 percent.
Compared with the prior art, the modified nickel-rich ternary material provided by the invention has the advantages that the surface of the nickel-rich ternary material is coated with lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) The single layer structure or the inner layer is lithium manganate (LiMn)2O4) The outer layer of the layer is a double-layer structure of a lithium nickel manganese oxide layer, and the electrochemical activity of lithium manganate and lithium nickel manganese oxide with high voltage characteristic is utilized, so that the capacity loss of inactive substances is reduced,compared with other coating materials, the lithium manganate and the nickel lithium manganate have better lithium ion migration channels, are more favorable for the insertion and the separation of lithium ions, improve the charge transfer efficiency of the electrolyte between a positive electrode and a negative electrode, and are favorable for the exertion of the capacity of a nickel-rich ternary material; meanwhile, the lithium manganate and the nickel lithium manganate have discharge platform voltages similar to those of the nickel-rich ternary material (and are slightly higher than the voltage platform of the nickel-rich ternary material) and good high-temperature cycling stability, and can effectively inhibit the attenuation of the platform voltages in the cycling process; in addition, the lithium manganate and the nickel lithium manganate have stable spinel structures, can inhibit the reconstruction of the surface structure of the nickel-rich ternary cathode material, stabilize the surface atomic layer and are beneficial to the improvement of the cycle performance of the nickel-rich material. The modified nickel-rich ternary material provided by the invention has excellent electrochemical performance under a high-voltage condition.
Furthermore, the chemical general formula of the modified nickel-rich ternary material is LiaNi1-m-nComMnnO2Wherein a is more than 1 and less than 1.1, m is more than 0 and less than 0.2, and n is more than 0 and less than 0.2.
Further, the nickel-rich ternary material matrix is prepared from a nickel-cobalt-manganese precursor nickel-cobalt-manganese hydroxide, and the chemical general formula of the nickel-rich ternary material matrix is Li (Ni)xCoyMnz)O2Wherein, x: y: z is 8:1:1 or 5:2:3 or 6:2:2, and x + y + z is 1, i.e. the nickel-rich ternary material NCM811, NCM523 or NCM622, enabling higher battery capacity to be guaranteed.
Further, in the double-layer structure, the mass ratio of the lithium manganate layer to the lithium nickel manganate layer is 0.8-1.2: 1, improving the stability of the nickel-rich ternary material while improving the lithium ion capacity.
The invention also provides a preparation method of the modified nickel-rich ternary material, which comprises the following steps:
s1: adding a nickel-cobalt-manganese precursor and a lithium source into an organic solvent, uniformly stirring, aging, separating, drying, and calcining in an oxygen atmosphere to obtain a nickel-rich ternary material matrix;
s2: mixing the nickel-rich ternary material matrix obtained in S1 with Mn2O7And Na2S2O8Carrying out ball milling under the protection of argon, washing the ball-milled powder with absolute ethyl alcohol, carrying out vacuum drying, then grinding and uniformly mixing the ball-milled powder with a lithium source, and sintering to obtain a lithium manganate-coated nickel-rich ternary material;
s3: preparing lithium salt, nickel salt and manganese salt for preparing lithium nickel manganese oxide into mixed salt solution, adding the obtained nickel-rich ternary material matrix or the nickel-rich ternary material coated by lithium nickel oxide, stirring and drying to obtain premix;
s4: and sequentially carrying out low-temperature calcination and high-temperature calcination treatment on the obtained premix in an oxygen atmosphere to obtain a nickel-rich ternary material coated with lithium nickel manganese oxide or a nickel-rich ternary material double-layer coated with lithium nickel oxide and lithium nickel manganese oxide, namely the modified nickel-rich ternary material.
Compared with the prior art, the preparation method of the modified nickel-rich ternary material provided by the invention comprises the steps of firstly preparing a nickel-rich ternary material matrix or a nickel-rich ternary material coated by lithium manganate from a nickel-cobalt-manganese precursor, then preparing lithium nickel manganate in situ on the basis of the nickel-rich ternary material matrix or the nickel-rich ternary material coated by lithium manganate, and forming a lithium nickel manganate layer on the surface of the material to obtain the nickel-rich ternary material coated by a single lithium nickel manganate layer or the nickel-rich ternary material coated by a lithium manganate and lithium nickel manganate double layer, namely the modified nickel-rich ternary material. The capacity, the cycle performance and the stability of the obtained modified nickel-rich ternary material are improved, and the modified nickel-rich ternary material has excellent electrochemical performance under the condition of high voltage.
Further, the lithium source is one of lithium nitrate, lithium chloride or lithium acetate.
Further, in the step S1, the aging time is 20-30 h, so that complete precipitation is ensured, and all components are fully reacted; the drying temperature is 100-110 ℃, and the drying time is 3-5 h; the calcining temperature is 700-850 ℃, the calcining time is 6-10 h, and Li generated by decomposition is enabled to be2O permeates into the nickel-cobalt-manganese precursor oxide to complete lattice recombination and further perfect the lattice structure, so that the obtained nickel-rich ternary material has more stable structure and more excellent electrochemical performance.
Further, in step S2, the lithium source is one of lithium nitrate, lithium chloride and lithium acetate; the sintering temperature is 700-850 ℃, the sintering time is 6-9 hours, the lithium manganate coated nickel-rich ternary material is obtained, and the capacity and stability of the nickel-rich ternary material are preliminarily improved.
Further, in the step S3, the stirring time is 0.5-1 h; and drying at the temperature of 80-120 ℃ for 10-20 hours to enable lithium salt, nickel salt and manganese salt to be attached to the surface of the material to obtain a premix, so that the lithium nickel manganese oxide can be conveniently formed and coated.
Further, in step S4, the mass ratio of the lithium salt, the nickel salt, and the manganese salt is 1.05: 0.5: 1.5.
further, in step S4, the lithium salt is one of lithium nitrate, lithium chloride or lithium acetate; the nickel salt is one of nickel nitrate, nickel chloride or nickel acetate; the manganese salt is one of manganese nitrate, manganese chloride or manganese acetate.
Further, in step S4, the low-temperature calcination temperature is 450-650 ℃, and the time is 3-5 h; and (3) performing high-temperature calcination at 700-900 ℃ for 5-8 h to form a lithium nickel manganese oxide coating layer and further improve the lattice structure of the lithium nickel manganese oxide, thereby obtaining a nickel-rich ternary material coated by a single lithium nickel manganese oxide layer or a nickel-rich ternary material coated by a double lithium manganese oxide layer and a double lithium nickel manganese oxide layer.
Further, in step S4, the heating rate of the low-temperature calcination is 2-4 ℃/S; the temperature rise rate of the high-temperature calcination is 4-6 ℃/s, and the phenomenon that the crystal structure of the material is damaged due to too fast temperature rise is avoided, so that the structural stability of the material is influenced.
Correspondingly, the invention provides the application of the modified nickel-rich ternary material in the field of lithium ion batteries.
The obtained modified nickel-rich ternary material is used as a positive electrode material of a lithium ion battery, and the electrochemical performance of the battery under a high-voltage condition is improved.
Drawings
FIG. 1 is an SEM image of a modified nickel-rich ternary material of an embodiment of the invention;
FIG. 2 is a TEM image of a modified nickel-rich ternary material of an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a modified nickel-rich ternary material, which comprises a nickel-rich ternary material substrate and a coating layer coated on the surface of the substrate, wherein the coating layer is of a single-layer structure of lithium nickel manganese oxide or a double-layer structure consisting of an inner lithium manganese oxide layer and an outer lithium nickel manganese oxide layer, and the content omega of the coating layer in the modified nickel-rich ternary material is as follows in percentage by mass: omega is more than or equal to 0.5 percent and less than or equal to 5 percent.
The preparation method of the modified nickel-rich ternary material comprises the following steps:
s1: adding a nickel-cobalt-manganese precursor and a lithium source into an organic solvent, uniformly stirring, aging, separating, drying, and calcining in an oxygen atmosphere to obtain a nickel-rich ternary material matrix;
s2: mixing the nickel-rich ternary material matrix obtained in S1 with Mn2O7And Na2S2O8Carrying out ball milling under the protection of argon, washing the ball-milled powder with absolute ethyl alcohol, carrying out vacuum drying, then grinding and uniformly mixing the ball-milled powder with a lithium source, and sintering to obtain a lithium manganate-coated nickel-rich ternary material;
s3: preparing lithium salt, nickel salt and manganese salt for preparing lithium nickel manganese oxide into mixed salt solution, adding the obtained nickel-rich ternary material matrix or the nickel-rich ternary material coated by lithium nickel oxide, stirring and drying to obtain premix;
s4: and sequentially carrying out low-temperature calcination and high-temperature calcination treatment on the obtained premix in an oxygen atmosphere to obtain a nickel-rich ternary material coated with lithium nickel manganese oxide or a nickel-rich ternary material double-layer coated with lithium nickel oxide and lithium nickel manganese oxide, namely the modified nickel-rich ternary material.
Specifically, in step S2, Mn on the surface of the Ni-rich ternary material substrate2O7And Na2S2O8Formation of MnO on reduction2And Na2SO4By passing throughEluting Na with water and ethanol2SO4And Na2S2O8；MnO2Sintering the mixture with a lithium source to form LiMn2O4Coated on the surface of the nickel-rich ternary material matrix.
In order to better illustrate the modified nickel-rich ternary material provided by the embodiments of the present invention, the following examples further illustrate the modified nickel-rich ternary material.
Example 1
The modified nickel-rich ternary material comprises a nickel-rich ternary material substrate NCM811 and a coating layer coated on the surface of the substrate, wherein the coating layer consists of an inner lithium manganate layer and an outer lithium nickel manganate layer, the content omega of the coating layer in the modified nickel-rich ternary material is 5% by mass, and the mass ratio of the lithium manganate layer to the lithium nickel manganate layer is 0.8: 1.
the preparation method of the modified nickel-rich ternary material comprises the following steps:
s1: calculating the use amounts of a nickel-cobalt-manganese precursor and lithium nitrate according to the content of each component in the material, adding the nickel-cobalt-manganese precursor and the lithium nitrate into absolute ethyl alcohol, uniformly stirring, aging for 25h, separating, drying at 100 ℃ for 4h, and calcining at 700 ℃ for 8h in an oxygen atmosphere to obtain a nickel-rich ternary material matrix;
s2: calculating the required Mn according to the ratio of the lithium manganate layer2O7、Na2S2O8And the dosage of lithium nitrate, and mixing the obtained nickel-rich ternary material matrix with Mn2O7And Na2S2O8Ball milling is carried out under the protection of argon, the powder after ball milling is washed by absolute ethyl alcohol, and Na is eluted2SO4And Na2S2O8After vacuum drying, grinding and uniformly mixing the lithium manganate and lithium nitrate, and sintering the mixture at 750 ℃ for 7 hours to obtain a lithium manganate coated nickel-rich ternary material;
s3: lithium nitrate, nickel nitrate and manganese nitrate for preparing lithium nickel manganese oxide are mixed according to the mass ratio of 1.05: 0.5: 1.5 preparing a mixed salt solution, adding the obtained lithium manganate coated nickel-rich ternary material, stirring for 0.5h, and drying at 120 ℃ for 10h to obtain a premix;
s4: and (3) placing the obtained premix in an oxygen atmosphere, heating to 500 ℃ at the rate of 3 ℃/s, calcining for 4h, heating to 750 ℃ at the rate of 5 ℃/s, and calcining for 6h to obtain the nickel-rich ternary material, namely the modified nickel-rich ternary material, coated by lithium manganate and lithium nickel manganate in a double-layer manner.
Example 2
The modified nickel-rich ternary material comprises a nickel-rich ternary material substrate NCM523 and a coating layer coated on the surface of the substrate, wherein the coating layer is a lithium nickel manganese oxide layer, and the content omega of the coating layer in the modified nickel-rich ternary material is 3% in percentage by mass.
The preparation method of the modified nickel-rich ternary material comprises the following steps:
s1: calculating the use amounts of a nickel-cobalt-manganese precursor and lithium nitrate according to the content of each component in the material, adding the nickel-cobalt-manganese precursor and the lithium nitrate into absolute ethyl alcohol, uniformly stirring, aging for 25h, separating, drying at 100 ℃ for 4h, and calcining at 800 ℃ for 8h in an oxygen atmosphere to obtain a nickel-rich ternary material matrix;
s2: lithium nitrate, nickel nitrate and manganese nitrate for preparing lithium nickel manganese oxide are mixed according to the mass ratio of 1.05: 0.5: 1.5 preparing a mixed salt solution, adding the obtained nickel-rich ternary material matrix, stirring for 1h, and drying at 80 ℃ for 20h to obtain a premix;
s3: and (3) placing the obtained premix in an oxygen atmosphere, heating to 650 ℃ at the rate of 3 ℃/s, calcining for 3h, heating to 900 ℃ at the rate of 5 ℃/s, and calcining for 6h to obtain the nickel-rich ternary material coated by the lithium nickel manganese oxide, namely the modified nickel-rich ternary material.
Example 3
A modified nickel-rich ternary material comprises a nickel-rich ternary material matrix Li1.02Ni0.8Co0.1Mn0.1O2And the coating layer is coated on the surface of the substrate, the coating layer is a lithium nickel manganese oxide layer, and the content omega of the coating layer in the modified nickel-rich ternary material is 2.5 percent by mass.
The preparation method of the modified nickel-rich ternary material comprises the following steps:
s1: calculating the use amounts of the required nickel-cobalt-manganese precursor and lithium chloride according to the content of each component in the material, adding the nickel-cobalt-manganese precursor and the lithium chloride into absolute ethyl alcohol, uniformly stirring, aging for 30h, separating, drying at 110 ℃ for 3h, and calcining at 700 ℃ for 9h in an oxygen atmosphere to obtain a nickel-rich ternary material matrix;
s2: lithium chloride, nickel chloride and manganese chloride used for preparing lithium nickel manganese oxide are mixed according to the mass ratio of 1.05: 0.5: 1.5 preparing a mixed salt solution, adding the obtained nickel-rich ternary material matrix, stirring for 0.5h, and drying at 100 ℃ for 15h to obtain a premix;
s3: and (3) placing the obtained premix in an oxygen atmosphere, heating to 450 ℃ at a rate of 4 ℃/s, calcining for 5h, and heating to 700 ℃ at a rate of 4 ℃/s, calcining for 7h to obtain the nickel-rich ternary material coated by the lithium nickel manganese oxide, namely the modified nickel-rich ternary material.
Example 4
The modified nickel-rich ternary material comprises a nickel-rich ternary material substrate NCM622 and a coating layer coated on the surface of the substrate, wherein the coating layer consists of an inner lithium manganate layer and an outer lithium nickel manganate layer, the content omega of the coating layer in the modified nickel-rich ternary material is 3% in mass percentage, and the mass ratio of the lithium manganate layer to the lithium nickel manganate layer is 1.2: 1.
the preparation method of the modified nickel-rich ternary material comprises the following steps:
s1: calculating the use amounts of the required nickel-cobalt-manganese precursor and lithium chloride according to the content of each component in the material, adding the nickel-cobalt-manganese precursor and the lithium chloride into absolute ethyl alcohol, uniformly stirring, aging for 20h, separating, drying at 105 ℃ for 5h, and calcining at 850 ℃ for 6h in an oxygen atmosphere to obtain a nickel-rich ternary material matrix;
s2: calculating the required Mn according to the ratio of the lithium manganate layer2O7、Na2S2O8And the dosage of lithium chloride, and mixing the obtained nickel-rich ternary material matrix with Mn2O7And Na2S2O8Ball milling is carried out under the protection of argon, the powder after ball milling is washed by absolute ethyl alcohol, and Na is eluted2SO4And Na2S2O8Vacuum drying, grinding and mixing with lithium chloride,sintering at 850 ℃ for 6h to obtain a lithium manganate coated nickel-rich ternary material;
s2: lithium chloride, nickel chloride and manganese chloride used for preparing lithium nickel manganese oxide are mixed according to the mass ratio of 1.05: 0.5: 1.5 preparing a mixed salt solution, adding the obtained lithium manganate coated nickel-rich ternary material, stirring for 1h, and drying at 90 ℃ for 12h to obtain a premix;
s3: and (3) placing the obtained premix in an oxygen atmosphere, heating to 500 ℃ at the speed of 2 ℃/s, calcining for 4h, heating to 800 ℃ at the speed of 4 ℃/s, and calcining for 7h to obtain the nickel-rich ternary material, namely the modified nickel-rich ternary material, coated by lithium manganate and lithium nickel manganate in a double-layer manner.
Example 5
The modified nickel-rich ternary material comprises a nickel-rich ternary material substrate NCM622 and a coating layer coated on the surface of the substrate, wherein the coating layer is a lithium nickel manganese oxide layer, and the content omega of the coating layer in the modified nickel-rich ternary material is 0.5% by mass.
The preparation method of the modified nickel-rich ternary material comprises the following steps:
s1: calculating the use amounts of a nickel-cobalt-manganese precursor and lithium nitrate according to the content of each component in the material, adding the nickel-cobalt-manganese precursor and the lithium nitrate into absolute ethyl alcohol, uniformly stirring, aging for 20h, separating, drying at 105 ℃ for 5h, and calcining at 750 ℃ for 6h in an oxygen atmosphere to obtain a nickel-rich ternary material matrix;
s2: lithium nitrate, nickel nitrate and manganese nitrate for preparing lithium nickel manganese oxide are mixed according to the mass ratio of 1.05: 0.5: 1.5 preparing a mixed salt solution, adding the obtained nickel-rich ternary material matrix, stirring for 0.8h, and drying at 100 ℃ for 11h to obtain a premix;
s4: and (3) placing the obtained premix in an oxygen atmosphere, heating to 500 ℃ at a rate of 4 ℃/s, calcining for 4h, heating to 850 ℃ at a rate of 6 ℃/s, and calcining for 6h to obtain the nickel-rich ternary material coated by the lithium nickel manganese oxide, namely the modified nickel-rich ternary material.
To better illustrate the characteristics of the modified nickel-rich ternary material provided in the embodiments of the present invention, the modified nickel-rich ternary materials prepared in embodiments 1 to 5 and the lithium manganate coated nickel-rich ternary material obtained in embodiment 1 are described belowTernary material (as comparative example 1) and Li by sol-gel method2MnO3Li prepared for the outer Shell2MnO3The coated ternary material (as comparative example 2) was used for lithium ion battery positive electrode material to perform related performance tests, and the results of electrochemical performance data of each material at a normal voltage (4.2V) are shown in table 1, and the results of electrochemical performance data of each material at a high voltage (4.5V) are shown in table 2.
TABLE 1
| Test index | Test Range/V | Specific capacity of initial discharge | Capacity retention after 300 cycles | Multiplying power |
| Example 1 | 2.8～4.2 | 174mAh/g | 78％ | 1C |
| Example 2 | 2.8～4.2 | 168mAh/g | 83％ | 1C |
| Example 3 | 2.8～4.2 | 176mAh/g | 79％ | 1C |
| Example 4 | 2.8～4.2 | 172mAh/g | 81％ | 1C |
| Example 5 | 2.8～4.2 | 173mAh/g | 80％ | 1C |
| Comparative example 1 | 2.8～4.2 | 172mAh/g | 65％ | 1C |
| Comparative example 2 | 2.8～4.2 | 161mAh/g | 70％ | 1C |
TABLE 2
The data in the table show that the modified nickel-rich ternary material provided by the embodiment of the invention has excellent electrochemical performance under a high-voltage condition, large first charge-discharge specific capacity and high capacity retention rate.
Meanwhile, the modified nickel-rich ternary material obtained in example 1 is subjected to electron microscopy characterization, wherein an SEM is shown in fig. 1, and a TEM is shown in fig. 2. As can be seen from the figure, the modified nickel-rich ternary material provided in the embodiment of the present invention has a core-shell structure, an inner core is a nickel-rich ternary material substrate, an inner layer is a lithium manganate layer, and an outer layer is a lithium nickel manganate layer.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A modified nickel-rich ternary material is characterized in that: the coating layer is of a single-layer structure or a double-layer structure, and the single-layer structure is a lithium nickel manganese oxide layer; the double-layer structure consists of an inner lithium manganate layer and an outer lithium nickel manganate layer, and the content omega of the coating layer in the modified nickel-rich ternary material is as follows in percentage by mass: omega is more than or equal to 0.5 percent and less than or equal to 5 percent.
2. The modified nickel-rich ternary material of claim 1, wherein: the chemical general formula of the nickel-rich ternary material matrix is LiaNi1-m-nComMnnO2Wherein a is more than 1 and less than 1.1, m is more than 0 and less than 0.2, and n is more than 0 and less than 0.2.
3. The modified nickel-rich ternary material of claim 1, wherein: the nickel-rich ternary material substrate is prepared from nickel-cobalt-manganese precursor nickel-cobalt-manganese hydroxide, and the chemical general formula of the nickel-rich ternary material substrate is Li (Ni)xCoyMnz)O2Wherein, x: y: z is 8:1:1 or 5:2:3 or 6:2:2, and x + y + z is 1.
4. The modified nickel-rich ternary material of claim 1, wherein: in the double-layer structure, the mass ratio of the lithium manganate layer to the nickel lithium manganate layer is 0.8-1.2: 1.
5. a method for preparing the modified nickel-rich ternary material according to any one of claims 1 to 4, wherein the method comprises the following steps: the method comprises the following steps:
s1: adding a nickel-cobalt-manganese precursor and a lithium source into an organic solvent, uniformly stirring, aging, separating, drying, and calcining in an oxygen atmosphere to obtain a nickel-rich ternary material matrix;
s2: mixing the nickel-rich ternary material matrix obtained in S1 with Mn2O7And Na2S2O8Carrying out ball milling under the protection of argon, washing the ball-milled powder with absolute ethyl alcohol, carrying out vacuum drying, then grinding and uniformly mixing the ball-milled powder with a lithium source, and sintering to obtain a lithium manganate-coated nickel-rich ternary material;
s3: preparing lithium salt, nickel salt and manganese salt for preparing lithium nickel manganese oxide into mixed salt solution, adding the obtained nickel-rich ternary material matrix or the nickel-rich ternary material coated by lithium nickel oxide, stirring and drying to obtain premix;
s4: and sequentially carrying out low-temperature calcination and high-temperature calcination treatment on the obtained premix in an oxygen atmosphere to obtain a nickel-rich ternary material coated with lithium nickel manganese oxide or a nickel-rich ternary material double-layer coated with lithium nickel oxide and lithium nickel manganese oxide, namely the modified nickel-rich ternary material.
6. The method of claim 5, wherein the modified nickel-rich ternary material comprises: in the step S1, the aging time is 20-30 h; the drying temperature is 100-110 ℃, and the drying time is 3-5 h; the calcining temperature is 700-850 ℃, and the time is 6-10 h.
7. The method of claim 5, wherein the modified nickel-rich ternary material comprises: in the step S2, the sintering temperature is 700-850 ℃, and the sintering time is 6-9 h.
8. The method of claim 5, wherein the modified nickel-rich ternary material comprises: in the step S3, the stirring time is 0.5-1 h; the drying temperature is 80-120 ℃, and the drying time is 10-20 h.
9. The method of any one of claims 5 to 8, wherein: in the step S4, the low-temperature calcination temperature is 450-650 ℃, and the time is 3-5 h; the high-temperature calcination temperature is 700-900 ℃, and the time is 5-8 h.
10. Use of the modified nickel-rich ternary material according to any of claims 1 to 4 in the field of lithium ion batteries.
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