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CN117894947B - A composite modified lithium-rich manganese-based positive electrode material and preparation method thereof and lithium-ion battery - Google Patents

A composite modified lithium-rich manganese-based positive electrode material and preparation method thereof and lithium-ion battery Download PDF

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CN117894947B
CN117894947B CN202410052577.0A CN202410052577A CN117894947B CN 117894947 B CN117894947 B CN 117894947B CN 202410052577 A CN202410052577 A CN 202410052577A CN 117894947 B CN117894947 B CN 117894947B
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lithium
compound
positive electrode
electrode material
rich manganese
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CN117894947A (en
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刘洋
王振尧
屈亚利
任志敏
李国华
卓浩翔
郭立豪
王翠凤
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China Automotive Battery Research Institute Co Ltd
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Abstract

本发明提供了一种复合改性的富锂锰基正极材料及其制备方法和锂离子电池，涉及锂离子电池材料技术领域。所述复合改性的富锂锰基正极材料的形貌结构为由一次颗粒团聚形成的类球状二次颗粒，一次颗粒的结构包括：组成为Li1+eMnaNibMcTdO2的内核以及LifTgO2的包覆层，其中内核中的T金属离子存在于内核的表层晶格中，M金属离子存在于内核的晶格中且由外向内含量逐渐降低。具有此种结构特征的富锂材料的循环稳定性能够得到显著改善，同时倍率性能也能得到一定程度的提升。

The present invention provides a composite modified lithium-rich manganese-based positive electrode material, a preparation method thereof and a lithium-ion battery, and relates to the technical field of lithium-ion battery materials. The morphology structure of the composite modified lithium-rich manganese-based positive electrode material is a spherical secondary particle formed by the agglomeration of primary particles, and the structure of the primary particles includes: a core composed of Li1 + eMn aNi bM cTdO2 and a coating layer of LifTgO2 , wherein the T metal ions in the core exist in the surface lattice of the core, and the M metal ions exist in the lattice of the core and the content gradually decreases from the outside to the inside. The cycle stability of the lithium-rich material with such structural characteristics can be significantly improved, and the rate performance can also be improved to a certain extent.

Description

Composite modified lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a composite modified lithium-rich manganese-based positive electrode material, a preparation method thereof and a lithium ion battery.
Background
The lithium-rich manganese-based layered oxide positive electrode with the characteristics of high capacity, low cost and the like is hopefully applied to the next-generation high specific energy lithium ion battery in a large scale, however, the material has the problems of rapid capacity and voltage decay during circulation, gas generation and the like, and the practical application of the material is influenced. For the common polycrystalline morphology lithium-rich material (spheroidal secondary particles formed by agglomeration of primary particles with smaller particle sizes), the problems in the above circulation process are mainly caused by (1) that lattice oxygen of the material is gradually separated out from the surfaces of the primary particles during circulation, mn ions are also dissolved out from the surfaces of the primary particles in a large quantity, and part of transition metal ions in the material lose electrochemical activity, and (2) that secondary particles of the material are gradually cracked during circulation, so that side reactions such as oxygen separation, mn dissolution and the like are aggravated, and the internal electric contact of the secondary particles is also worsened.
The surface doping of the material by using electrochemical inert elements (such as Al 3+,Ti4+,Zr4+) can effectively improve the structural stability of the surface layer of the material, so that the material is a common means for improving the cycle performance of the lithium-rich material. However, the above method tends to cause a significant decrease in initial capacity and rate capability of the material, and also fails to exert an inhibitory effect on cracking of secondary particles upon circulation. Literature (Energy environment. Sci.,2021,14,6616-6626) reports a modification strategy for reducing the primary particle size of a high nickel material and changing the primary particle stacking mode by using high-valence (5-valence, 6-valence) transition metal ions, and the method can obviously inhibit secondary particle cracking of the high nickel material during circulation, thereby obviously improving the circulation performance. However, for lithium-rich materials, the reduction of primary particle size can lead to more serious problems of oxygen precipitation and Mn dissolution, which in turn is detrimental to cycle performance. Chinese patent CN110383542B discloses a doped lithium-rich material covered with tungsten compound/lithium tungsten compound on the surface, and the protection effect of the tungsten compound/lithium tungsten compound can improve the electrochemical performance of the material. However, the tungsten-containing compound is introduced on the surface of the finished material rather than the surface of the precursor, and the particle size and stacking mode of the primary particles of the material cannot be further regulated in the process, so that the capacity attenuation and gas production problems caused by the cracking of the secondary particles of the material during circulation cannot be effectively improved. Chinese patent CN113078316a discloses a lithium molybdate coated lithium-rich manganese-based cathode material and a preparation method thereof, but the capacity attenuation and gas production problems caused by secondary particle cracking of the material prepared by the method during circulation are not effectively inhibited.
Therefore, how to more effectively improve the cycle stability of the lithium-rich material is a problem that needs to be solved in order to advance the practical use of the lithium-rich material.
Disclosure of Invention
According to the method, M metal ions which are easy to enter the layered structure of the lithium-rich material during sintering and T metal ions which are difficult to enter the layered structure of the lithium-rich material during sintering and can play a role in regulating and controlling the morphology and stacking mode of primary particles of the lithium-rich material are simultaneously introduced on the surface of the precursor of the lithium-rich material. And then carrying out high-temperature sintering to obtain the surface in-situ composite modified lithium-rich manganese-based anode material. The oxide of T is mainly segregated on the surface and grain boundary of primary particles after high-temperature sintering, and little diffuses into the surface lattice of the material, and M ions enter the primary particle lattice after high-temperature sintering and are distributed in a gradient manner (the content gradually decreases from outside to inside). The cycle stability of the lithium-rich material with the structural characteristics can be obviously improved, and the rate performance can be improved to a certain extent.
The invention aims at providing a composite modified lithium-rich manganese-based positive electrode material.
The second purpose of the invention is to provide a preparation method of the composite modified lithium-rich manganese-based positive electrode material.
The invention further aims at providing a lithium ion battery comprising the composite modified lithium-rich manganese-based positive electrode material.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
In a first aspect, the invention provides a composite modified lithium-rich manganese-based positive electrode material, which comprises the following components in percentage by weight ：xLi1+eMnaNibMcTdO2@(1-x)LifTgO2,
Wherein, x is more than or equal to 0.95 and less than or equal to 0.995, 0.5< a; less than or equal to 0.9, less than or equal to 0.5, less than or equal to 0< c less than or equal to 0.9,0< b < less than or equal to 0.5,0< c < less than or equal to;
M is one or more selected from Ti, zr, sn, mg, ca, al and La, T is one or more selected from W, mo, ta and Nb;
the morphology structure of the composite modified lithium-rich manganese-based positive electrode material is similar spherical secondary particles formed by agglomeration of primary particles, and the primary particles comprise an inner core of Li 1+eMnaNibMcTdO2 and a coating layer of Li fTgO2, wherein T metal ions in the inner core exist in a surface layer lattice of the inner core, M metal ions exist in the lattice of the inner core, and the content of the M metal ions gradually decreases from outside to inside.
The following is a detailed description:
The composition of the composite modified lithium-rich manganese-based positive electrode material is ：xLi1+eMnaNibMcTdO2@(1-x)LifTgO2,, x is more than or equal to 0.95 and less than or equal to 0.995, a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.2, d is more than or equal to 0 and less than or equal to 0.01, and e is more than or equal to 0 0.2,0< f is less than or equal to 1,0.1 g is less than or equal to 1;M, and is one or more selected from Ti, zr, sn, mg, ca, al and La; T is one or more selected from W, mo, ta and Nb;
The composition of the composite modified lithium-rich manganese-based positive electrode material is, for example, 0.98Li 1.19Mn0.575Ni0.2Ti0.02W0.005O2@0.02Li2WO4, but is not limited thereto.
The material has the following structural characteristics:
(1) The morphology is similar spherical secondary particles formed by the agglomeration of primary particles with smaller particle size;
Preferably, the primary particles are flaky crystals, the sizes of the primary particles in three directions perpendicular to each other are respectively in the ranges of 20-500 nm, 20-500 nm and 10-200 nm, and the particle size of the spheroidal secondary particles is in the range of 1-20 mu m.
(2) The primary particle structure is shown in FIG. 1 and comprises an inner core of Li 1+eMnaNibMcTdO2 and a coating layer of Li fTgO2. According to the method, T metal ions and M metal ions are simultaneously introduced into the surface of the lithium-rich manganese-based positive electrode material precursor, wherein the T ions are mainly segregated on the surface of primary particles and grain boundaries after high-temperature sintering to form a Li fTgO2 coating layer, and are slightly diffused into the surface layer lattice of the inner core, and the M ions enter the inner core lattice after high-temperature sintering and are distributed in a gradient manner (the content of the M ions gradually decreases from outside to inside).
In a second aspect, the invention provides a preparation method of a composite modified lithium-rich manganese-based positive electrode material, which comprises the following steps:
(1) Weighing a Li compound, a Mn compound, a Ni compound, an M compound and a T compound according to the stoichiometric ratio of each element in the composition of the composite modified lithium-rich manganese-based oxide positive electrode material xLi1+eMnaNibMcTdO2@(1-x)LifTgO2 (namely the stoichiometric ratio of each element in the core and the shell);
(2) Then adding aqueous solution of soluble alkali or aqueous solution of soluble carbonate into the liquid phase mixture under stirring, filtering, washing and drying the obtained precipitate to obtain a precursor of the lithium-rich manganese-based positive electrode material;
(3) Introducing the compound of M and the compound of T into the surface of the lithium-rich manganese-based positive electrode material precursor obtained in the step (2) by using a liquid phase method or a solid phase method to obtain a composite modified lithium-rich manganese-based positive electrode material precursor;
(4) Uniformly mixing the precursor of the composite modified lithium-rich manganese-based positive electrode material obtained in the step (3) with a Li compound, presintering and calcining under a mixed atmosphere consisting of inert gas and oxygen, and cooling to obtain the composite modified lithium-rich manganese-based positive electrode material.
The following details the steps:
step (1):
Li, mn, ni, M and T are weighed according to the stoichiometric ratio of each element in xLi1+eMnaNibMcTdO2@(1-x)LifTgO2.
The Li compound is one or more selected from lithium carbonate, lithium oxide, lithium hydroxide and lithium nitrate;
the Mn compound is one or more selected from Mn oxide, mn hydroxide, mn carbonate, mn nitrate, mn chloride and Mn sulfate;
the compound of Ni is one or more selected from the group consisting of an oxide of Ni, a hydroxide of Ni, a carbonate of Ni, a nitrate of Ni, a chloride of Ni and a sulfate of Ni;
The compound of M is one or more selected from the group consisting of an oxide of M, a hydroxide of M, a carbonate of M, a nitrate of M, a chloride of M and a sulfate of M;
The compound of T is one or more selected from oxide of T, hydroxide of T, carbonate of T, nitrate of T, chloride of T, sulfate of T and oxysalt corresponding to T.
Step (2):
The aqueous solution of the soluble base or the aqueous solution of the soluble carbonate is excessively added so that the precipitation of Ni ions and Mn ions is completed.
Step (3):
step (3) includes the following cases:
A. when both the compound of M and the compound of T are soluble in water, a liquid phase method is selected, which includes the following two methods:
(a) Dispersing the precursor of the lithium-rich manganese-based positive electrode material obtained in the step (2) in water, then dissolving the compound M and the compound T in water, respectively dripping the aqueous solution of the compound M and the aqueous solution of the compound T into the water under stirring to obtain a liquid-phase mixture, and finally evaporating the liquid-phase mixture under continuous heating and stirring to obtain the composite modified precursor of the lithium-rich manganese-based positive electrode material.
(B) Dispersing the precursor of the lithium-rich manganese-based positive electrode material obtained in the step (2) in water, dissolving the compound M and the compound T in water, respectively dripping the aqueous solution of the compound M and the aqueous solution of the compound T into the water under stirring to obtain a liquid-phase mixture, adding the aqueous solution of soluble alkali or the aqueous solution of soluble carbonate into the liquid-phase mixture under stirring, and filtering, washing and drying the obtained precipitate to obtain the composite modified precursor of the lithium-rich manganese-based positive electrode material.
B. When the compounds of M and T are insoluble in water, a solid phase method is selected, which comprises the steps of:
And (3) placing the lithium-rich manganese-based positive electrode material precursor obtained in the step (2), the compound of M and the compound of T into a high-speed mixer or a ball mill for solid phase mixing to obtain the composite modified lithium-rich manganese-based positive electrode material precursor.
Preferably, the rotating speed of the high-speed mixer is 500-10000 r/min, and the mixing time is 1-72 h;
Preferably, the rotating speed of the ball mill is 200-800 r/min, the ball milling time is 1-72 h, and the weight ratio of ball materials is 5-50:1.
Step (4):
Preferably, the volume ratio of the inert gas to the oxygen is 1 (0.001-100), and the inert gas is one or more of nitrogen and argon.
Preferably, the presintering temperature is 200-700 ℃, and the presintering time is 0.5-10 h;
preferably, the calcination temperature is 500-1000 ℃ and the calcination time is 2-25 h.
The composition of the composite modified lithium-rich manganese-based positive electrode material obtained by the method in the second aspect is ：xLi1+ eMnaNibMcTdO2@(1-x)LifTgO2,, wherein x is more than or equal to 0.95 and less than or equal to 0.995, a is more than or equal to 0.5 and less than or equal to 0.9, b is more than or equal to 0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.2, d is more than or equal to 0 and less than or equal to 0.01, e is more than or equal to 0 and less than or equal to 1, g is more than or equal to 0.1 and less than or equal to 1;M is one or more selected from Ti, zr, sn, mg, ca, al and La, T is one or more selected from W, mo, ta and Nb, the morphology of the composite modified lithium-rich manganese-based positive electrode material is spheroidal secondary particles formed by agglomeration of primary particles, and the primary particles comprises a core with a composition of Li 1+ eMnaNibMcTdO2 and a coating layer of Li fTgO2, wherein T metal ions in the core exist in the surface layer lattice of the core and M metal ions gradually decrease from outside to inside.
In a third aspect, the invention also provides a lithium ion battery, which comprises the positive electrode material.
Advantageous effects
(1) The regulation and control effect of the T oxide segregated on the surface of the primary particles in the material preparation sintering process on the morphology and stacking mode of the primary particles of the material can inhibit cracking of the secondary particles in the circulating process, and the uniform coating effect can be achieved on the primary particles of the material, so that the improvement of the circulating performance of the material is facilitated. In addition, the effect of reducing the primary particle size also contributes to improvement of the rate performance of the material.
(2) The small amount of T ions diffused into the surface crystal lattice during high-temperature sintering contributes to the improvement of the structural stability of the surface layer of the material.
(3) The M ions entering the material lattice in a large amount can further improve the structural stability of the surface layer and the bulk phase of the primary particles, so that the problems of cycle performance reduction and gas production caused by the reduction of the particle size of the primary particles are solved.
The present invention has been described in detail hereinabove, but the above embodiments are merely exemplary in nature and are not intended to limit the present invention. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or summary or the following examples.
Drawings
Fig. 1 shows a schematic diagram of primary particle structure and element distribution of the composite modified lithium-rich manganese-based cathode material of the invention.
Detailed Description
The invention is further illustrated by the following examples, which are provided for illustrative purposes only and are not to be construed as limiting the scope of the invention as claimed.
Unless otherwise indicated, all materials, reagents, methods and the like used in the examples are those conventionally used in the art.
Comparative example 1 lithium-rich manganese-based oxide Material Li 1.2Mn0.6Ni0.2O2
The preparation method comprises the following steps:
li 2CO3、MnSO4、NiSO4 is weighed according to the stoichiometric ratio of each element. Firstly, niSO 4、MnSO4 is dissolved in water to obtain a liquid phase mixture, then, an excessive sodium carbonate aqueous solution (the amount of sodium carbonate is required to exceed the sum of the amounts of NiSO 4 and MnSO 4) is added into the liquid phase mixture under stirring, and the obtained carbonate precipitate is filtered, washed and dried to obtain the lithium-rich manganese-based positive electrode material precursor.
And uniformly mixing the precursor with the weighed Li 2CO3, and pre-sintering at 500 ℃ and 5 hours and calcining at 900 ℃ and 15 hours under a mixed atmosphere (volume ratio of 1:1) composed of nitrogen and oxygen to obtain the lithium-rich manganese-based positive electrode material Li 1.2Mn0.6Ni0.2O2.
Comparative example 2Li 1.2Mn0.58Ni0.2Ti0.02O2
The preparation method comprises the following steps:
Li 2CO3、MnSO4、NiSO4、TiO2 is weighed according to the stoichiometric ratio of each element. First, a lithium-rich manganese-based positive electrode material precursor was prepared according to the procedure in comparative example 1.
Then, the weighed TiO 2 (particle size 20 nm) and the precursor are mixed for 2 hours at a rotation speed of 2000r/min by a high-speed mixer, and then are uniformly mixed with the weighed Li 2CO3. Finally, presintering at 500 ℃ and 5 hours and calcining at 900 ℃ and 15 hours are carried out under the mixed atmosphere (volume ratio of 1:1) composed of nitrogen and oxygen, and the modified lithium-rich manganese-based anode material Li 1.2Mn0.58Ni0.2Ti0.02O2 can be obtained.
Comparative example 3.98 Li 1.19Mn0.595Ni0.2W0.005O2@0.02Li2WO4
Li 2CO3、MnSO4、NiSO4、Li2WO4 is weighed according to the stoichiometric ratio of each element. First, a lithium-rich manganese-based positive electrode material precursor was prepared according to the procedure in comparative example 1.
And then mixing the weighed Li 2WO4 with the precursor for 2 hours at the rotating speed of 2000r/min by using a high-speed mixer, and uniformly mixing the mixture with the weighed Li 2CO3. Finally, presintering at 500 ℃ and 5 hours and calcining at 900 ℃ and 15 hours are carried out under the mixed atmosphere (volume ratio of 1:1) composed of nitrogen and oxygen, and the modified lithium-rich manganese-based anode material 0.98Li 1.19Mn0.595Ni0.2W0.005O2@0.02Li2WO4 can be obtained.
Example 1.98 Li 1.19Mn0.575Ni0.2Ti0.02W0.005O2@0.02Li2WO4
Li 2CO3、MnSO4、NiSO4、TiO2、Li2WO4 is weighed according to the stoichiometric ratio of each element. First, a lithium-rich manganese-based positive electrode material precursor was prepared according to the procedure in comparative example 1.
Then, the weighed TiO 2 (particle size 20 nm) and Li 2WO4 are mixed with the precursor for 2 hours at a rotation speed of 2000r/min by a high-speed mixer, and then are uniformly mixed with the weighed Li 2CO3. Finally, presintering at 500 ℃ and 5 hours and calcining at 900 ℃ and 15 hours are carried out under the mixed atmosphere (volume ratio of 1:1) composed of nitrogen and oxygen, and the lithium-rich manganese-based anode material 0.98Li 1.19Mn0.575Ni0.2Ti0.02W0.005O2@0.02Li2WO4 can be obtained.
Example 2.98 Li 1.19Mn0.575Ni0.2Zr0.02Mo0.005O2@0.02Li2MoO4
Li 2CO3、MnSO4、NiSO4、ZrO2、MoO3 is weighed according to the stoichiometric ratio of each element. First, a lithium-rich manganese-based positive electrode material precursor was prepared according to the procedure in comparative example 1.
Then mixing the weighed ZrO 2 (particle size 20 nm) and MoO 3 (particle size 20 nm) with the precursor for 2 hours at the rotating speed of 2000r/min by using a high-speed mixer, and uniformly mixing with the weighed Li 2CO3. Finally, presintering at 500 ℃ and 5 hours and calcining at 900 ℃ and 15 hours are carried out under the mixed atmosphere (volume ratio of 1:1) composed of nitrogen and oxygen, and the lithium-rich manganese-based anode material 0.98Li 1.19Mn0.575Ni0.2Zr0.02Mo0.005O2@0.02Li2MoO4 can be obtained.
Example 3 0.98Li 1.19Mn0.6Ni0.19Mg0.01Nb0.01O2@0.02LiNbO3
Li 2CO3、MnSO4、NiSO4、MgO、Nb2O5 is weighed according to the stoichiometric ratio of each element. First, a lithium-rich manganese-based positive electrode material precursor was prepared according to the procedure in comparative example 1.
Then, the weighed MgO (particle size 20 nm) and Nb 2O5 (particle size 20 nm) were mixed with the above precursor at a rotation speed of 2000r/min for 2 hours by using a high-speed mixer, and then mixed with the weighed Li 2CO3 uniformly. Finally, presintering at 500 ℃ and 5 hours and calcining at 900 ℃ and 15 hours are carried out under the mixed atmosphere (volume ratio of 1:1) composed of nitrogen and oxygen, and the lithium-rich manganese-based anode material 0.98Li 1.19Mn0.6Ni0.19Mg0.01Nb0.01O2@0.02LiNbO3 can be obtained.
Example 4 0.99Li 1.2Mn0.575Ni0.2Al0.02Mo0.005O2@0.01Li2MoO4
Li 2CO3、MnSO4、NiSO4、Al2O3、MoO3 is weighed according to the stoichiometric ratio of each element. First, a lithium-rich manganese-based positive electrode material precursor was prepared according to the procedure in comparative example 1.
Then, the weighed Al 2O3 (particle size 20 nm) and MoO 3 (particle size 20 nm) were mixed with the above precursor at a rotational speed of 1500r/min for 3 hours by using a high-speed mixer, and then mixed with the weighed Li 2CO3 uniformly. Finally, presintering at 500 ℃ and 5 hours and calcining at 900 ℃ and 15 hours are carried out under the mixed atmosphere (volume ratio of 1:1) composed of nitrogen and oxygen, and the lithium-rich manganese-based anode material 0.99Li 1.2Mn0.575Ni0.2Al0.02Mo0.005O2@0.01Li2MoO4 can be obtained.
Example 5.99 Li 1.19Mn0.575Ni0.2Sn0.02W0.005O2@0.01Li2WO4
Li 2CO3、MnSO4、NiSO4、SnO2、WO3 is weighed according to the stoichiometric ratio of each element. First, a lithium-rich manganese-based positive electrode material precursor was prepared according to the procedure in comparative example 1.
Then, the weighed SnO 2 (particle size 20 nm) and WO 3 (particle size 20 nm) are mixed with the precursor for 1h at the rotating speed of 2500r/min by a high-speed mixer, and then are uniformly mixed with the weighed Li 2CO3. Finally, presintering at 500 ℃ and 5 hours and calcining at 900 ℃ and 15 hours are carried out under the mixed atmosphere (volume ratio of 1:1) composed of nitrogen and oxygen, and the lithium-rich manganese-based anode material 0.99Li 1.19Mn0.575Ni0.2Sn0.02W0.005O2@0.01Li2WO4 can be obtained.
And (3) taking the prepared material as a positive electrode material and graphite as a negative electrode material, assembling the material into a battery, and performing constant-current charge and discharge test at 25 ℃ with the charge and discharge voltage range of 2-4.8V and the current density of 200mA/g of 1C. The results are shown in Table 1.
TABLE 1
Note that the gas generation amount was obtained by measuring the volume change before and after the battery cycle by the drainage method.
The test results in comparative examples 1-3 and example 1 show that:
(1) The surface doping modification of the lithium-rich material particles by using TiO 2 alone can obviously improve the cycle capacity retention rate and gas production rate of the material, but the initial capacity and rate capability can be obviously reduced.
(2) The Li 2WO4 is independently utilized to carry out morphology regulation and control on the lithium-rich material particles, so that the initial capacity and multiplying power of the material are improved, the cyclic capacity retention rate is improved to a certain extent due to the inhibition effect on secondary particle cracking, but the reduction of the particle size is unfavorable for the remarkable improvement of the cyclic performance of the material, and the gas production problem during the cycle is aggravated.
(3) Meanwhile, the surface in-situ composite modification of the lithium-rich material by utilizing TiO 2 and Li 2WO4 can obviously improve the cycle capacity retention rate of the material, and the problems of initial capacity, rate capability and gas production of the material are improved to a certain extent, so that the comprehensive effect is optimal.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for in part or all of the technical features thereof, without departing from the spirit and scope of the present invention as defined in the appended claims.

Claims (10)

1. A composite modified lithium-rich manganese-based positive electrode material is characterized in that the composition of the composite modified lithium-rich manganese-based positive electrode material is that ：xLi1+eMnaNibMcTdO2@(1-x)LifTgO2,
Wherein, x is more than or equal to 0.95 and less than or equal to 0.995, 0.5< a; less than or equal to 0.9, less than or equal to 0.5, less than or equal to 0< c less than or equal to 0.9,0< b < less than or equal to 0.5,0< c < less than or equal to;
M is one or more selected from Ti, zr, sn, mg, ca, al and La, T is one or more selected from W, mo, ta and Nb;
The morphology structure of the composite modified lithium-rich manganese-based positive electrode material is similar spherical secondary particles formed by agglomeration of primary particles, wherein the primary particles comprise an inner core of Li 1+eMnaNibMcTdO2 and a coating layer of Li fTgO2, T metal ions in the inner core exist in a surface layer lattice of the inner core, M metal ions exist in the lattice of the inner core, and the content of the M metal ions gradually decreases from outside to inside;
the preparation method of the composite modified lithium-rich manganese-based positive electrode material comprises the following steps of:
(1) Weighing a Li compound, a Mn compound, a Ni compound, an M compound and a T compound according to the stoichiometric ratio of each element in the composition xLi1+eMnaNibMcTdO2@(1-x)LifTgO2 of the composite modified lithium-rich manganese-based oxide positive electrode material;
(2) Then adding aqueous solution of soluble alkali or aqueous solution of soluble carbonate into the liquid phase mixture under stirring, filtering, washing and drying the obtained precipitate to obtain a precursor of the lithium-rich manganese-based positive electrode material;
(3) Introducing the compound of M and the compound of T into the surface of the lithium-rich manganese-based positive electrode material precursor obtained in the step (2) by using a liquid phase method or a solid phase method to obtain a composite modified lithium-rich manganese-based positive electrode material precursor;
(4) Uniformly mixing the precursor of the composite modified lithium-rich manganese-based positive electrode material obtained in the step (3) with a Li compound, presintering and calcining under a mixed atmosphere consisting of inert gas and oxygen, and cooling to obtain the composite modified lithium-rich manganese-based positive electrode material.
2. The composite modified lithium-rich manganese-based positive electrode material according to claim 1, wherein the primary particles are flaky crystals, the sizes of the primary particles in three directions perpendicular to each other are respectively in the range of 20-500 nm, 20-500 nm and 10-200 nm, and the particle size of the spheroidal secondary particles is in the range of 1-20 μm.
3. A method for preparing the composite modified lithium-rich manganese-based positive electrode material according to claim 1 or 2, comprising the steps of:
(1) Weighing a Li compound, a Mn compound, a Ni compound, an M compound and a T compound according to the stoichiometric ratio of each element in the composition xLi1+eMnaNibMcTdO2@(1-x)LifTgO2 of the composite modified lithium-rich manganese-based oxide positive electrode material;
(2) Then adding aqueous solution of soluble alkali or aqueous solution of soluble carbonate into the liquid phase mixture under stirring, filtering, washing and drying the obtained precipitate to obtain a precursor of the lithium-rich manganese-based positive electrode material;
(3) Introducing the compound of M and the compound of T into the surface of the lithium-rich manganese-based positive electrode material precursor obtained in the step (2) by using a liquid phase method or a solid phase method to obtain a composite modified lithium-rich manganese-based positive electrode material precursor;
(4) Uniformly mixing the precursor of the composite modified lithium-rich manganese-based positive electrode material obtained in the step (3) with a Li compound, presintering and calcining under a mixed atmosphere consisting of inert gas and oxygen, and cooling to obtain the composite modified lithium-rich manganese-based positive electrode material.
4. A process according to claim 3, wherein in step (1),
The Li compound is one or more selected from lithium carbonate, lithium oxide, lithium hydroxide and lithium nitrate;
the Mn compound is one or more selected from Mn oxide, mn hydroxide, mn carbonate, mn nitrate, mn chloride and Mn sulfate;
the compound of Ni is one or more selected from the group consisting of an oxide of Ni, a hydroxide of Ni, a carbonate of Ni, a nitrate of Ni, a chloride of Ni and a sulfate of Ni;
The compound of M is one or more selected from the group consisting of an oxide of M, a hydroxide of M, a carbonate of M, a nitrate of M, a chloride of M and a sulfate of M;
The compound of T is one or more selected from oxide of T, hydroxide of T, carbonate of T, nitrate of T, chloride of T, sulfate of T and oxysalt corresponding to T.
5. The process according to claim 3, wherein in the step (3),
The liquid phase method comprises the following two methods:
(a) Dispersing the precursor of the lithium-rich manganese-based positive electrode material obtained in the step (2) in water, then dissolving the compound M and the compound T in water, and respectively dripping the aqueous solution of the compound M and the aqueous solution of the compound T into the water under stirring to obtain a liquid-phase mixture;
(b) Dispersing the precursor of the lithium-rich manganese-based positive electrode material obtained in the step (2) in water, dissolving the compound M and the compound T in water, respectively dripping the aqueous solution of the compound M and the aqueous solution of the compound T into the water under stirring to obtain a liquid-phase mixture, adding the aqueous solution of soluble alkali or the aqueous solution of soluble carbonate into the liquid-phase mixture under stirring, and filtering, washing and drying the obtained precipitate to obtain the composite modified precursor of the lithium-rich manganese-based positive electrode material.
6. The process according to claim 3, wherein in the step (3),
The solid phase method comprises the following steps:
And (3) placing the lithium-rich manganese-based positive electrode material precursor obtained in the step (2), the compound of M and the compound of T into a high-speed mixer or a ball mill for solid phase mixing to obtain the composite modified lithium-rich manganese-based positive electrode material precursor.
7. The preparation method according to claim 6, wherein the rotation speed of the high-speed mixer is 500-10000 r/min, and the mixing time is 1-72 h;
The rotating speed of the ball mill is 200-800 r/min, the ball milling time is 1-72 h, and the weight ratio of ball materials is 5-50:1.
8. The process according to claim 3, wherein in the step (4),
The volume ratio of the inert gas to the oxygen is 1 (0.001-100), and the inert gas is one or more of nitrogen and argon.
9. The process according to claim 3, wherein in the step (4),
The presintering temperature is 200-700 ℃, and the presintering time is 0.5-10 h;
The calcination temperature is 500-1000 ℃, and the calcination time is 2-25 h.
10. A lithium ion battery comprising the composite modified lithium-rich manganese-based positive electrode material according to claim 1 or 2 or the composite modified lithium-rich manganese-based positive electrode material prepared by the preparation method according to any one of claims 3 to 9.
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